WO2022099883A1 - 低蛋白天然橡胶及其制备方法 - Google Patents

低蛋白天然橡胶及其制备方法 Download PDF

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WO2022099883A1
WO2022099883A1 PCT/CN2020/139735 CN2020139735W WO2022099883A1 WO 2022099883 A1 WO2022099883 A1 WO 2022099883A1 CN 2020139735 W CN2020139735 W CN 2020139735W WO 2022099883 A1 WO2022099883 A1 WO 2022099883A1
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antioxidant
rubber
preparation
natural rubber
natural
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PCT/CN2020/139735
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English (en)
French (fr)
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廖禄生
林宏图
邓东华
钟杰平
许逵
彭政
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中国热带农业科学院农产品加工研究所
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Publication of WO2022099883A1 publication Critical patent/WO2022099883A1/zh

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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of rubber materials, in particular to a low-protein natural rubber and a preparation method thereof.
  • Low-protein natural rubber has the characteristics of low water absorption, creep resistance and low heat generation. oxide, etc.) mixed with natural rubber latex, and after a period of reaction, the latex is coagulated to obtain a coagulum, and the coagulum is washed, creped, granulated and dried to obtain a low-protein natural rubber.
  • the low-protein natural rubber is prepared by the above-mentioned process, the rubber material tends to become sticky and entrapped during the drying process, and the drying time needs to be prolonged; and the prolongation of the drying time will easily change the aging resistance and mechanical properties of the low-protein natural rubber. inferior.
  • the object of the present invention is to provide a low-protein natural rubber and a preparation method thereof.
  • the method provided by the present invention can prevent stickiness and entrapment of the rubber material during drying, improve drying efficiency, and simultaneously improve the resistance of low-protein natural rubber. Aging properties and mechanical properties.
  • the invention provides a preparation method of low-protein natural rubber, comprising the following steps:
  • the mixed material is sequentially coagulated, washed, creped, granulated and dried to obtain low-protein natural rubber.
  • the rubber antioxidant is a natural antioxidant and/or a synthetic antioxidant.
  • the natural antioxidant is a natural phenolic antioxidant
  • the synthetic antioxidant is at least one of a synthetic phenolic antioxidant, a synthetic amine antioxidant and a synthetic heterocyclic antioxidant.
  • the natural phenolic antioxidant is at least one of tocopherol and tocotriene;
  • the synthetic phenolic antioxidant includes at least one of antioxidant 1010, antioxidant 264, antioxidant 2246 and antioxidant DOD;
  • the synthetic amine antioxidant includes at least one of antioxidant H, antioxidant D, antioxidant RD, antioxidant DNP, antioxidant KY-405, antioxidant 4010 and antioxidant 4010NA;
  • the synthetic heterocyclic antioxidant includes at least one of antioxidant DBH and antioxidant MB.
  • the rubber antioxidant-containing dispersion includes the following components:
  • the stabilizer is at least one of diffusing agent NF, casein and sodium pyrophosphate; the dispersing agent is at least one of ammonium oleate, ammonium laurate and triethanolamine oleate.
  • the stabilizer is a diffusing agent NF and casein, and the mass ratio of the diffusing agent NF and casein is 6:(7-9).
  • the deproteinized natural latex is obtained by deproteinizing natural rubber latex, and the dry rubber content of the natural rubber latex is 20-50 wt%.
  • the mass of the natural rubber latex is calculated as dry rubber, and the mass of the rubber antioxidant in the mixture is 0.01-1% of the mass of the natural rubber latex.
  • the deproteinization treatment agent used in the deproteinization treatment includes at least one of protease, sodium lauryl sulfate, urea, fumed silica and metal hydroxide.
  • the deproteinizing agent is protease and sodium dodecyl sulfate, and the mass ratio of the protease and sodium dodecyl sulfate is (3-9):5.
  • the mass of the natural rubber latex is calculated as dry rubber, and the mass ratio of the natural rubber latex to the deproteinized treatment agent is 30:(0.10-0.13).
  • the temperature of the deproteinization treatment is 30-40° C., and the time is 8-12 h.
  • the drying temperature is 80-130° C.
  • the drying time is 2-10 h.
  • the present invention provides the low-protein natural rubber prepared by the preparation method described in the above technical solution, the low-protein natural rubber contains a rubber antioxidant, and the nitrogen content in the low-protein natural rubber is ⁇ 0.2wt%.
  • the invention provides a method for preparing low-protein natural rubber, comprising the following steps: providing a dispersion containing a rubber antioxidant; mixing the deproteinized natural latex with the dispersion containing the rubber antioxidant to obtain a mixed material; The mixed material is sequentially coagulated, washed, creped, granulated and dried to obtain low-protein natural rubber.
  • the deproteinized natural latex and the rubber antioxidant are mixed and then coagulated and other operations are carried out.
  • the rubber antioxidant can be adsorbed on the surface of the deproteinized rubber particles to compensate for the loss of protein caused by the deproteinization treatment, and can improve the antioxidant capacity of the rubber particles.
  • the oxidative degradation of the rubber molecular chain prevents the rubber from sticking and entrapped during drying, improves the drying efficiency, and at the same time improves the aging resistance and mechanical properties of the low-protein natural rubber.
  • the results of the examples show that, compared with the low-protein natural rubber prepared without adding a rubber antioxidant, the plasticity retention (PRI) of the low-protein natural rubber prepared by the method provided by the present invention is increased by at least 20%, and the tensile strength is increased by at least 20%. Tensile strength retention after aging increased by at least 25%.
  • the invention provides a preparation method of low-protein natural rubber, comprising the following steps:
  • the mixed material is sequentially coagulated, washed, creped, granulated and dried to obtain low-protein natural rubber.
  • the used preparation raw materials are all commercially available commodities well known to those skilled in the art.
  • the present invention provides dispersions containing rubber antioxidants.
  • the rubber antioxidant is specifically a natural antioxidant and/or a synthetic antioxidant, preferably a natural antioxidant or a synthetic antioxidant.
  • the natural antioxidant is preferably a natural phenolic antioxidant
  • the natural phenolic antioxidant is preferably at least one of tocopherol and tocotriene, more preferably tocopherol or tocotriene .
  • the synthetic antioxidant is preferably at least one of synthetic phenolic antioxidants, synthetic amine antioxidants and synthetic heterocyclic antioxidants, more preferably synthetic phenolic antioxidants, synthetic amine antioxidants Or synthetic heterocyclic antioxidants.
  • the synthetic phenolic antioxidant preferably includes 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 includes at least one of antioxidant H, antioxidant D, antioxidant RD, antioxidant DNP, antioxidant KY-405, antioxidant 4010 and antioxidant 4010NA, More preferably, it is antioxidant H, antioxidant D, antioxidant RD, antioxidant DNP, antioxidant KY-405, antioxidant 4010 or antioxidant 4010NA;
  • the synthetic heterocyclic antioxidant includes antioxidant DBH and antioxidant MB. At least one, more preferably antioxidant DBH or antioxidant MB.
  • the dispersion containing the rubber antioxidant preferably includes the following components:
  • the dispersion provided by the present invention includes 3-50 parts, preferably 3-35 parts, of the rubber antioxidant.
  • the dispersion provided by the present invention includes 0-5 parts of stabilizer, preferably 3-5 parts.
  • the stabilizer is preferably at least one of diffusing agent NF, casein and sodium pyrophosphate, more preferably diffusing agent NF and casein, and the mass ratio of the diffusing agent NF and casein is preferably 6: (7-9).
  • the stabilizer can improve the stability of the dispersion containing the rubber antioxidant, which is beneficial to the uniform distribution of the rubber antioxidant in the latex.
  • the dispersion provided by the present invention includes 0-5 parts, preferably 0.5-2 parts, of a dispersant.
  • the dispersant is preferably at least one of ammonium oleate, ammonium laurate and triethanolamine oleate, more preferably ammonium oleate, ammonium laurate or triethanolamine oleate.
  • the dispersant can reduce the interfacial tension between the rubber anti-aging agent and water, so that the rubber anti-aging agent particles are uniformly dispersed in the aqueous solution, which is conducive to maintaining the dispersed state of the rubber anti-aging agent.
  • the dispersion provided by the present invention includes 40-97 parts of water, preferably 45-80 parts.
  • the water is preferably deionized water.
  • the preparation method of the dispersion containing the rubber antioxidant is based on the uniform mixing of the components; in the present invention, the dispersion containing the rubber antioxidant preferably adopts either of the following two methods kind:
  • Mode 1 After mixing the components of the dispersion, perform a homogenization treatment to obtain a dispersion.
  • the rotation speed of the homogenization treatment is preferably 8000-12000r/min, more preferably 10000r/min; the time of the homogenization treatment is preferably 5-15min, more preferably 10min; the homogenization treatment It is preferably carried out in a high shear homogenizer.
  • Method 2 The components of the dispersion are stirred and mixed with glass sand, and then the glass sand is removed by filtration to obtain a dispersion.
  • the particle size of the glass sand is preferably 2-3 mm; the mass ratio of the bulk volume of the glass sand to the rubber antioxidant is preferably (180-220) mL: 100 g, more preferably 200 mL: 100 g;
  • the present invention uses glass sand as the grinding medium.
  • the rotational speed of the stirring and mixing is preferably based on fast speed without droplet splashing, specifically 1500 r/min; the stirring and mixing time is preferably 10-15h, more preferably 12h.
  • the glass sand is preferably removed by filtering with a screen.
  • a dispersion containing the rubber antioxidant can be prepared in a specific way; when the rubber antioxidant is antioxidant 4010NA or antioxidant 264, Specifically, the second method can be used to prepare the dispersion containing the rubber antioxidant.
  • the present invention mixes the deproteinized natural latex with the dispersion containing the rubber antioxidant to obtain a mixed material.
  • the deproteinized natural rubber latex is preferably obtained by deproteinizing natural rubber latex.
  • 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 %, more preferably 30 wt %.
  • the deproteinization treatment agent used in the deproteinization treatment preferably includes at least one of protease, sodium lauryl sulfate, urea, fumed silica and metal hydroxide, and the protease is preferably papaya At least one of protease and 2709 alkaline protease; in the present invention, the deproteinized treatment agent is more preferably protease and sodium dodecyl sulfate, and the mass ratio of the protease and sodium dodecyl sulfate is preferably (3 to 9): 5, more preferably 6:5.
  • the sodium dodecyl sulfate is preferably used in the form of an aqueous sodium dodecyl sulfate solution, and the concentration of the sodium dodecyl sulfate aqueous solution is preferably 8-12 wt %, more preferably 10 wt %.
  • the mass of the natural rubber latex is based on dry rubber, and the mass ratio of the natural rubber latex to the deproteinizing agent is preferably 30:(0.10-0.13), more preferably 30:0.11.
  • the natural rubber latex, ammonia water and a deproteinizing agent are preferably mixed and then deproteinized to obtain a deproteinized natural latex.
  • the concentration of the ammonia water is preferably 22-28 wt%, more preferably 25 wt%; the mass of the natural rubber latex is calculated as dry rubber, and the mass ratio of the natural rubber latex to the ammonia water is preferably 30: (0.35 ⁇ 0.45), more preferably 30:0.4.
  • the present invention is beneficial to improve the stability of natural rubber latex through ammonia water.
  • the temperature of the deproteinization treatment is preferably 30-40°C, more preferably 35°C; the time is preferably 8-12h, more preferably 10h.
  • the mass of the natural rubber latex is calculated as dry rubber, and the mass of the rubber antioxidant in the mixture is preferably 0.01-1% of the mass of the natural rubber latex, more preferably 0.02-0.5%, and even more preferably 0.05 ⁇ 0.2%.
  • the present invention does not specifically limit the mixing method of the deproteinized natural latex and the dispersion containing the rubber antioxidant, and a method well known to those skilled in the art is adopted to ensure that the components are mixed uniformly.
  • the present invention sequentially performs coagulation, washing, crepe pressing, granulation and drying on the mixed material to obtain low-protein natural rubber.
  • the coagulation reagent used for the coagulation is preferably formic acid, acetic acid or hydrochloric acid, more preferably formic acid.
  • the mixture is preferably mixed with a coagulation reagent for coagulation to obtain a clot; the mass of the coagulation reagent is preferably 1.5-2.5% of the mass of the mixture, more preferably 2%.
  • the present invention sequentially washes and crepes the curd to obtain a film.
  • the washing agent is preferably water; the thickness of the film obtained after the creping is preferably 2-3 mm; the washing and creping are preferably performed in a crepe machine.
  • the film is sequentially granulated and dried to obtain low-protein natural rubber.
  • the particle size of the colloidal particles obtained after the granulation is preferably 2-5 mm; the granulation is preferably carried out in a granulator, and the colloidal particles obtained by granulation are dripped and then dried.
  • the drying temperature is preferably 80-130°C, more preferably 115°C; the time is preferably 2-10 h, more preferably 3-4 h; the drying is preferably performed in a hot air drying oven.
  • the present invention provides the low-protein natural rubber prepared by the preparation method described in the above technical solution.
  • the nitrogen content in the low-protein natural rubber is less than or equal to 0.2 wt%
  • the low-protein natural rubber contains a rubber antioxidant.
  • the rubber antioxidant will capture free radicals in the system, So as to play the role of protecting the colloidal particles.
  • the mixed material is mixed with formic acid to solidify to obtain a clot; the mass of the formic acid is 2% of the mass of the mixed material;
  • the clot is washed and creped with clean water through a crepe machine to obtain a film with a thickness of 2 to 3 mm, which is then granulated with a tearing machine to obtain colloidal particles with a particle size of 2 to 5 mm. Dry in a hot air drying oven at 115°C for 4 hours to obtain low-protein natural rubber.
  • antioxidant 4010NA and 6g diffusing agent NF in an enamel cup, add 80mL casein solution with a concentration of 10wt% (solvent is water), 64mL deionized water and glass sand with a stacking volume of 200mL (particle size is 2-3mm) ), cover after stirring and use an electric mixer with stainless steel stirring paddle to stir for 12h (the stirring speed is 1500rpm), then filter the glass sand with a screen to obtain a stable antioxidant 4010NA dispersion;
  • the mixed material is mixed with formic acid and solidified to obtain a clot; the mass of the formic acid is 2% of the mass of the mixed material;
  • the clot is washed and creped with clean water through a crepe machine to obtain a film with a thickness of 2 to 3 mm, which is then granulated with a tearing machine to obtain colloidal particles with a particle size of 2 to 5 mm. Dry in a hot air drying oven at 115°C for 3.5 hours to obtain low-protein natural rubber.
  • antioxidant 264 and 6g diffusing agent NF in an enamel cup, add 80mL casein solution with a concentration of 10wt% (the solvent is water), 64mL deionized water and glass sand with a bulk volume of 200mL (particle size is 2-3mm) ), cover after stirring and use an electric mixer with stainless steel stirring paddle to stir for 12h (the stirring speed is 1500rpm), then filter the glass sand with a screen to obtain a stable antioxidant 264 dispersion;
  • the deproteinized natural rubber latex was mixed with 150 g of the antioxidant 264 dispersion to obtain a mixed material;
  • the mixed material is mixed with formic acid to solidify to obtain a clot; the mass of the formic acid is 2% of the mass of the mixed material;
  • the clot is washed and creped with clean water through a crepe machine to obtain a film with a thickness of 2 to 3 mm, which is then granulated with a tearing machine to obtain colloidal particles with a particle size of 2 to 5 mm. Dry in a hot air drying oven at 115°C for 3 hours to obtain low-protein natural rubber.
  • the deproteinized natural rubber latex is mixed with formic acid for coagulation to obtain a curd; the mass of the formic acid is 2% of the mass of the deproteinized natural rubber latex;
  • the coagulum was washed and creped by a crepe machine with clean water, and then granulated by a tearing machine. After dripping water, the colloidal particles were dried in a hot air drying box at 115° C. for 8 hours to obtain low-protein natural rubber.
  • the properties of the low-protein natural rubbers prepared in Examples 1 to 3 and Comparative Example 1 were tested, wherein the test samples for drying, ash content, volatile matter, nitrogen content, impurities, initial plasticity value and plasticity retention rate were raw rubber, namely The low-protein natural rubbers prepared in Examples 1 to 3 and Comparative Example 1; the test samples for tensile strength and tensile strength retention are the vulcanized rubbers obtained after the raw rubber is vulcanized, and the vulcanized rubber adopts the ACS1 formula.
  • the test results are detailed in Table 1.
  • the method provided by the present invention can prevent the sizing material from being sticky and entrapped; compared with Comparative Example 1, the low-protein natural rubber prepared by the method provided by the present invention has more excellent performance, and the plasticity retention rate (PRI ) by at least 20%, tensile strength by at least 15%, and retention of tensile strength after aging by at least 25%.
  • PRI plasticity retention rate

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Abstract

低蛋白天然橡胶及其制备方法。制备方法包括以下步骤：提供含有橡胶防老剂的分散体；将脱蛋白天然胶乳与含有橡胶防老剂的分散体混合，得到混合物料；将混合物料依次进行凝固、洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。该制备方法能够防止胶料在干燥时出现发粘、夹生现象，提高干燥效率，同时能够提高低蛋白天然橡胶的耐老化性能和力学性能。

Description

[根据细则37.2由ISA制定的发明名称]　低蛋白天然橡胶及其制备方法
本申请要求于2020年11月13日提交中国专利局、申请号为CN202011268694.9、发明名称为“一种低蛋白天然橡胶及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及橡胶材料技术领域，具体涉及一种低蛋白天然橡胶及其制备方法。
背景技术
低蛋白天然橡胶具有低吸水性、抗蠕变和低生热等特点，其常规制备工艺是：将脱蛋白处理剂(如蛋白酶、十二烷基硫酸钠、尿素、气相二氧化硅或金属氢氧化物等)与天然橡胶胶乳混合，反应一段时间后，将胶乳凝固得到凝块，凝块再经洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。但是，采用上述工艺制备低蛋白天然橡胶，在干燥过程中容易出现胶料发粘、夹生现象，需延长干燥时间；而干燥时间的延长又容易使低蛋白天然橡胶的耐老化性能和力学性能变劣。
发明内容
本发明的目的在于提供一种低蛋白天然橡胶及其制备方法，采用本发明提供的方法能够防止胶料在干燥时出现发粘、夹生现象，提高干燥效率，同时能够提高低蛋白天然橡胶的耐老化性能和力学性能。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种低蛋白天然橡胶的制备方法，包括以下步骤：
提供含有橡胶防老剂的分散体；
将脱蛋白天然胶乳与所述含有橡胶防老剂的分散体混合，得到混合物料；
将所述混合物料依次进行凝固、洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。
优选地，所述橡胶防老剂为天然防老剂和/或合成防老剂。
优选地，所述天然防老剂为天然酚类防老剂；所述合成防老剂为合成 酚类防老剂、合成胺类防老剂和合成杂环类防老剂中的至少一种。
优选地，所述天然酚类防老剂为生育酚和三烯生育酚中的至少一种；
所述合成酚类防老剂包括抗氧剂1010、防老剂264、防老剂2246和防老剂DOD中的至少一种；
所述合成胺类防老剂包括防老剂H、防老剂D、防老剂RD、防老剂DNP、防老剂KY-405、防老剂4010和防老剂4010NA中的至少一种；
所述合成杂环类防老剂包括防老剂DBH和防老剂MB中的至少一种。
优选地，按质量份数计，所述含有橡胶防老剂的分散体包括以下组分：
橡胶防老剂 3～50份；
稳定剂 0～5份；
分散剂 0～5份；
水 40～97份。
优选地，所述稳定剂为扩散剂NF、酪素和焦磷酸钠中的至少一种；所述分散剂为油酸铵、月桂酸铵和油酸三乙醇胺中的至少一种。
优选地，所述稳定剂为扩散剂NF和酪素，所述扩散剂NF和酪素的质量比为6：(7～9)。
优选地，所述脱蛋白天然胶乳由天然橡胶胶乳经脱蛋白处理得到，所述天然橡胶胶乳的干胶含量为20～50wt％。
优选地，所述天然橡胶胶乳的质量以干胶计，所述混合物料中橡胶防老剂的质量为天然橡胶胶乳质量的0.01～1％。
优选地，所述脱蛋白处理采用的脱蛋白处理剂包括蛋白酶、十二烷基硫酸钠、尿素、气相二氧化硅和金属氢氧化物中的至少一种。
优选地，所述脱蛋白处理剂为蛋白酶和十二烷基硫酸钠，所述蛋白酶和十二烷基硫酸钠的质量比为(3～9)：5。
优选地，所述天然橡胶胶乳的质量以干胶计，天然橡胶胶乳与脱蛋白处理剂的质量比为30：(0.10～0.13)。
优选地，所述脱蛋白处理的温度为30～40℃，时间为8～12h。
优选地，所述干燥的温度为80～130℃，时间为2～10h。
本发明提供了上述技术方案所述制备方法制备得到的低蛋白天然橡 胶，所述低蛋白天然橡胶中含有橡胶防老剂，所述低蛋白天然橡胶中氮含量≤0.2wt％。
本发明提供了一种低蛋白天然橡胶的制备方法，包括以下步骤：提供含有橡胶防老剂的分散体；将脱蛋白天然胶乳与所述含有橡胶防老剂的分散体混合，得到混合物料；将所述混合物料依次进行凝固、洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。本发明将脱蛋白天然胶乳和橡胶防老剂混合后再进行凝固等操作，橡胶防老剂能够吸附在脱蛋白橡胶粒子表面，补偿脱蛋白处理导致的蛋白质流失，能够提高橡胶粒子的抗氧化能力，减少橡胶分子链的氧化降解，防止胶料在干燥时出现发粘、夹生现象，提高干燥效率，同时能够提高低蛋白天然橡胶的耐老化性能和力学性能。实施例的结果显示，与不添加橡胶防老剂制备的低蛋白天然橡胶相比，采用本发明提供的方法制备的低蛋白天然橡胶塑性保持率(PRI)至少提高了20％，拉伸强度至少提高了15％，老化后拉伸强度保持率至少提高了25％。
具体实施方式
本发明提供了一种低蛋白天然橡胶的制备方法，包括以下步骤：
提供含有橡胶防老剂的分散体；
将脱蛋白天然胶乳与所述含有橡胶防老剂的分散体混合，得到混合物料；
将所述混合物料依次进行凝固、洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。
在本发明中，若无特殊说明，所用制备原料均为本领域技术人员熟知的市售商品。
本发明提供含有橡胶防老剂的分散体。在本发明中，所述橡胶防老剂具体为天然防老剂和/或合成防老剂，优选为天然防老剂或合成防老剂。在本发明中，所述天然防老剂优选为天然酚类防老剂，所述天然酚类防老剂优选为生育酚和三烯生育酚中的至少一种，更优选为生育酚或三烯生育酚。在本发明中，所述合成防老剂优选为合成酚类防老剂、合成胺类防老剂和合成杂环类防老剂中的至少一种，更优选为合成酚类防老剂、合成胺类防老剂或合成杂环类防老剂。在本发明中，所述合成酚类防老剂优选包括抗氧剂1010、防老剂264、防老剂2246和防老剂DOD中的至少一种， 更优选为抗氧剂1010、防老剂264、防老剂2246或防老剂DOD；所述合成胺类防老剂优选包括防老剂H、防老剂D、防老剂RD、防老剂DNP、防老剂KY-405、防老剂4010和防老剂4010NA中的至少一种，更优选为防老剂H、防老剂D、防老剂RD、防老剂DNP、防老剂KY-405、防老剂4010或防老剂4010NA；所述合成杂环类防老剂包括防老剂DBH和防老剂MB中的至少一种，更优选为防老剂DBH或防老剂MB。
在本发明中，按质量份数计，所述含有橡胶防老剂的分散体优选包括以下组分：
橡胶防老剂 3～50份；
稳定剂 0～5份；
分散剂 0～5份；
水 40～97份。
按质量份数计，本发明提供的分散体包括橡胶防老剂3～50份，优选为3～35份。
以所述橡胶防老剂的质量份数为基准，本发明提供的分散体包括稳定剂0～5份，优选为3～5份。在本发明中，所述稳定剂优选为扩散剂NF、酪素和焦磷酸钠中的至少一种，更优选为扩散剂NF和酪素，所述扩散剂NF和酪素的质量比优选为6：(7～9)。在本发明中，所述稳定剂能够提高所述含有橡胶防老剂的分散体的稳定性，有利于橡胶防老剂均匀分布于胶乳中。
以所述橡胶防老剂的质量份数为基准，本发明提供的分散体包括分散剂0～5份，优选为0.5～2份。在本发明中，所述分散剂优选为油酸铵、月桂酸铵和油酸三乙醇胺中的至少一种，更优选为油酸铵、月桂酸铵或油酸三乙醇胺。在本发明中，所述分散剂能够降低橡胶防老剂与水的界面张力，使橡胶防老剂微粒均匀地分散在水溶液中，有利于橡胶防老剂保持分散状态。
以所述橡胶防老剂的质量份数为基准，本发明提供的分散体包括水40～97份，优选为45～80份。在本发明中，所述水优选为去离子水。
在本发明中，所述含有橡胶防老剂的分散体的制备方法以各组分混合均匀为基准；在本发明中，所述含有橡胶防老剂的分散体优选采用以下两 种方式中的任一种：
方式一：将分散体的各组分混合后进行均质处理，得到分散体。在本发明中，所述均质处理的转速优选为8000～12000r/min，更优选为10000r/min；所述均质处理的时间优选为5～15min，更优选为10min；所述均质处理优选在高剪切均质机中进行。
方式二：将分散体的各组分与玻璃砂搅拌混合，之后过滤去除玻璃砂，得到分散体。在本发明中，所述玻璃砂的粒径优选为2～3mm；所述玻璃砂的堆积体积与橡胶防老剂的质量比优选为(180～220)mL：100g，更优选为200mL：100g；本发明通过玻璃砂作为研磨介质。在本发明中，所述搅拌混合的转速优选以快而无液滴飞溅为基准，具体可以为1500r/min；所述搅拌混合的时间优选为10～15h，更优选为12h。本发明优选采用筛网过滤去除所述玻璃砂。
在本发明的实施例中，当橡胶防老剂为生育酚或三烯生育酚时，具体可以采用方式一制备含有橡胶防老剂的分散体；当橡胶防老剂为防老剂4010NA或防老剂264时，具体可以采用方式二制备含有橡胶防老剂的分散体。
得到含有橡胶防老剂的分散体后，本发明将脱蛋白天然胶乳与所述含有橡胶防老剂的分散体混合，得到混合物料。在本发明中，所述脱蛋白天然胶乳优选由天然橡胶胶乳经脱蛋白处理得到。在本发明中，所述天然橡胶胶乳优选为新鲜天然橡胶胶乳，所述天然橡胶胶乳的干胶含量优选为20～50wt％，更优选为30wt％。
在本发明中，所述脱蛋白处理采用的脱蛋白处理剂优选包括蛋白酶、十二烷基硫酸钠、尿素、气相二氧化硅和金属氢氧化物中的至少一种，所述蛋白酶优选为木瓜蛋白酶和2709碱性蛋白酶中的至少一种；在本发明中，所述脱蛋白处理剂更优选为蛋白酶和十二烷基硫酸钠，所述蛋白酶和十二烷基硫酸钠的质量比优选为(3～9)：5，更优选为6：5。在本发明中，所述十二烷基硫酸钠优选以十二烷基硫酸钠水溶液形式使用，所述十二烷基硫酸钠水溶液的浓度优选为8～12wt％，更优选为10wt％。在本发明中，所述天然橡胶胶乳的质量以干胶计，天然橡胶胶乳与脱蛋白处理剂的质量比优选为30：(0.10～0.13)，更优选为30：0.11。
本发明优选将天然橡胶胶乳、氨水和脱蛋白处理剂混合后进行脱蛋白处理，得到脱蛋白天然胶乳。在本发明中，所述氨水的浓度优选为22～28wt％，更优选为25wt％；所述天然橡胶胶乳的质量以干胶计，天然橡胶胶乳与氨水的质量比优选为30：(0.35～0.45)，更优选为30：0.4。本发明通过氨水有利于提高天然橡胶胶乳的稳定性。
在本发明中，所述脱蛋白处理的温度优选为30～40℃，更优选为35℃；时间优选为8～12h，更优选为10h。
在本发明中，所述天然橡胶胶乳的质量以干胶计，所述混合物料中橡胶防老剂的质量优选为天然橡胶胶乳质量的0.01～1％，更优选为0.02～0.5％，进一步优选为0.05～0.2％。本发明对脱蛋白天然胶乳与含有橡胶防老剂的分散体混合的方式没有特殊限定，采用本领域技术人员熟知的方式，保证各组分混合均匀即可。
得到混合物料后，本发明将所述混合物料依次进行凝固、洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。在本发明中，所述凝固采用的凝固试剂优选为甲酸、乙酸或盐酸，更优选为甲酸。本发明优选将所述混合物料与凝固试剂混合进行凝固，得到凝块；所述凝固试剂的质量优选为所述混合物料质量的1.5～2.5％，更优选为2％。
得到凝块后，本发明将所述凝块依次进行洗涤和压绉，得到胶片。在本发明中，所述洗涤用试剂优选为水；所述压绉后所得胶片的厚度优选为2～3mm；所述洗涤和压绉优选在绉片机中进行。
得到胶片后，本发明将所述胶片依次进行造粒和干燥，得到低蛋白天然橡胶。在本发明中，所述造粒后所得胶粒的粒径优选为2～5mm；所述造粒优选在撕粒机中进行，造粒所得胶粒滴水后进行干燥。在本发明中，所述干燥的温度优选为80～130℃，更优选为115℃；时间优选为2～10h，更优选为3～4h；所述干燥优选在热风干燥箱中进行。
本发明提供了上述技术方案所述制备方法制备得到的低蛋白天然橡胶。在本发明中，所述低蛋白天然橡胶中氮含量≤0.2wt％，所述低蛋白天然橡胶中含有橡胶防老剂，在制备低蛋白天然橡胶过程中，橡胶防老剂会捕捉体系中自由基，从而起到保护胶粒的作用。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
取新鲜天然橡胶胶乳100kg，测得干胶含量为30.0wt％；将所述新鲜天然橡胶胶乳与浓度为25wt％的氨水0.4kg、浓度为10wt％的十二烷基硫酸钠水溶液0.5kg和木瓜蛋白酶60g混合，在35℃条件下反应10h，得到脱蛋白天然胶乳；
将15g生育酚、2g油酸铵和300mL去离子水加入烧杯中，用高剪切均质机在10000r/min条件下处理10min，得到稳定的生育酚分散体；
将所述脱蛋白天然胶乳与生育酚分散体混合，得到混合物料；
将所述混合物料与甲酸混合进行凝固，得到凝块；所述甲酸的质量为所述混合物料质量的2％；
所述凝块用清水经绉片机进行洗涤和压绉，得到厚度为2～3mm的胶片，再用撕粒机进行造粒，得到粒径为2～5mm的胶粒，胶粒滴水后，在115℃的热风干燥箱内干燥4h，得到低蛋白天然橡胶。
实施例2
取新鲜天然橡胶胶乳100kg，测得干胶含量为30.0wt％；将所述新鲜天然橡胶胶乳与浓度为25wt％的氨水0.4kg、浓度为10wt％的十二烷基硫酸钠水溶液0.5kg和木瓜蛋白酶60g混合，在35℃条件下反应10h，得到脱蛋白天然胶乳；
将100g防老剂4010NA和6g扩散剂NF置于搪瓷杯内，加入80mL浓度为10wt％的酪素溶液(溶剂为水)、去离子水64mL以及堆积体积为200mL的玻璃砂(粒度为2～3mm)，搅和后加盖并利用具不锈钢搅拌浆的电动搅拌机搅拌12h(搅拌速度为1500rpm)，之后用筛网滤去玻璃砂，得到稳定的防老剂4010NA分散体；
将所述脱蛋白天然胶乳与75g所述防老剂4010NA分散体混合，得到混合物料；
将所述混合物料与甲酸混合进行凝固，得到凝块；所述甲酸的质量为 所述混合物料质量的2％；
所述凝块用清水经绉片机进行洗涤和压绉，得到厚度为2～3mm的胶片，再用撕粒机进行造粒，得到粒径为2～5mm的胶粒，胶粒滴水后，在115℃的热风干燥箱内干燥3.5h，得到低蛋白天然橡胶。
实施例3
取新鲜天然橡胶胶乳100kg，测得干胶含量为30.0wt％；将所述新鲜天然橡胶胶乳与浓度为25wt％的氨水0.4kg、浓度为10wt％的十二烷基硫酸钠水溶液0.5kg和2709碱性蛋白酶60g混合，在35℃条件下反应10h，得到脱蛋白天然胶乳；
将100g防老剂264和6g扩散剂NF置于搪瓷杯内，加入80mL浓度为10wt％的酪素溶液(溶剂为水)、去离子水64mL以及堆积体积为200mL的玻璃砂(粒度为2～3mm)，搅和后加盖并利用具不锈钢搅拌浆的电动搅拌机搅拌12h(搅拌速度为1500rpm)，之后用筛网滤去玻璃砂，得到稳定的防老剂264分散体；
将所述脱蛋白天然胶乳与150g所述防老剂264分散体混合，得到混合物料；
将所述混合物料与甲酸混合进行凝固，得到凝块；所述甲酸的质量为所述混合物料质量的2％；
所述凝块用清水经绉片机进行洗涤和压绉，得到厚度为2～3mm的胶片，再用撕粒机进行造粒，得到粒径为2～5mm的胶粒，胶粒滴水后，在115℃的热风干燥箱内干燥3h，得到低蛋白天然橡胶。
对比例1
取新鲜天然橡胶胶乳100kg，测得干胶含量为30.0wt％；将所述新鲜天然橡胶胶乳与浓度为25wt％的氨水0.4kg、浓度为10wt％的十二烷基硫酸钠水溶液0.5kg和木瓜蛋白酶60g混合，在35℃条件下反应10h，得到脱蛋白天然胶乳；
将所述脱蛋白天然胶乳与甲酸混合进行凝固，得到凝块；所述甲酸的质量为所述脱蛋白天然胶乳质量的2％；
所述凝块用清水经绉片机进行洗涤和压绉，再用撕粒机进行造粒，胶粒滴水后，在115℃的热风干燥箱内干燥8h，得到低蛋白天然橡胶。
性能测试：
对实施例1～3以及对比例1制备的低蛋白天然橡胶进行性能测试，其中，干燥情况、灰分、挥发分、氮含量、杂质、塑性初值和塑性保持率的测试样品为生胶，即实施例1～3以及对比例1制备的低蛋白天然橡胶；拉伸强度和拉伸强度保持率的测试样品为所述生胶经硫化处理后所得硫化胶，所述硫化胶采用ACS1配方。测试结果具体见表1。
表1 实施例1～3以及对比例1制备的低蛋白天然橡胶性能测试结果
Figure PCTCN2020139735-appb-000001
由表1可知，采用本发明提供的方法能够防止胶料发粘、夹生；与对比例1相比，采用本发明提供的方法制备的低蛋白天然橡胶具有更优异的性能，塑性保持率(PRI)至少提高了20％，拉伸强度至少提高了15％，老化后拉伸强度保持率至少提高了25％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (15)

  1. 一种低蛋白天然橡胶的制备方法，包括以下步骤：
    提供含有橡胶防老剂的分散体；
    将脱蛋白天然胶乳与所述含有橡胶防老剂的分散体混合，得到混合物料；
    将所述混合物料依次进行凝固、洗涤、压绉、造粒和干燥，得到低蛋白天然橡胶。
  2. 根据权利要求1所述的制备方法，其特征在于，所述橡胶防老剂为天然防老剂和/或合成防老剂。
  3. 根据权利要求2所述的制备方法，其特征在于，所述天然防老剂为天然酚类防老剂；所述合成防老剂为合成酚类防老剂、合成胺类防老剂和合成杂环类防老剂中的至少一种。
  4. 根据权利要求3所述的制备方法，其特征在于，所述天然酚类防老剂为生育酚和三烯生育酚中的至少一种；
    所述合成酚类防老剂包括抗氧剂1010、防老剂264、防老剂2246和防老剂DOD中的至少一种；
    所述合成胺类防老剂包括防老剂H、防老剂D、防老剂RD、防老剂DNP、防老剂KY-405、防老剂4010和防老剂4010NA中的至少一种；
    所述合成杂环类防老剂包括防老剂DBH和防老剂MB中的至少一种。
  5. 根据权利要求1～4任一项所述的制备方法，其特征在于，按质量份数计，所述含有橡胶防老剂的分散体包括以下组分：
    橡胶防老剂3～50份；
    稳定剂0～5份；
    分散剂0～5份；
    水40～97份。
  6. 根据权利要求5所述的制备方法，其特征在于，所述稳定剂为扩散剂NF、酪素和焦磷酸钠中的至少一种；所述分散剂为油酸铵、月桂酸铵和油酸三乙醇胺中的至少一种。
  7. 根据权利要求6所述的制备方法，其特征在于，所述稳定剂为扩散剂NF和酪素，所述扩散剂NF和酪素的质量比为6：(7～9)。
  8. 根据权利要求1所述的制备方法，其特征在于，所述脱蛋白天然胶乳由天然橡胶胶乳经脱蛋白处理得到，所述天然橡胶胶乳的干胶含量为20～50wt％。
  9. 根据权利要求8所述的制备方法，其特征在于，所述天然橡胶胶乳的质量以干胶计，所述混合物料中橡胶防老剂的质量为天然橡胶胶乳质量的0.01～1％。
  10. 根据权利要求8所述的制备方法，其特征在于，所述脱蛋白处理采用的脱蛋白处理剂包括蛋白酶、十二烷基硫酸钠、尿素、气相二氧化硅和金属氢氧化物中的至少一种。
  11. 根据权利要求10所述的制备方法，其特征在于，所述脱蛋白处理剂为蛋白酶和十二烷基硫酸钠，所述蛋白酶和十二烷基硫酸钠的质量比为(3～9)：5。
  12. 根据权利要求10或11所述的制备方法，其特征在于，所述天然橡胶胶乳的质量以干胶计，天然橡胶胶乳与脱蛋白处理剂的质量比为30：(0.10～0.13)。
  13. 根据权利要求8所述的制备方法，其特征在于，所述脱蛋白处理的温度为30～40℃，时间为8～12h。
  14. 根据权利要求1所述的制备方法，其特征在于，所述干燥的温度为80～130℃，时间为2～10h。
  15. 权利要求1～14任一项所述制备方法制备得到的低蛋白天然橡胶，所述低蛋白天然橡胶中含有橡胶防老剂，所述低蛋白天然橡胶中氮含量≤0.2wt％。
PCT/CN2020/139735 2020-11-13 2020-12-26 低蛋白天然橡胶及其制备方法 WO2022099883A1 (zh)

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