WO2013097317A1 - Method for blending natural latex and silica slurry - Google Patents

Method for blending natural latex and silica slurry Download PDF

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WO2013097317A1
WO2013097317A1 PCT/CN2012/070708 CN2012070708W WO2013097317A1 WO 2013097317 A1 WO2013097317 A1 WO 2013097317A1 CN 2012070708 W CN2012070708 W CN 2012070708W WO 2013097317 A1 WO2013097317 A1 WO 2013097317A1
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natural latex
silica
silica slurry
blending
dry
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PCT/CN2012/070708
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French (fr)
Chinese (zh)
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王永庆
夏洪庆
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确成硅化学股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C08J2307/02—Latex

Definitions

  • the invention belongs to the field of rubber preparation, and in particular relates to a method for blending natural latex and silica slurry.
  • the appearance of precipitated hydrated silica is powder, microbeads and granules, also known as white carbon black. Due to the requirements of energy saving, emission reduction and green environmental protection, more and more white carbon black is used in the tire rubber industry.
  • the use of silica as a filler in a mixture with natural rubber and synthetic rubber can be applied to tires to reduce rolling resistance and improve wet skid performance, thereby reducing fuel consumption and reducing exhaust emissions.
  • the use of white carbon black as a filler in rubber can improve the wear resistance, tear strength and hardness of the product, but the dry white carbon black and dry rubber are poorly mixed and dispersible, and the product has high heat generation and high abrasion.
  • the tear strength is low, the tire rolling resistance is large, and more energy is consumed during the mixing process.
  • the object of the present invention is to provide a natural latex (also known as natural glue, which is a liquid which flows out when rubber tree is tapped. a method of blending with a silica slurry.
  • a natural latex also known as natural glue
  • a method for blending natural latex with a silica slurry is to mix and stir natural latex with a silica slurry under normal temperature and normal pressure, and according to the weight of dry glue of natural latex and dry matter of silica And 1 ⁇ 6 ⁇ Add organic acid and emulsifier separately.
  • silica is precipitated hydrated silica.
  • the organic acid is formic acid (CH 2 O 2 ) or acetic acid (CH 3 COOH);
  • the emulsifier is cetyltrimethylammonium bromide (CTAB) or cetyltrimethyl chloride Ammonium (CTAC).
  • the weight ratio of the dry glue in the natural latex to the dry matter in the silica slurry is 10:3 ⁇ 13.
  • weight of the added organic acid and emulsifier is 1 ⁇ 3 of the sum of the dry gum in the natural latex and the dry matter weight in the silica, respectively.
  • the natural latex has a gel content of 30 to 60% by weight.
  • the silica slurry has a solid content of 15 to 30%, preferably 24 to 25%.
  • the solids content is obtained by dividing the total mass of solids in the slurry by the mass of all components constituting the slurry.
  • the viscosity of the silica slurry is from 100 to 1000 cP (centipoise).
  • the natural latex and the silica slurry are mixed and stirred, and further comprise a curing and drying step.
  • the rubber material obtained by the blending method is the rubber material obtained by the blending method.
  • the process of the invention can make the silica and the natural latex better mix and disperse better, and the obtained rubber material has excellent wear resistance, tear strength and hardness, and can be applied to tire manufacturing and shoe making, etc. related industry.
  • Figure 1 is a flow chart of the process of blending natural latex with silica slurry of the present invention.
  • Test method for wear BS 903: Part A9; Test method for breaking strength: ASTM D 412-1998A Test method for heat generation: ASTM D 623-1999; Test method for tear strength: ISO 34-1.
  • Comparative Example 5kg natural latex (60% by mass) and 5kg of silica (20% solids) , viscosity 200 cP) was added to the reactor with a stirring device, and the mixture was thoroughly stirred to obtain a dry rubber, and the mechanical properties of the obtained rubber product were tested.
  • Example 2 Example 3
  • Example 4 Wear Cm 3 /1.61Km 0.7 0.2 0.25 0.23 0.2 Tear strength MPa 17 27.2 26.7 27.6 26.4 Heat °C twenty two 12 13 11 13 Elongation at break % 649% 743% 729% 749% 735% Tear strength KN/m 55 154 148 154 153
  • the method for blending natural latex and silica slurry disclosed in the present invention is to mix and stir natural latex and silica slurry under normal temperature and normal pressure conditions, and mix with dry silica weight according to the weight of natural latex. Sum of material weight Add organic acids and emulsifiers to 1 ⁇ 6 ⁇ .
  • the process of the invention can better mix the silica and the rubber compound, and has better dispersibility, and the obtained rubber material has excellent wear resistance, tear strength and hardness, and can be applied to tire manufacturing and related industries.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A method for blending natural latex and silica slurry. Under the conditions of normal temperature and normal pressure, the natural latex and the silica slurry are mixed and stirred. An organic acid and an emulsifier are added at a proportion of 1‰ to 6‰ of the sum of the dry weight of the natural latex and the dry weight of the silica respectively during mixing. Through the technology provided by the present invention, the silica and the latex can be mixed better, and the dispersity is better; and the obtained rubber material has excellent wear resistance, tear resistance strength and hardness and can be applied to the tire manufacturing and related industries.

Description

一种 天然乳胶与二氧化硅浆液共混的方法  Method for blending natural latex with silica slurry
技术领域 Technical field
本发明属橡胶制备领域，具体来说涉及天然乳胶和二氧化硅浆液的共混的方法。 The invention belongs to the field of rubber preparation, and in particular relates to a method for blending natural latex and silica slurry.
背景技术 Background technique
沉淀水合二氧化硅外观形态为粉状、微珠、颗粒状，又称白炭黑，由于节能减排与绿色环保的要求，越来越多的白炭黑应用于轮胎橡胶工业。将二氧化硅作为填料与天然胶和合成胶混炼，应用于轮胎可以降低滚动阻力，改善湿滑性能，因而使汽车耗油低、减少废气排放。 The appearance of precipitated hydrated silica is powder, microbeads and granules, also known as white carbon black. Due to the requirements of energy saving, emission reduction and green environmental protection, more and more white carbon black is used in the tire rubber industry. The use of silica as a filler in a mixture with natural rubber and synthetic rubber can be applied to tires to reduce rolling resistance and improve wet skid performance, thereby reducing fuel consumption and reducing exhaust emissions.
白炭黑应用于轮胎中作为橡胶的填充剂可以提高制品的耐磨性、耐撕裂强度和硬度，但是干品白炭黑和干胶混炼分散性差，制品的生热高，磨耗高，撕裂强度低，做出的轮胎滚动阻力大，并且在混炼过程中消耗更多的能源。 The use of white carbon black as a filler in rubber can improve the wear resistance, tear strength and hardness of the product, but the dry white carbon black and dry rubber are poorly mixed and dispersible, and the product has high heat generation and high abrasion. The tear strength is low, the tire rolling resistance is large, and more energy is consumed during the mixing process.
发明内容 Summary of the invention
本发明的目的是提供一种应用于天然乳胶（ 又称 天然胶水，是橡胶树割胶时流出的液体 ）与二氧化硅浆液的共混工艺方法。 The object of the present invention is to provide a natural latex (also known as natural glue, which is a liquid which flows out when rubber tree is tapped. a method of blending with a silica slurry.
本发明目的通过下述技术方案来实现： The object of the present invention is achieved by the following technical solutions:
一种天然乳胶与二氧化硅浆液共混的方法，是在常温常压条件下，将天然乳胶与二氧化硅浆液混合并搅拌，混合时按照天然乳胶的干胶与二氧化硅干物质重量之和的 1~6 ‰分别添加有机酸和乳化剂。 A method for blending natural latex with a silica slurry is to mix and stir natural latex with a silica slurry under normal temperature and normal pressure, and according to the weight of dry glue of natural latex and dry matter of silica And 1~6 有机Add organic acid and emulsifier separately.
其中，所述二氧化硅是沉淀水合二氧化硅。 Wherein the silica is precipitated hydrated silica.
其中，所述有机酸是甲酸 (CH2O2) 或醋酸 (CH3COOH) ；所述乳化剂是十六烷基三甲基溴化铵 (CTAB) 或十六烷基三甲基氯化铵 (CTAC) 。Wherein the organic acid is formic acid (CH 2 O 2 ) or acetic acid (CH 3 COOH); the emulsifier is cetyltrimethylammonium bromide (CTAB) or cetyltrimethyl chloride Ammonium (CTAC).
其中，所述天然乳胶中干胶与二氧化硅浆液中干物质的重量比为 10:3~13 。 Wherein, the weight ratio of the dry glue in the natural latex to the dry matter in the silica slurry is 10:3~13.
其中，所述加入的有机酸和乳化剂重量分别为所述天然乳胶中的干胶和所述二氧化硅中的干物质重量之和的 1~3 ‰。 Wherein the weight of the added organic acid and emulsifier is 1~3 of the sum of the dry gum in the natural latex and the dry matter weight in the silica, respectively. Hey.
其中，所述天然乳胶的含胶量为 30~60% 重量比例。 Wherein, the natural latex has a gel content of 30 to 60% by weight.
其中，所述二氧化硅浆液的含固量为 15~30% ，优选为 24~25% 。 含固量是浆液中固体总质量除以组成浆液的所有组份的质量得到的。 Wherein, the silica slurry has a solid content of 15 to 30%, preferably 24 to 25%. The solids content is obtained by dividing the total mass of solids in the slurry by the mass of all components constituting the slurry.
其中，所述二氧化硅浆液的粘度为 100~1000cP （厘泊）。 Wherein, the viscosity of the silica slurry is from 100 to 1000 cP (centipoise).
其中，所述天然乳胶与二氧化硅浆液搅拌混合后，还包括固化和干燥步骤。 Wherein, the natural latex and the silica slurry are mixed and stirred, and further comprise a curing and drying step.
所述的共混的方法得到的橡胶材料。 The rubber material obtained by the blending method.
本发明的有益效果： The beneficial effects of the invention:
经过本发明工艺能够使二氧化硅与天然乳胶更好的混炼，分散性更好，得到的橡胶材料具有优良的耐磨性、耐撕裂强度和硬度，可应用于轮胎制造及制鞋等相关行业。 The process of the invention can make the silica and the natural latex better mix and disperse better, and the obtained rubber material has excellent wear resistance, tear strength and hardness, and can be applied to tire manufacturing and shoe making, etc. related industry.
附图说明 DRAWINGS
图 1 为本发明天然乳胶与二氧化硅浆液共混的工艺流程图 。 Figure 1 is a flow chart of the process of blending natural latex with silica slurry of the present invention.
具体实施方式 detailed description
以下实施例用于说明本发明，但不用来限制本发明的范围。 The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
磨耗的测试方法： BS 903:Part A9 ；扯断强度的测试方法 ： ASTM D 412-1998A ；生热的测试方法： ASTM D 623-1999 ；撕裂强度的测试方法： ISO 34-1 。 Test method for wear: BS 903: Part A9; Test method for breaking strength: ASTM D 412-1998A Test method for heat generation: ASTM D 623-1999; Test method for tear strength: ISO 34-1.
实施例 1 Example 1
将 10kg 天然乳胶 （含胶量 6 0% 质量比例）和 14.4kg 二氧化硅浆液（含固量为 25% ，粘度 300cP ）加入具有搅拌装置的反应器中，同时 分别加入 28.8g 甲酸 (CH2O2) 和 28.8g 十六烷基三甲基溴化铵 (CTAB, 白色粉末 ) 。充分搅拌均匀后，导入料槽固化，干燥得到干 混胶。干混胶经过混炼，测试所得橡胶产品的机械物理性能。结果见表 1 。10 kg of natural latex (60% by mass of the rubber content) and 14.4 kg of silica slurry (solid content: 25%, viscosity 300 cP) were added to the reactor with a stirring device while adding 28.8 g of formic acid (CH 2 ) O 2 ) and 28.8 g of cetyltrimethylammonium bromide (CTAB, white powder). After fully stirring, the feed trough is solidified and dried to obtain a dry blend. The dry blend is kneaded to test the mechanical and physical properties of the resulting rubber product. The results are shown in Table 1.
实施例 2 Example 2
将 10kg 天然乳胶 （含胶量 30% 质量比例）和 7.2kg 浆型二氧化硅（含固量为 25% ，粘度 400cP ）加入有搅拌装置的反应器中，同时分别加入 14.4g 醋酸 (CH3COOH) 和 14.4g 十六烷基三甲基溴化铵 (CTAB ，白色粉末 ) 。搅拌均匀后导入料槽固化，干燥后得到干 混胶。干混胶经过混炼，测试所得橡胶产品的机械物理性能。结果见表 1.10 kg of natural latex (30% by mass) and 7.2 kg of silica (containing 25% solids and 400 cP viscosity) were added to the reactor with a stirring device while adding 14.4 g of acetic acid (CH 3 ). COOH) and 14.4 g of cetyltrimethylammonium bromide (CTAB, white powder). After stirring evenly, the trough is solidified, and after drying, a dry blend is obtained. The dry blend is kneaded to test the mechanical and physical properties of the resulting rubber product. The results are shown in Table 1.
实施例 3 Example 3
将 10kg 天然乳胶 （含胶量 30% 质量比例）和 8kg 浆型二氧化硅（含固量为 20% ，粘度 200cP ）加入具有搅拌装置的反应器中，同时分别加入 9.2g 甲酸和 9.2g 十六烷基三甲基氯化铵（ CTAC ，白色粉末）。充分搅拌均匀后导入料槽固化，干燥后得到 干混胶。干混胶经过混炼，测试所得橡胶产品的机械物理性能。结果见表 1 。 10kg natural latex (30% by mass) and 8kg of silica (20% solids, viscosity) 200cP) was added to the reactor with a stirring device while adding 9.2 g of formic acid and 9.2 g of cetyltrimethylammonium chloride (CTAC) ,White powder). Stir well and then introduce into the trough to solidify. After drying, dry blend is obtained. The dry blend is kneaded to test the mechanical and physical properties of the resulting rubber product. The results are shown in Table 1.
实施例 4 Example 4
将 5kg 天然乳胶 （含胶量 60% 质量比例）和 5kg 浆型二氧化硅（含固量为 20% ，粘度 200cP ）加入具有搅拌装置的反应器中，同时分别加入 8g 甲酸和 8g 十六烷基三甲基氯化铵（ CTAC ，白色粉末）。充分搅拌均匀后导入料槽固化，干燥得到干 混胶。干混胶经过混炼，测试所得产品的机械物理性能。结果见表 1 。 5kg natural latex (60% by mass) and 5kg of silica (20% solids, viscosity) 200cP) was added to the reactor with a stirring device while adding 8 g of formic acid and 8 g of cetyltrimethylammonium chloride (CTAC) ,White powder). Stir well and then introduce into the trough to solidify and dry to obtain a dry mix. The dry blend is kneaded and tested for mechanical and physical properties of the resulting product. The results are shown in Table 1.
对比例： 将 5kg 天然乳胶（含胶量 60% 质量比例）和 5kg 浆型二氧化硅（含固量为 20% ，粘度 200cP ）加入具有搅拌装置的反应器中，充分搅拌均匀后得到干胶经过混炼，测试所得橡胶产品的机械物理性能。 Comparative Example: 5kg natural latex (60% by mass) and 5kg of silica (20% solids) , viscosity 200 cP) was added to the reactor with a stirring device, and the mixture was thoroughly stirred to obtain a dry rubber, and the mechanical properties of the obtained rubber product were tested.
表 1 ：产品的机械物理性能参数 Table 1: Mechanical physical properties of the product
测试项目 Test items 单位 unit 对比例 Comparative example 实施例 1 Example 1 实施例 2 Example 2 实施例 3 Example 3 实施例 4 Example 4
磨耗 Wear cm3/1.61KmCm 3 /1.61Km 0.7 0.7 0.2 0.2 0.25 0.25 0.23 0.23 0.2 0.2
扯断强度 Tear strength MPa MPa 17 17 27.2 27.2 26.7 26.7 27.6 27.6 26.4 26.4
生热 Heat ℃ °C 22 twenty two 12 12 13 13 11 11 13 13
扯断伸长率 Elongation at break % % 649% 649% 743% 743% 729% 729% 749% 749% 735% 735%
撕裂强度 Tear strength KN/m KN/m 55 55 154 154 148 148 154 154 153 153
工业实用性 Industrial applicability
本发明公开的天然乳胶与二氧化硅浆液共混的方法，是在常温常压条件下，将天然乳胶与二氧化硅浆液混合并搅拌，混合时按照天然乳胶的干胶重量与二氧化硅干物质重量之和的 1~6 ‰添加有机酸和乳化剂。 The method for blending natural latex and silica slurry disclosed in the present invention is to mix and stir natural latex and silica slurry under normal temperature and normal pressure conditions, and mix with dry silica weight according to the weight of natural latex. Sum of material weight Add organic acids and emulsifiers to 1~6 ‰.
本发明工艺能够使二氧化硅与胶料更好的混炼，分散性更好，得到的橡胶材料具有优良的耐磨性、耐撕裂强度和硬度，可应用于轮胎制造及相关行业。 The process of the invention can better mix the silica and the rubber compound, and has better dispersibility, and the obtained rubber material has excellent wear resistance, tear strength and hardness, and can be applied to tire manufacturing and related industries.

Claims (1)

1、一种天然乳胶与二氧化硅浆液共混的方法，是在常温常压条件下，将天然乳胶与二氧化硅浆液混合并搅拌，混合时按照天然乳胶的干胶重量与二氧化硅干物质重量之和的1~6‰分别添加有机酸和乳化剂。1. A method for blending natural latex with silica slurry, which is to mix and stir natural latex and silica slurry under normal temperature and pressure conditions, and mix with dry silica weight according to the weight of natural latex. The organic acid and emulsifier are added separately from 1 to 6 ‰ of the sum of the weights of the substances.
2、如权利要求1所述的天然乳胶与二氧化硅浆液共混的方法，其特征在于，所述二氧化硅是沉淀水合二氧化硅。2. A method of blending natural latex with a silica slurry according to claim 1 wherein said silica is precipitated hydrated silica.
3、如权利要求1所述的共混的方法，其特征在于，所述有机酸是甲酸或醋酸；所述乳化剂是十六烷基三甲基溴化铵或十六烷基三甲基氯化铵。3. The method of blending according to claim 1, wherein the organic acid is formic acid or acetic acid; and the emulsifier is cetyltrimethylammonium bromide or cetyltrimethyl Ammonium chloride.
4、如权利要求1~3任一所述的共混的方法，其特征在于，所述天然乳胶中干胶与二氧化硅浆液中干物质的重量比为10:3~13。The method of blending according to any one of claims 1 to 3, wherein the weight ratio of the dry glue in the natural latex to the dry matter in the silica slurry is 10:3 to 13.
5、如权利要求1~3任一所述的共混的方法，其特征在于，所述加入的有机酸和乳化剂重量分别为所述天然乳胶中的干胶和所述二氧化硅中的干物质重量之和的1~3‰。The method of blending according to any one of claims 1 to 3, wherein the added organic acid and the emulsifier are respectively the dry gum in the natural latex and the silica. The sum of the dry matter weights is 1~3‰.
6、如权利要求1~3任一所述的共混的方法，其特征在于，所述天然乳胶的含胶量为30~60%重量比例。The method of blending according to any one of claims 1 to 3, wherein the natural latex has a gel content of 30 to 60% by weight.
7、如权利要求1~3任一所述的共混的方法，其特征在于，所述二氧化硅浆液的含固量为15~30%，The method of blending according to any one of claims 1 to 3, wherein the silica slurry has a solid content of 15 to 30%.
8、如权利要求7所述的共混的方法，其特征在于，所述二氧化硅浆液的含固量为20~25%。8. The method of blending according to claim 7, wherein the silica slurry has a solid content of 20 to 25%.
9、如权利要求1~3任一所述的共混的方法，其特征在于，所述二氧化硅浆液的粘度为100~1000cP。The method of blending according to any one of claims 1 to 3, wherein the silica slurry has a viscosity of from 100 to 1000 cP.
10、如权利要求1所述的共混的方法，其特征在于，还包括将所述天然乳胶与二氧化硅浆液搅拌混合后，导入料槽中固化，固化之后干燥。10. The method of blending according to claim 1, further comprising the step of mixing the natural latex with the silica slurry, solidifying in an introduction trough, and drying after solidification.
11、权利要求1~10所述的共混的方法得到的橡胶材料。  11. A rubber material obtained by the method of blending according to claims 1 to 10.
PCT/CN2012/070708 2011-12-27 2012-01-21 Method for blending natural latex and silica slurry WO2013097317A1 (en)

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WO2013097317A1 (en) * 2011-12-27 2013-07-04 确成硅化学股份有限公司 Method for blending natural latex and silica slurry
CN104893024B (en) * 2015-06-29 2016-09-14 确成硅化学股份有限公司 The method that natural emulsion is blended with precipitated silica
CN105419008A (en) * 2015-12-28 2016-03-23 宁波卡利特新材料有限公司 Method for obtaining rubber master batch product by adding rubber reinforcing agent through wet coprecipitation
CN108503906B (en) * 2018-06-29 2024-05-14 海南省先进天然橡胶复合材料工程研究中心有限公司 Efficient blending method of nanoclay rubber

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