Formula and preparation method of stabilizer for producing ammonia-free rubber

Abstract

The invention provides a stabilizer formula for producing ammonia-free rubber and a preparation method, and belongs to the technical field of natural rubber production and processing. The stabilizer is prepared from, by weight, 3.6-4.8 parts of chitosan, 1-3 parts of sodium diacetate, 2-4 parts of methyl p-hydroxybenzoate, 1-2 parts of alginate, 3-4 parts of citric acid, 0.5-0.8 part of sodium sorbate and 1.2-1.6 parts of a specially-made active agent, camellia seed oil is adopted as a raw material to prepare the specially-made active agent, and the weight part ratio of chitosan to the specially-made active agent is 3: 1. The stabilizer disclosed by the invention can effectively prolong the preservation time of the rubber latex and improve the stability of the natural rubber latex through multiple mechanisms of inhibiting the growth of microorganisms, adjusting the pH value, enhancing a protective film and the like, and is beneficial to improving the environmental protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of natural rubber production and processing, and relates to a stabilizer for producing ammonia-free rubber, in particular to a stabilizer formula and preparation method for producing ammonia-free rubber. Background Art

[0002] Rubber is an important industrial raw material and is known as one of the four major industrial raw materials together with steel, petroleum, and coal. Due to its unique high elasticity, good physical and mechanical properties, and electrical insulation properties, rubber has extremely wide applications.

[0003] The commonly used rubbers include natural rubber and synthetic rubber. Currently, the global annual demand reaches 20 million tons, including 12 million tons of synthetic rubber and 8 million tons of natural rubber. However, synthetic rubber cannot replace natural rubber. Natural rubber is extracted from rubber-containing plants. The latex collected from rubber trees is a milky white liquid, similar in appearance to milk. It is a product of the biosynthesis of rubber trees, and its composition is very complex. In addition to rubber hydrocarbons and water, it also contains abundant non-rubber substances such as proteins, sugars, lipids, inorganic salts, and enzymes. Under the action of bacteria and enzymes, it is very easy and quick to deteriorate, thus affecting product quality and economic benefits.

[0004] In the prior art, in order to improve the stability effect of natural rubber latex, ammonia water is usually added to natural rubber latex. However, ammonia water has a strong pungent smell and strong volatility, which is likely to affect the working environment and endanger the health of operators. Since ammonia water needs to be deammoniated by downstream manufacturers after being added, the processing procedure is increased and the production cost is raised. When using ammonia water as a stabilizer, the stability is often poor and is easily affected by external factors such as temperature and humidity, resulting in unstable stabilizer effects. In addition, traditional ammonia water is not applicable in the production of some special types of natural rubber, and additional process parameters need to be adjusted, increasing the production complexity.

[0005] Therefore, there is an urgent need for a stabilizer to replace ammonia water to solve the above corresponding problems. Summary of the Invention

[0006] The object of the present invention is to address the above problems existing in the prior art and propose a stabilizer formula and preparation method for producing ammonia-free rubber.

[0007] The purpose of the present invention can be achieved by the following technical scheme: a stabilizer formula for producing ammonia-free rubber, which comprises the following components in parts by weight: 3.6-4.8 parts of chitosan, 1-3 parts of sodium diacetate, 2-4 parts of methyl parahydroxybenzoate, 1-2 parts of alginate, 3-4 parts of citric acid, 0.5-0.8 parts of sodium sorbate and 1.2-1.6 parts of a special active agent, wherein the special active agent is prepared by using camellia seed oil as a raw material, and the weight ratio of chitosan to the special active agent is 3:1.

[0008] Through the coordinated action of multiple components in the stabilizer, it can act on the enzyme system in the microorganism, inhibit the activity of the enzyme in the microorganism, interfere with the normal metabolic pathway of the microorganism, and thus further weaken the survival ability of the microorganism. The active ingredients contained can act on the cell wall and cell membrane of the microorganism, destroy or damage the cell wall of the microorganism, interfere with the synthesis mechanism of the cell wall of the microorganism, cause the leakage of substances in the microorganism cell, thereby inhibiting the growth and reproduction of the microorganism and improving the stabilization effect on natural rubber latex.

[0009] A method for preparing a stabilizer for producing ammonia-free rubber, using the above stabilizer formula for producing ammonia-free rubber to prepare the stabilizer, the method for preparing the stabilizer comprises the following steps:

[0010] S1 Preparation of special active agent: S1.1 Distillation extraction: distill camellia oil to obtain camellia oil distillate; S1.2 Pretreatment: add camellia oil distillate to chloroform, stir and mix evenly to obtain camellia oil distillate solution; keep the camellia oil distillate solution warm; S1.3 Sulfonation treatment: add chlorosulfonic acid to chloroform, stir and mix evenly to obtain chlorosulfonic acid solution; add chlorosulfonic acid solution dropwise to the camellia oil distillate solution after the warm-keeping operation, stir while adding, after the addition is completed, adjust the temperature of the reaction system to the target temperature, continue the warm-keeping and stirring operation, and obtain the reaction solution after the warm-keeping and stirring operation is completed; S1.4 Post-treatment: remove the solvent, neutralize the reaction, dissolve the neutralization product, separate and remove the inorganic salt, and dry the reaction solution in sequence to obtain the special active agent;

[0011] S2 raw material mixing: according to the formula of the stabilizer, chitosan, sodium diacetate, methyl parahydroxybenzoate, alginate, citric acid, sodium sorbate and a special active agent are weighed, added into a stirring device for stirring, and after stirring evenly, a stabilizer is obtained.

[0012] In step S1.1, the distillation extraction operation is carried out at a temperature of 225-250°C and a pressure of 5-6 mmHg.

[0013] In the camellia seed oil distillate solution in step S1.2, the ratio of camellia seed oil distillate to chloroform is 20 - 24 g : 100 mL.

[0014] In the chlorosulfonic acid solution in step S1.3, the ratio of chlorosulfonic acid to chloroform is 8 - 10 g : 40 mL.

[0015] In step S1.2, the heat preservation operation parameters are as follows: the temperature is 0 - 2 °C, and the heat preservation time is 30 - 40 minutes. The camellia seed oil distillate contains some components with strong hydrophobicity. By controlling the temperature (heat preservation at 2 °C), the interaction between the solvent and the solute can be accelerated, promoting the dissolution of the camellia seed oil distillate while maintaining the stability of the solution. Heat preservation helps reduce the viscosity of some components in the oil that are difficult to dissolve, and thus enables them to disperse better in chloroform. By heat preservation at a low temperature, the stability and uniformity of the solution can be maintained. A lower temperature helps reduce the phenomenon of thermal instability or component separation that may occur in the solution, thereby providing a more uniform and stable solution for the subsequent step (sulfonation reaction).

[0016] In step S1.3, the target temperature is 25 °C, and the heat preservation and stirring time is 2 - 3 hours. When the sulfonation reaction itself is carried out at a lower temperature (25 °C), the intensity of the reaction can be controlled, avoiding the phenomenon of thermal instability at too high a temperature, especially in the presence of the organic solvent chloroform, to avoid volatilization or decomposition. At 25 °C, the temperature is moderate, enabling the reaction to proceed evenly without being too intense, ensuring the stability and controllability of the reaction between the chemical components in the camellia seed oil distillate and chlorosulfonic acid.

[0017] In step S1.4, the solvent is removed by rotary evaporation in the solvent removal operation. In the neutralization reaction operation, a sodium hydroxide solution with a mass fraction of 10 wt% is used to adjust the pH value of the reaction solution after solvent removal to 8.5 at 20 °C for the neutralization reaction to obtain a neutralization product; in the operation of dissolving the neutralization product, anhydrous ethanol is used as the solvent; in the drying operation, rotary evaporation drying is used for drying. Since in natural rubber latex, the activities of microorganisms produce acidic metabolites, these metabolites will reduce the stability of the latex. The alkaline pH value of the stabilizer can neutralize these acidic metabolites, prevent the natural rubber latex from coagulating due to excessive acidity, avoid a significant decline in the stabilization effect, and is beneficial to extending the storage time of the natural rubber latex, ensuring the stabilization effect of the natural rubber latex.

[0018] In step S2, the stirring operation parameters are as follows: the stirring speed is 800-850r / min; the stirring time is 40-50 minutes. Setting the stirring speed of 800-850r / min: it can effectively evenly distribute the various solid and liquid components during the mixing process. A lower stirring speed cannot fully disperse the solid components, and a too high stirring speed will lead to excessive foam generation or temperature increase of the solution, and even cause the degradation of the components. Therefore, selecting 800-850r / min as a suitable stirring speed can ensure that the components are fully mixed within a reasonable time. Stirring time 40-50 minutes: This stirring time is to ensure that all ingredients can be completely and evenly mixed. Too short a stirring time will cause some ingredients in the formula to not be fully dissolved or evenly distributed, affecting the final effect of the stabilizer; and too long a stirring time will lead to a waste of energy, and may even produce too much foam or volatilization of the solvent, affecting the stability and concentration of the product. The setting of the above parameters is intended to ensure that the various components of the stabilizer are fully and evenly mixed, so that each component can function in its best state. The appropriate stirring speed can avoid excessive foaming or temperature rise caused by over-stirring, and the reasonable stirring time can effectively avoid precipitation or stratification of ingredients, thereby improving the performance and stability of the final stabilizer. The setting of these parameters can help obtain the final stabilizer product with high efficiency in inhibiting microbial growth and improving the stability of natural rubber.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1. No ammonia component: The stabilizer prepared by the present invention does not contain ammonia, thus avoiding the environmental pollution problem caused by the use of ammonia water. Since no deammoniation treatment is required, downstream manufacturers can save the cumbersome deammoniation process, thereby improving production efficiency and saving production costs.

[0021] 2. Improve the stability and preservation effect of natural rubber: The present invention can effectively extend the preservation time of natural rubber through the synergistic effect of the ingredients such as chitosan, sodium diacetate, methyl paraben and special active agents in the formula, ensure the stability of natural rubber latex during storage and transportation, and reduce oxidation, deterioration and other problems. By inhibiting the growth of microorganisms and reducing the production of acidic metabolites, the stabilization effect of latex is further improved.

[0022] 3. Preparation of special surfactants: The special surfactants are prepared using camellia seed oil as raw material. They undergo sophisticated processing techniques such as distillation extraction and sulfonation treatment. During the preparation process, key parameters such as temperature, time and the ratio of reactants are carefully designed to ensure the high purity and high activity of the special surfactants. They can better cooperate with other ingredients to further improve the stability of natural rubber.

[0023] 4. Strengthening of the protective film in latex: The rubber particles in the latex are surrounded by a mixed film formed by proteins and other substances. This protective film is crucial to maintaining the stability of the latex. The stabilizer prepared by the present invention can strengthen the strength of this protective film and prevent it from being destroyed, thereby avoiding coagulation of the latex due to the rupture of the protective film, and ensuring the long-term stability of the latex.

[0024] In summary, the stabilizer of the present invention can effectively prolong the shelf life of rubber latex, improve the stability of natural rubber latex, and help improve environmental protection through multiple mechanisms such as inhibiting microbial growth, adjusting pH value, and enhancing protective film. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a comparison chart of mechanical stability test results. DETAILED DESCRIPTION

[0026] The following are specific embodiments of the present invention and the accompanying drawings to further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0027] Embodiment 1:

[0028] A stabilizer formula for producing ammonia-free rubber comprises the following components by weight: 3.6 parts of chitosan, 1 part of sodium diacetate, 2 parts of methyl parahydroxybenzoate, 1 part of alginate, 3 parts of citric acid, 0.5 parts of sodium sorbate and 1.2 parts of a special active agent.

[0029] A method for preparing a stabilizer for producing ammonia-free rubber, using the above stabilizer formula for producing ammonia-free rubber to prepare the stabilizer, the method for preparing the stabilizer comprises the following steps:

[0030] S1 Preparation of special active agent: S1.1 Distillation extraction: distill camellia oil to obtain camellia oil distillate; S1.2 Pretreatment: add camellia oil distillate to chloroform, stir and mix evenly to obtain camellia oil distillate solution; keep the camellia oil distillate solution warm; S1.3 Sulfonation treatment: add chlorosulfonic acid to chloroform, stir and mix evenly to obtain chlorosulfonic acid solution; add chlorosulfonic acid solution dropwise to the camellia oil distillate solution after the warm-keeping operation, stir while adding, after 1 hour of dropping, adjust the temperature of the reaction system to the target temperature, continue the warm-keeping and stirring operation, and obtain the reaction solution after the warm-keeping and stirring operation is completed; S1.4 Post-treatment: remove the solvent, neutralize the reaction, dissolve the neutralization product, separate and remove the inorganic salt, and dry the reaction solution in sequence to obtain the special active agent;

[0031] S2 Raw material mixing: Weigh chitosan, sodium diacetate, methyl p-hydroxybenzoate, alginate, citric acid, sodium sorbate and a special surfactant according to the formula of the stabilizer, then add them to a stirring device for stirring operation. After stirring evenly, a stabilizer is obtained.

[0032] In step S1.1, a rectification extraction operation is carried out under the conditions of a temperature of 225 °C and a pressure of 5 mmHg.

[0033] In the camellia seed oil rectification solution of step S1.2, the ratio of camellia seed oil rectification product to chloroform is 20 g: 100 mL.

[0034] In the chlorosulfonic acid solution of step S1.3, the ratio of chlorosulfonic acid to chloroform is 8 g: 40 mL.

[0035] In step S1.2, the heat preservation operation parameters are as follows: the temperature is 2 °C and the heat preservation time is 30 minutes.

[0036] In step S1.3, the target temperature is 25 °C and the heat preservation stirring time is 2 hours.

[0037] In step S1.4, the solvent is removed by rotary evaporation in the solvent removal operation. In the neutralization reaction operation, a sodium hydroxide solution with a mass fraction of 10 wt% is used to adjust the pH value of the reaction solution after solvent removal to 8.5 at a temperature of 20 °C for neutralization reaction to obtain a neutralization product; in the operation of dissolving the neutralization product, anhydrous ethanol is used as the solvent.

[0038] In step S2, the stirring operation parameters are as follows: the stirring speed is 800 r / min; the stirring time is 40 minutes.

[0039] Example 2:

[0040] A stabilizer formula for producing ammonia-free rubber, calculated by weight, the stabilizer formula includes the following components: 3.9 parts of chitosan, 2 parts of sodium diacetate, 3 parts of methyl p-hydroxybenzoate, 1.2 parts of alginate, 3.6 parts of citric acid, 0.7 parts of sodium sorbate and 1.3 parts of special surfactant.

[0041] A preparation method of a stabilizer for producing ammonia-free rubber, using the above stabilizer formula for producing ammonia-free rubber to prepare the stabilizer, and the preparation method of the stabilizer includes the following steps:

[0042] S1 Preparation of special surfactant: S1.1 Rectification extraction: Perform rectification extraction on camellia seed oil to obtain camellia seed oil rectification product; S1.2 Pretreatment: Add the camellia seed oil rectification product to chloroform, stir and mix evenly to obtain a camellia seed oil rectification product solution; Keep the camellia seed oil rectification product solution at a certain temperature; S1.3 Sulfonation treatment: Add chlorosulfonic acid to chloroform, stir and mix evenly to obtain a chlorosulfonic acid solution; Dropwise add the chlorosulfonic acid solution to the camellia seed oil rectification product solution that has undergone heat preservation operation, stir while adding, after adding for 1 hour, adjust the temperature of the reaction system to the target temperature, and then continue the heat preservation and stirring operation. After the heat preservation and stirring operation is completed, obtain a reaction solution; S1.4 Post-treatment: After successively performing solvent removal operation, neutralization reaction operation, dissolution of neutralization product operation, separation and removal of inorganic salts operation and drying operation on the reaction solution, obtain a special surfactant;

[0043] S2 Raw material mixing: Weigh chitosan, sodium diacetate, methyl p-hydroxybenzoate, alginate, citric acid, sodium sorbate and special surfactant according to the formula of the stabilizer, and then add them to a stirring device for stirring operation. After stirring evenly, obtain a stabilizer.

[0044] In step S1.1, the rectification extraction operation is carried out under the conditions of a temperature of 230 °C and a pressure of 5.5 mmHg.

[0045] In the camellia seed oil rectification product solution in step S1.2, the ratio of camellia seed oil rectification product to chloroform is 21 g:100 mL.

[0046] In the chlorosulfonic acid solution in step S1.3, the ratio of chlorosulfonic acid to chloroform is 8 g:40 mL.

[0047] In step S1.2, the heat preservation operation parameters are as follows: the temperature is 2 °C and the heat preservation time is 30 minutes.

[0048] In step S1.3, the target temperature is 25 °C and the heat preservation and stirring time is 2 hours.

[0049] In step S1.4, in the solvent removal operation, rotary evaporation is used to remove the solvent. In the neutralization reaction operation, a sodium hydroxide solution with a mass fraction of 10 wt% is used to adjust the pH value of the reaction solution after solvent removal to 8.5 at a temperature of 20 °C for neutralization reaction to obtain a neutralization product; In the operation of dissolving the neutralization product, anhydrous ethanol is used as the solvent;

[0050] In step S2, the stirring operation parameters are as follows: the stirring speed is 800 r / min; the stirring time is 40 minutes.

[0051] Example 3:

[0052] A stabilizer formulation for producing ammonia-free rubber, by weight, the stabilizer formulation includes the following components: 4.2 parts of chitosan, 2 parts of sodium diacetate, 2.5 parts of methyl p-hydroxybenzoate, 1.8 parts of alginate, 3.5 parts of citric acid, 0.7 part of sodium sorbate, and 1.4 parts of a special surfactant.

[0053] A preparation method of a stabilizer for producing ammonia-free rubber, using the above stabilizer formulation for producing ammonia-free rubber to prepare the stabilizer, the preparation method of the stabilizer includes the following steps:

[0054] S1 Prepare a special surfactant: S1.1 Rectification extraction: Perform rectification extraction on camellia seed oil to obtain a camellia seed oil rectification product; S1.2 Pretreatment: Add the camellia seed oil rectification product to chloroform, stir and mix evenly to obtain a camellia seed oil rectification product solution; Keep the camellia seed oil rectification product solution under heat preservation; S1.3 Sulfonation treatment: Add chlorosulfonic acid to chloroform, stir and mix evenly to obtain a chlorosulfonic acid solution; Dropwise add the chlorosulfonic acid solution to the camellia seed oil rectification product solution that has been under heat preservation, stir while dropping, after dropping for 1 hour, adjust the temperature of the reaction system to the target temperature, and then continue the heat preservation and stirring operation. After the heat preservation and stirring operation is completed, obtain a reaction solution; S1.4 Post-treatment: Perform solvent removal operation, neutralization reaction operation, dissolution of the neutralization product operation, separation and removal of inorganic salts operation, and drying operation on the reaction solution in sequence to obtain a special surfactant;

[0055] S2 Raw material mixing: Weigh chitosan, sodium diacetate, methyl p-hydroxybenzoate, alginate, citric acid, sodium sorbate, and the special surfactant according to the stabilizer formulation, then add them to a stirring device for stirring operation. After stirring evenly, obtain the stabilizer.

[0056] In step S1.1, the rectification extraction operation is carried out under the conditions of a temperature of 240 °C and a pressure of 5.2 mmHg.

[0057] In the camellia seed oil rectification product solution in step S1.2, the ratio of camellia seed oil rectification product to chloroform is 21 g: 100 mL.

[0058] In the chlorosulfonic acid solution in step S1.3, the ratio of chlorosulfonic acid to chloroform is 9 g: 40 mL.

[0059] In step S1.2, the heat preservation operation parameters are as follows: temperature is 2 °C, and heat preservation time is 30 minutes.

[0060] In step S1.3, the target temperature is 25 °C, and the heat preservation and stirring time is 2 hours.

[0061] In step S1.4, rotary evaporation is used to remove the solvent. In the neutralization reaction operation, a sodium hydroxide solution with a mass fraction of 10 wt% is used to adjust the pH value of the reaction solution after solvent removal to 8.5 at a temperature of 20 °C for neutralization reaction to obtain a neutralization product. In the operation of dissolving the neutralization product, absolute ethanol is used as the solvent.

[0062] In step S2, the stirring operation parameters are as follows: the stirring speed is 800 r / min; the stirring time is 40 minutes.

[0063] Example 4:

[0064] A stabilizer formulation for producing ammonia-free rubber, by weight, the stabilizer formulation includes the following components: 4.8 parts of chitosan, 3 parts of sodium diacetate, 4 parts of methyl p-hydroxybenzoate, 2 parts of alginate, 4 parts of citric acid, 0.8 part of sodium sorbate, and 1.6 parts of a special surfactant.

[0065] A preparation method of a stabilizer for producing ammonia-free rubber, using the above stabilizer formulation for producing ammonia-free rubber to prepare the stabilizer, and the preparation method of the stabilizer includes the following steps:

[0066] S1 Prepare a special surfactant: S1.1 Rectification extraction: Perform rectification extraction on camellia seed oil to obtain a rectification product of camellia seed oil; S1.2 Pretreatment: Add the rectification product of camellia seed oil to chloroform, stir and mix evenly to obtain a solution of the rectification product of camellia seed oil; Keep the solution of the rectification product of camellia seed oil warm; S1.3 Sulfonation treatment: Add chlorosulfonic acid to chloroform, stir and mix evenly to obtain a chlorosulfonic acid solution; Dropwise add the chlorosulfonic acid solution to the solution of the rectification product of camellia seed oil after the heat preservation operation, stir while dropping, after dropping for 1 hour, adjust the temperature of the reaction system to the target temperature, and then continue the heat preservation stirring operation. After the heat preservation stirring operation is completed, obtain a reaction solution; S1.4 Post-treatment: After performing solvent removal operation, neutralization reaction operation, dissolution of neutralization product operation, separation and removal of inorganic salts operation, and drying operation on the reaction solution in sequence, obtain a special surfactant;

[0067] S2 Raw material mixing: Weigh chitosan, sodium diacetate, methyl p-hydroxybenzoate, alginate, citric acid, sodium sorbate, and a special surfactant according to the stabilizer formulation, add them to a stirring device for stirring operation, and after stirring evenly, obtain a stabilizer.

[0068] In step S1.1, the rectification extraction operation is carried out under the conditions of a temperature of 250 °C and a pressure of 6 mmHg.

[0069] In the solution of the rectification product of camellia seed oil in step S1.2, the rectification product of camellia seed oil: chloroform is 24 g: 100 mL.

[0070] In the chlorosulfonic acid solution in step S1.3, the ratio of chlorosulfonic acid to chloroform is 10 g:40 mL.

[0071] In step S1.2, the heat preservation operation parameters are as follows: the temperature is 2°C, and the heat preservation time is 30 minutes.

[0072] In step S1.3, the target temperature is 25°C, and the heat preservation and stirring time is 2 hours.

[0073] In step S1.4, the solvent is removed by rotary evaporation in the solvent removal operation. In the neutralization reaction operation, a sodium hydroxide solution with a mass fraction of 10 wt% is used to adjust the pH value of the reaction solution after solvent removal to 8.5 at a temperature of 20°C for the neutralization reaction to obtain a neutralization product. In the operation of dissolving the neutralization product, anhydrous ethanol is used as the solvent.

[0074] In step S2, the stirring operation parameters are as follows: the stirring speed is 800 r / min; the stirring time is 40 minutes.

[0075] Comparative Example 1: On the basis of the technical solution of Example 1, no special surfactant is added, and the rest of the technical solutions remain unchanged.

[0076] Comparative Example 2: On the basis of the technical solution of Example 1, no chitosan is added, and the rest of the technical solutions remain unchanged.

[0077] Verification of usage results: The stabilizers prepared in Example 1, 2, 3, 4, Comparative Example 1, and Comparative Example 2 are respectively added to natural rubber fresh latex. The addition amounts are 1%, 1.3%, 1.4%, 1.5%, 1%, and 1% based on the total amount of natural rubber fresh latex. Ammonia water is selected as the stabilizer and added to natural rubber fresh latex as the control group. They are uniformly stored in an environment with a temperature of 25°C, and finally tested. The results are shown in Table 1.

[0078]

[0079] Table 1

[0080] The analysis is as follows: The storage times of all examples (Examples 1 to 4) far exceeded the results of the control group. In particular, Example 3 (≥830 hours) and Example 4 (≥825 hours) showed the best stability, significantly superior to Comparative Example 1 (≥550 hours) and Comparative Example 2 (≥680 hours). The control group (5% ammonia water) had extremely poor stability, with a storage time of only ≤10 hours, far lower than any other group, indicating that ammonia water as a stabilizer has very limited stability effects in fresh natural rubber latex. From the performance of the examples, using the above stabilizers is significantly superior to conventional methods. These stabilizers significantly extended the storage time of natural rubber latex and effectively improved its stability, indicating that the synergistic effects of these components can effectively inhibit the growth and reproduction of microorganisms. Compared with ammonia water, using the stabilizer of the present invention has a longer preservation time.

[0081] As Figure 1 shown, for the mechanical stability detection, it was determined with reference to "GB / T8301-2008 Determination of Mechanical Stability of Concentrated Natural Rubber Latex". The storage time was: 30 days; the average value results are shown in Table 2 as follows:

[0082] Mechanical stability s Example 1 638 Example 2 627 Example 3 615 Example 4 622 Comparative Example 1 813 Comparative Example 2 765

[0083] Table 2

[0084] It can be seen from Table 2 that after using the preservative of the present invention for 30 days, the natural rubber latex has a more suitable mechanical stability. In the actual use process of rubber, it is not that the higher the mechanical strength, the better. For the needs of flexibility, elasticity or other specific functions, too high strength may lead to unsuitability, and too high mechanical strength will affect the flexibility and adaptability of rubber.

[0085] Based on Example 1 as the basic sample, the changes in the mechanical stability of the natural rubber latex were compared under different storage times as shown in Table 3:

[0086] Storage time d Mechanical stability s 0 60 10 112 20 338 30 638 40 694 50 725 60 760

[0087] Table 3

[0088] It can be seen from Table 3 that as the storage time increases, the mechanical stability of the natural rubber latex first increases relatively quickly and then the increasing rate continuously decreases.

[0089] The specific embodiments described herein are merely illustrative of the spirit of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar means for substitution, but will not deviate from the spirit of the present invention or exceed the defined scope. Although the present invention has been described in detail in the accompanying drawings and the foregoing description, such description and description are considered to be illustrative or exemplary rather than restrictive. It should be understood that within the scope of the following claims, those of ordinary skill in the art can make changes and modifications. Specifically, the present invention encompasses additional embodiments having any combination of features from the different embodiments described above. In terms of the use of the expressions "generally" or "substantially", this patent application should be understood as disclosing that the same fully meets these features and values, i.e., without the foregoing being characterized as "generally" or "substantially".

Claims

1. A stabilizer formulation for producing ammonia-free rubber, characterized in that: The stabilizer formula includes the following ingredients in parts by weight: 3.6-4.8 parts of chitosan, 1-3 parts of sodium diacetate, 2-4 parts of methyl parahydroxybenzoate, 1-2 parts of alginate, 3-4 parts of citric acid, 0.5-0.8 parts of sodium sorbate and 1.2-1.6 parts of a special active agent, wherein the special active agent is prepared using camellia seed oil as raw material, and the weight ratio of chitosan to the special active agent is 3:

1.

2. A method for preparing a stabilizer for producing ammonia-free rubber, using the stabilizer formula for producing ammonia-free rubber according to claim 1 to prepare the stabilizer, characterized in that: The preparation method of the stabilizer for producing ammonia-free rubber comprises the following steps: S1. Preparation of a special active agent: S1.1 Distillation extraction: distilling and extracting camellia oil to obtain camellia oil distillate; S1.2 Pretreatment: adding the camellia oil distillate to chloroform, stirring and mixing evenly to obtain a camellia oil distillate solution; heat-insulating the camellia oil distillate solution; S1.3 Sulfonation treatment: add chlorosulfonic acid to chloroform, stir and mix evenly to obtain chlorosulfonic acid solution; add chlorosulfonic acid solution to the camellia oil distillate solution after heat preservation operation, stir while adding, after the addition is completed, adjust the temperature of the reaction system to the target temperature, and perform heat preservation and stirring operation, after the heat preservation and stirring operation is completed, obtain the reaction liquid; S1.4 Post-treatment: remove the solvent operation, neutralize the reaction operation, dissolve the neutralization product operation, separate and remove the inorganic salt operation and dry the reaction liquid in sequence to obtain the special active agent; S2 raw material mixing: according to the formula of the stabilizer, chitosan, sodium diacetate, methyl parahydroxybenzoate, alginate, citric acid, sodium sorbate and a special active agent are weighed, added into a stirring device for stirring, and after stirring evenly, a stabilizer is obtained.

3. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In step S1.1, the distillation extraction operation is carried out at a temperature of 225-250°C and a pressure of 5-6 mmHg.

4. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In the camellia oil distillate solution of step S1.2, the ratio of camellia oil distillate to chloroform is 20-24 g: 100 mL.

5. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In step S1.2, the insulation operation parameters are as follows: temperature is 0-2°C, and the insulation time is 30-40 minutes.

6. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In the chlorosulfonic acid solution of step S1.3, the ratio of chlorosulfonic acid to chloroform is 8-10 g:40 mL.

7. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In step S1.3, the target temperature is 25°C and the stirring time is 2-3 hours.

8. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In step S1.4, the solvent is removed by rotary evaporation in the solvent removal process, and in the neutralization reaction process, a sodium hydroxide solution with a mass fraction of 10wt% is used to adjust the pH value of the reaction solution after the solvent is removed to 8.5 at a temperature of 20°C to perform a neutralization reaction to obtain a neutralized product; In the process of dissolving and neutralizing the product, anhydrous ethanol is used as the solvent; in the process of drying, rotary evaporation drying is used for drying.

9. The method for preparing a stabilizer for producing ammonia-free rubber according to claim 2, characterized in that: In step S2, the stirring operation parameters are as follows: the stirring speed is 800-850 r / min; the stirring time is 40-50 minutes.

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