WO2020037831A1 - 一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法 - Google Patents

一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法 Download PDF

Info

Publication number
WO2020037831A1
WO2020037831A1 PCT/CN2018/113797 CN2018113797W WO2020037831A1 WO 2020037831 A1 WO2020037831 A1 WO 2020037831A1 CN 2018113797 W CN2018113797 W CN 2018113797W WO 2020037831 A1 WO2020037831 A1 WO 2020037831A1
Authority
WO
WIPO (PCT)
Prior art keywords
hexane
bis
dibenzothiazolecarbamoyl
disulfide
reaction
Prior art date
Application number
PCT/CN2018/113797
Other languages
English (en)
French (fr)
Inventor
彭华龙
潘胜节
王莹莹
姚翔
房建明
Original Assignee
江苏麒祥高新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏麒祥高新材料有限公司 filed Critical 江苏麒祥高新材料有限公司
Publication of WO2020037831A1 publication Critical patent/WO2020037831A1/zh

Links

Images

Classifications

    • 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
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/30—Dithiocarbamic acids; Derivatives thereof having sulfur atoms of dithiocarbamic groups bound to other sulfur atoms

Definitions

  • the invention relates to the field of synthetic technology of rubber processing aids, in particular to a new method for synthesizing anti-vulcanization reversion agent for rubber.
  • This invention claims the priority of China's prior invention patent application with application number CN2018109624028, with a filing date of August 22, 2018.
  • 1,6-bis (N, N , -dibenzothiazolecarbamoyl disulfide) -hexane is a new type of high-efficiency composite anti-reversion agent. Its anti-reversion mechanism: during the vulcanization process of rubber The sulfur-sulfur bond in the molecular structure is broken, and the C6 fatty chain in the middle together with the sulfur atoms at both ends is connected to the rubber molecule. The carbon-carbon bond energy in the C6 fatty chain is greater than the sulfur-sulfur bond formed by sulfur vulcanization, thereby forming The more stable vulcanization cross-linking network makes the vulcanizate not to undergo vulcanization reversion during production and use, and maintains good mechanical and dynamic properties.
  • a method for preparing a dithiol derivative is reported in the patent CN 100522941C, which uses hexamethylene-1,6-bisthiosulfate disodium salt and sodium dibenzyl dithiocarbamate as raw materials, and uses water / Toluene was used as the reaction solvent.
  • the pH value of the reaction system was adjusted by adding sodium bicarbonate.
  • the product was obtained by post-processing units such as extraction, reduced pressure concentration, and crystallization.
  • the preparation method has the following disadvantages: 1) Low mass transfer efficiency in water / toluene in a homogeneous system, resulting in slower reaction rates, longer industrial production cycles, and lower industrial industrial production capacity; 2) a large amount of alkaline wastewater (containing a small amount of organic solvent toluene), its chemical oxygen The higher the amount of COD, the higher the cost of biochemical treatment.
  • Chinese patent CN105503677B discloses a method for preparing an environmentally friendly, highly efficient sulfurized cross-linking agent 1,6-bis (N, N-dibenzylcarbamoyldisulfide) hexane: firstly synthesize sodium dibenzyldithiocarbamate Alcohol solution, then heated under reflux with 1,6-dichlorohexane, washed with suction, filtered and washed with water to obtain intermediate 1,6-bis (N, N-dibenzylcarbamoyl monosulfide) hexane.
  • the present invention provides an anti-vulcanization reversion agent for rubber of 40-100 ⁇ m and a new method for synthesizing the same.
  • the method is an anti-vulcanization reversion agent 1,6-bis (N, N , -Dibenzothiazole carbamoyl disulfide) -Hexane is a new method for the industrialized synthesis of hexane.
  • the process is simple and easy, the operation is simple, the solvent can be recycled and applied, and the industrialization cost is low.
  • the prepared rubber anti-reversion agent has a large particle size. And the particle size distribution is narrow, and it has good processing performance, which can effectively reduce dust flying in the subsequent rubber processing.
  • an anti-vulcanization reversion agent for rubber 1,6-bis (N, N , -dibenzothiazolecarbamoyl disulfide) -hexane, of which at least 90% The particle size is 40-100 ⁇ m;
  • a new method for synthesizing anti-vulcanization reversion agent for rubber is also provided, which is characterized by including the following steps:
  • Dibenzylamine, carbon disulfide, sodium hydroxide solution, 1,6-dichlorohexane were used as raw materials, and a phase transfer catalyst was used as a catalyst.
  • the reaction mixture was added to a reaction kettle containing water or a mother liquor. After the reaction was completed, the mixture was centrifuged, washed, and filtered. The cake was dried to obtain 1,6-bis (N, N , -dibenzothiazolecarbamoyl monosulfide) -hexane, and the mother liquor A was washed and collected for reuse;
  • step (2) Into the initial 1,6-bis (N, N , -dibenzothiazolecarbamoyl disulfide) -hexane prepared in step (2), put ethyl acetate, heat and dissolve, cool down to less than At 10 ° C, the powder was centrifuged to obtain a white powder, and mother liquor B was collected and reused. Then, the white powder was dried, sprayed with oil, crushed, and packaged to obtain a finished product.
  • step (2) Into 1,6-bis (N, N , -dibenzothiazolecarbamoyl monosulfide) -hexane prepared in step (1), add sulfur and an organic solvent in this order at a temperature of 80-100 ° C. The reaction is carried out for 6-8 hours. After the reaction is completed, the organic solvent is distilled off under reduced pressure to obtain a 1,6-bis (N, N , -dibenzothiazolecarbamoyl disulfide) -hexane initial product.
  • step (3) Into the 1,6-bis (N, N , -dibenzothiazolecarbamoyl disulfide) -hexane prepared in step (2), put ethyl acetate, heat and dissolve under reflux for 30 minutes, and cool down to When the temperature is lower than 10 °C, the powder is centrifuged to obtain a white powder product. The mother liquor B is collected and reused.
  • step (3) Dry and inject the product obtained in the above step (3) (the specific injection process is: pumping into the 2000L vacuum double cone rotary dryer 300 kg of dried 1,6-double (N, N, -II) Benzothiazole carbamoyl disulfide) -hexane was rotated and mixed, and the temperature started to rise. When the temperature of the rotary dryer kettle rose to 45-50 ° C, the fuel injection valve was opened, and 25 kg of white oil was injected into the rotary dryer.
  • the specific injection process is: pumping into the 2000L vacuum double cone rotary dryer 300 kg of dried 1,6-double (N, N, -II) Benzothiazole carbamoyl disulfide) -hexane was rotated and mixed, and the temperature started to rise.
  • the fuel injection valve was opened, and 25 kg of white oil was injected into the rotary dryer.
  • the temperature of the fuel injection is increased to 62-65 °C, and 1,6-bis (N, N, -dibenzothiazolecarbamoyl disulfide) -hexane oil-filled product is obtained after discharging, crushing, Packaging to obtain a finished anti-vulcanization reversion agent 1,6-bis (N, N, -dibenzothiazolecarbamoyl disulfide) -hexane.
  • the mixing process is: 100 parts of natural rubber, 25 parts of N234 carbon black, 4.4 parts of zinc oxide, 2 parts of SA stearic acid, 1.5 parts of 4020 antioxidant, 1 part of 9332F rubber protective wax.
  • N234 carbon black 25 parts were added to the mixer in order to mix 260S, cleaned, drained, put the rubber compound in the mixer for 5min, and then cooled naturally in the air for 4h to obtain the masterbatch; two-stage mixing
  • the process conditions are (roller temperature 60 °C, stick rotation speed 40rpm), and the mixing process is as follows: a section of master batch, 0.6 part of sulfur yellow, 1 part of accelerator and 1.5 parts of 1,6-bis (N, N , -Dibenzothiazole carbamoyl disulfide) -hexane was sequentially added to the internal mixer and kneaded for 100S, and then discharged to obtain the final rubber, which was rolled and rolled on an open mixer for 5 times, and then cut into pieces.
  • the weight ratio of carbon disulfide, 1,6-dichlorohexane, sodium hydroxide solution, dibenzylamine, and solvent water in step (1) is 1: (0.8-2.0): (1.0-2.0): (1.0- 3.0): (10-15), preferably 1: (1-1.5): (1.0-1.5): (1.0-2.5): (12-15), further preferably 1: (1-1.2): (1.2- 1.5): (1.2-2.3): (12.5-13.5).
  • step (1) the preferred temperature for dropping carbon disulfide is 3-5 ° C
  • the preferred temperature for dropping sodium hydroxide aqueous solution is 8-10 ° C
  • the preferred temperature for dropping 1,6-dichlorohexane is 3-5 ° C.
  • phase transfer catalyst used in step (1) is tetrabutylammonium bromide or triethylbenzyl ammonium chloride, and the preferred amount of the catalyst is 6-8% of the mass of dibenzylamine.
  • the preferred reaction time in step (1) is 3-6 h after the completion of the dropwise addition of 1,6-dichlorohexane.
  • the preferred organic solvent in step (2) is toluene, xylene or chlorobenzene.
  • the preferred molar ratio of 1,6-bis (N, N , -dibenzylcarbamoyl-thio) hexane to sulfur in step (2) is 1: (2.0-2.5), 1,6-bis (N
  • the mass ratio of N , -dibenzothiazolecarbamoyl monosulfide) -hexane to the organic solvent is 1: (2-5).
  • step (3) the mass ratio of 1,6-bis (N, N , -dibenzothiazolecarbamoyl disulfide) -hexane to ethyl acetate is 1: (1.0-2.0), preferably 1 :( 1.5-2.0).
  • the synthetic route of the present invention is as follows:
  • the mother liquor can be recycled and applied without generating waste water, which is green, environmentally friendly and economical.
  • the synthesis method uses a crystallization process to make the obtained product high in purity and wide in application value.
  • the product obtained by this synthesis method has a narrow particle size distribution and a large particle size.
  • the material has good fluidity during the processing of the downstream rubber compound, and the dust concentration is lower in the actual processing and production process, which reduces the degree of occupational disease.
  • FIG. 1 is a flow chart of a production process of the present invention.
  • the sedimentation medium is deionized water, and the dispersant is an aqueous solution of sodium hexametaphosphate.
  • a new method for synthesizing anti-vulcanization reversion agent for rubber the preparation steps are as follows:
  • step (3) To the 1,6-bis (N, N , -dibenzothiazolecarbamoyldisulfide) -hexane prepared in step (2), put 760 kg of ethyl acetate, heat and dissolve for 30 min, and cool The temperature was lowered to less than 10 ° C, and the powder was centrifuged to obtain a white powder product. The mother liquor B was collected and reused.
  • the obtained filter cake product is dried under vacuum double cone at 70 ° C for 5 hours, and the fuel is sprayed (the specific fuel injection process is: pump the dried 300kg 1,6-double (N, N into a 2000L vacuum double cone rotary dryer) , -Dibenzothiazole carbamoyl disulfide) -hexane rotation mixing, began to heat up, when the temperature of the rotary dryer kettle rose to 46 °C, open the fuel injection valve to spray 25kg of white oil into the rotary dryer, injection time After 25 minutes, the temperature of the fuel injection was increased to 63 ° C.
  • the specific fuel injection process is: pump the dried 300kg 1,6-double (N, N into a 2000L vacuum double cone rotary dryer) , -Dibenzothiazole carbamoyl disulfide) -hexane rotation mixing, began to heat up, when the temperature of the rotary dryer kettle rose to 46 °C, open the fuel injection valve to spray 25kg of white oil into the rotary dryer, injection
  • the above-mentioned synthetic anti-vulcanization reversion agent 1,6-bis (N, N , -dibenzothiazolecarbamyl disulfide) was measured by JC-1000 handheld intelligent dust detector. ) -Dust concentration on site during the hexane feed into the mixer was 88.5 mg / m 3 .
  • Example 2 In Examples 2, 3, and 4, the steps of Example 1 were repeated, except that the reaction time in step (1) was 4, 5, and 6 hours, respectively.
  • the analysis results are shown in Table 1.
  • Example 1 The steps of Example 1 were repeated, except that the catalyst used in step (1) was 19 kg of triethylbenzyl ammonium chloride, and the final yield was 92.3%. After analysis, the content of the product was 98.2%, and the melting point was 91.5 ° C. The ash content is 0.03%, the oil content is 6.7%, the particle size d (90) is 72.33 ⁇ m, and the on-site dust concentration is 85.1 mg / m 3 .
  • the catalyst used in step (1) was 19 kg of triethylbenzyl ammonium chloride, and the final yield was 92.3%. After analysis, the content of the product was 98.2%, and the melting point was 91.5 ° C. The ash content is 0.03%, the oil content is 6.7%, the particle size d (90) is 72.33 ⁇ m, and the on-site dust concentration is 85.1 mg / m 3 .
  • Example 1 The procedure of Example 1 was repeated, except that the solvent in step (2) was 1000 kg of chlorobenzene, and the final yield was 91.3%. After testing, the product content was 98.2%, the melting point was 92.0 ° C, the ash content was 0.07%, and the oil content was The amount is 6.5%, the particle diameter d (90) is 71.33 ⁇ m, and the on-site dust concentration is 86.1 mg / m 3 .
  • Example 2 The 2292 kg of the filtrate recovered by centrifugation in step (1) in Example 1 was directly reused as a solvent. The other steps were the same as those in Example 1.
  • the obtained product was calculated to obtain a total yield of 90.7%, and the content of the product was 96.1%.
  • the melting point was 91.2 ° C.
  • the ash content is 0.04%, the oil content is 6.9%, the particle size d (90) is 58.13 ⁇ m, and the on-site dust concentration is 89.1 mg / m 3 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成方法，其合成步骤包括：首先采用绿色合成工艺水溶剂法在相转移催化剂的作用下室温合成中间体1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷，得到的中间体与硫磺反应得到初品1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷，初品经重结晶提纯工艺得到1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷纯品。所述合成方法溶剂可以回收套用，不产生废水，环保经济，反应时间短，产品纯度高，生产效率高，合成工艺简单，能耗低；制备橡胶用抗硫化返原剂产品粒度大且粒径分布窄，具有良好的加工性能。

Description

一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法 技术领域
本发明涉及橡胶加工助剂合成工艺领域，具体地说是一种橡胶用抗硫化返原剂的合成新方法。本发明要求申请号CN2018109624028，申请日2018年8月22日专利的中国在先发明专利申请的优先权。
背景技术
1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷是一种新型高效复合抗硫化返原剂，其抗硫化返原机理：在胶料硫化过程中其分子结构中硫硫键断裂，中间的C6脂肪链连同其两端的硫原子一起连接到橡胶分子中，C6脂肪链中碳碳键的键能大于硫磺硫化形成的硫硫键的键能，从而形成更稳定的硫化交联网络，使得硫化胶在生产过程和使用过程中不会发生硫化返原现象，保持较好的力学性能和动态性能。
在专利CN 100522941C中报道了双硫醇衍生物的制备方法，该专利采用六亚甲基-1,6-双硫代硫酸二钠盐和二苄基二硫代氨基甲酸钠为原料，以水/甲苯做为反应溶剂，通过投入碳酸氢钠来调节反应体系的PH值，合成反应完毕后经萃取、减压浓缩、结晶等后处理单元操作得到产品，该制备方法存在以下缺点：1)在非均相体系水/甲苯中传质效率较低，导致反应速率较慢，工业生产周期较长，产品工业化产能较低；2)产生大量碱性废水(含少量有机溶剂甲苯)，其化学需氧量COD较高，即生化处理成本较高。
中国专利CN105503677B公开了一种环保、高效硫化交联剂1,6-二(N,N-二苄基氨基甲酰二硫)己烷的制备方法：首先合成二苄基二硫代氨基甲酸钠的醇溶液，然后与1,6-二氯己烷加热回流反应，经抽滤水洗得到中间体1,6-二(N,N-二苄基氨基甲酰一硫)己烷，该中间体再与硫磺加热反应生成产品抗硫化返原剂1,6-二(N,N-二苄基氨基甲酰二硫)己烷。此合成方法采用了有毒的挥发性溶剂甲醇，并且产生大量废水，污染环境，而且回流反应能耗较高。
发明内容
为了克服上述现有技术的不足，本发明提供了一种40-100μm的橡胶用抗硫化返原剂及其合成新方法，该方法为抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷的工业化合成新方法，其工艺简单易行、操作简便、溶剂可 以回收套用且工业化成本低；制备的橡胶用抗硫化返原剂产品粒度大且粒径分布窄，具有良好的加工性能，在后续胶料加工中能有效地减少粉尘飞扬。
在本发明的一个实施方案中，提供了一种橡胶用抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷，其中至少90％的颗粒粒径为40-100μm；
在本发明另一个实施方案中还提供一种橡胶用抗硫化返原剂的合成新方法，其特征在于包含以下步骤：
(1)1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷中间体的合成
以二苄胺、二硫化碳、氢氧化钠溶液、1，6-二氯己烷为原料，相转移催化剂为催化剂，加入到含有水或者套用母液的反应釜中，反应完成后，离心、水洗、滤饼烘干后得到1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷，水洗母液A收集回用；
(2)1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品的合成
向步骤(1)合成的1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷中，依次投入硫磺和有机溶剂，进行反应，反应结束后，减压蒸馏脱除有机溶剂，得到1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品；
(3)1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷的提纯
向步骤(2)中制得的1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品中，投入乙酸乙酯，加热溶解，冷却降温至低于10℃，放料离心分离得到白色粉末，母液B收集回用；接着将所述白色粉末，干燥，喷油，粉碎，包装即得成品。
进一步地，提供了一种橡胶用抗硫化返原剂的合成新方法，包括以下步骤：
(1)先将溶剂水或者套用母液投入反应釜，然后依次投入二苄胺与相转移催化剂，冷却降温至0-5℃，开始滴加二硫化碳，1-2h滴加完毕，继续滴加32％的氢氧化钠水溶液，滴加温度不超过10℃，滴加完毕紧接着缓慢滴加1,6-二氯己烷，滴加温度0-5℃，滴加完毕室温下搅拌反应2.5-6h，反应完毕后，离心，水洗，母液A收集回用，滤饼烘干后得到1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷；
(2)向步骤(1)制得的1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷中，依次投入硫磺与有机溶剂，在温度80-100℃下反应6-8h，反应结束后，减压蒸 馏脱除有机溶剂，得到1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品；
(3)向步骤(2)制得的1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷中，投入乙酸乙酯，加热溶解回流30min，冷却降温至低于10℃，放料离心分离得到白色粉末产品，母液B收集回用；
(4)将上述步骤(3)得到的产品干燥、喷油(具体的喷油流程为：向2000L真空双锥回转干燥机中抽入已干燥的300kg1,6-双(N,N,-二苯并噻唑氨基甲酰二硫)-己烷旋转混合，开始升温，当回转干燥机釜温升至45-50℃，开启喷油阀向回转干燥机中喷入25kg白油，喷油时间不少于20min，喷油结束继续升温至62-65℃，放料即得1,6-双(N,N,-二苯并噻唑氨基甲酰二硫)-己烷充油产品)、粉碎、包装，得到成品抗硫化返原剂1,6-双(N,N,-二苯并噻唑氨基甲酰二硫)-己烷。
抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷后续炼胶两段加工工艺：一段混炼工艺的条件为(辊温80℃，棍子转速60rpm)，混炼工艺为：将称量好的100份天然胶，25份N234炭黑，4.4份氧化锌，2份SA硬脂酸，1.5份4020防老剂，1份9332F橡胶防护蜡，25份N234炭黑依次加入密炼机中混炼260S，清扫，排胶，将胶料放入开炼机混炼5min后置于空气中自然冷却4h，得到母炼胶；二段混炼工艺条件为(辊温60℃，棍子转速40rpm)，混炼工艺为：将一段母炼胶、称量好的0.6份硫黄、1份促进剂及1.5份1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷依次加入密炼机中混炼100S后排胶得到终炼胶，将其在开炼机上包辊翻炼5次后割胶出片。
其中，步骤(1)中二硫化碳、1,6-二氯己烷、氢氧化钠溶液、二苄胺、溶剂水的重量比为1：(0.8-2.0)：(1.0-2.0)：(1.0-3.0)：(10-15)，优选为1：(1-1.5)：(1.0-1.5)：(1.0-2.5)：(12-15)，进一步优选1：(1-1.2)：(1.2-1.5)：(1.2-2.3)：(12.5-13.5)。
步骤(1)中优选的滴加二硫化碳温度为3-5℃，优选的滴加氢氧化钠水溶液温度为8-10℃，优选的滴加1,6-二氯己烷温度3-5℃。
步骤(1)中所用相转移催化剂为四丁基溴化铵或氯化三乙基苄铵，优选催化剂的用量为二苄胺质量的6-8％。
步骤(1)中优选的1,6-二氯己烷滴加完毕后反应时间3-6h。
步骤(2)中优选的有机溶剂为甲苯、二甲苯或氯苯。
步骤(2)中优选的1，6-二(N,N ,-二苄基氨基甲酰一硫)己烷与硫磺的摩尔比为1：(2.0-2.5)，1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷与有机溶剂的质量比为1：(2-5)。
步骤(3)中1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷与乙酸乙酯的质量比为1：(1.0-2.0)，优选为1：(1.5-2.0)。
具体地，本发明的合成路线如下：
步骤(1)合成途径
Figure PCTCN2018113797-appb-000001
步骤(2)合成途径
Figure PCTCN2018113797-appb-000002
与现有技术相比，本发明的有益效果如下：
1)反应结束后母液可以回收套用，不产生废水，绿色、环保、经济。
2)中间体1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷的合成工艺采用水为溶剂，绿色环保，配合使用相转移催化剂，相转移催化剂可以提高油/水两相传质效率，加快反应速率，提高产率。
3)中间体1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷的合成反应在室温下进行，所需能量消耗较低，操作简便易行。
4)该合成方法采用了结晶工艺，使得到的产品纯度高，其应用价值广。
5)该合成方法得到的产品粒径分布窄且粒度大，物料在下游胶料的加工过程中具有良好的流动性，且在实际加工生产过程中粉尘浓度较低，降低了职业病的危害程度。
附图说明
图1为本发明的生产工艺流程图。
具体实施方式
下面结合具体实施例对本发明做进一步阐述，但本发明所保护范围不限于此，其他从本发明内容中直接导出或联想到的所有变形，均应认为是本发明的保护范围。
本文所述抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷的粒径用BT-9300S激光粒度分布仪通过米氏散射原理进行粒度分布测量所得。沉降介质为去离子水，分散剂为六偏磷酸钠的水溶液。
实施例1
一种橡胶用抗硫化返原剂的合成新方法，其制备步骤如下：
(1)向5000L反应釜中依次投入1670kg去离子水、315.2kg二苄胺与19kg催化剂四丁基溴化铵，通冷冻盐水冷却搅拌降温至5℃，通过高位槽向反应釜中缓慢滴加133.6kg二硫化碳，滴加温度不超过5℃，2h内滴加完毕后，继续滴加32％氢氧化钠溶液199kg，滴加温度不超过10℃，滴加完毕紧接着向上述反应釜中缓慢滴加125kg 1,6-二氯己烷，滴加温度不超过5℃，滴加完毕室温下搅拌3h，反应完毕后，离心、水洗、滤饼干燥后得到中间体1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷，母液A收集回用。
(2)向上述反应釜中依次投入上述步骤(1)制得的1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷、52kg硫磺和1000kg甲苯溶剂，在80℃下反应6h后，减压蒸馏脱除甲苯，得到1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品，馏分收集回用。
(3)向步骤(2)制得的1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品中，投入760kg乙酸乙酯，加热溶解30min，冷却降温至低于10℃，放料离心分离得到白色粉末产品，母液B收集回用。
(4)得到的滤饼产品70℃下真空双锥干燥5h，喷油(具体的喷油流程为：向2000L真空双锥回转干燥机中抽入已干燥的300kg1,6-双(N,N,-二苯并噻唑氨基甲酰二硫)-己烷旋转混合，开始升温，当回转干燥机釜温升至46℃，开启喷油阀向回转干燥机中喷入25kg白油，喷油时间25min，喷油结束继续升温至63℃，放料即得1,6-双(N,N,-二苯并噻唑氨基甲酰二硫)-己烷充油产品)、粉碎、包装， 得到成品抗硫化返原剂1,6-双(N,N,-二苯并噻唑氨基甲酰二硫)-己烷，计算可得总产率91.3％，经检测分析产品含量98.8％，熔点91.7℃，灰分0.05％，含油量7.2％，粒径d(90)59.26μm。
在下游终炼胶加工工艺过程中，通过JC-1000手持式智能粉尘检测仪测得上述合成的抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷投入密炼机的过程中现场粉尘浓度为88.5mg/m 3。
实施例2、3、4，重复实施例1的步骤，不同之处在于：步骤(1)反应时间分别为4、5、6h。分析结果见表1。
表1步骤(1)不同反应时间的实施例
Figure PCTCN2018113797-appb-000003
实施例5
重复实施例1的步骤，不同之处在于：步骤(1)所用催化剂为19kg氯化三乙基苄铵，最终计算可得总产率92.3％，经检测分析产品含量98.2％，熔点91.5℃，灰分0.03％，含油量6.7％，粒径d(90)72.33μm，现场粉尘浓度为85.1mg/m 3。
实施例6
重复实施例1的步骤，不同之处在于：步骤(2)中溶剂为1000kg氯苯，最终计算可得总产率91.3％，经检测分析产品含量98.2％，熔点92.0℃，灰分0.07％， 含油量6.5％，粒径d(90)71.33μm，现场粉尘浓度为86.1mg/m 3。
实施例7
将实施例1中步骤(1)离心回收滤液2292kg直接回用当溶剂，其他步骤同实施例1，得到的产品经计算可得总产率90.7％，经检测分析产品含量96.1％，熔点91.2℃，灰分0.04％，含油量6.9％，粒径d(90)58.13μm，现场粉尘浓度为89.1mg/m 3。
对照实例：
按照专利CN100522941C双硫醇衍生物的制备方法的实例完成了一组验证实验，得到的1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷粒径d(90)12.99μm，通过JC-1000手持式智能粉尘检测仪测得1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷投入密炼机的过程现场粉尘浓度为150.2mg/m 3。

Claims (11)

  1. 一种橡胶用抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷，其中至少90％的颗粒粒径为40-100μm。
  2. 权利要求1所述橡胶用抗硫化返原剂的合成新方法，其特征在于包含以下步骤：
    (1)1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷中间体的合成
    以二苄胺、二硫化碳、氢氧化钠溶液、1，6-二氯己烷为原料，相转移催化剂为催化剂，加入到水或者套用母液的反应釜中，反应完成后，离心，水洗，滤饼烘干后得到1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷，水洗母液A收集回用；
    (2)1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品的合成
    向步骤(1)合成的1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷中，依次投入硫磺和有机溶剂，进行反应，反应结束后，减压蒸馏脱除有机溶剂，得到1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品；
    (3)1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷的提纯
    向步骤(2)中制得的1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷初品中，投入乙酸乙酯，加热溶解，冷却降温至低于10℃，放料离心分离得到白色粉末，母液B收集回用；接着将所述白色粉末，干燥，喷油，粉碎，包装即得成品。
  3. 根据权利要求2任一项所述的方法，其特征在于：所述二硫化碳、1,6-二氯己烷、氢氧化钠溶液、二苄胺、溶剂水的重量比为1：(0.8-2.0)：(1.0-2.0)：(1.0-3.0)：(10-15)。
  4. 根据权利要求2-3任一项所述的方法，其特征在于：步骤(2)中1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷与硫磺的摩尔比为1：(2.0-2.5)，1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷与有机溶剂的质量比为1：(2-5)。
  5. 根据权利要求2-4任一项所述的方法，其特征在于：步骤(3)中1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷与乙酸乙酯的质量比为1：(1.0-2.0)
  6. 根据权利要求2-5任一项所述方法，其特征在于：步骤(1)具体制备步骤为：
    先将溶剂水或者套用母液投入反应釜，然后依次投入二苄胺与相转移催化剂，冷却降温至0-5℃，开始滴加二硫化碳，1-2h滴加完毕，继续滴加32％的氢氧化 钠水溶液，滴加温度不超过10℃，滴加完毕紧接着缓慢滴加1,6-二氯己烷，滴加温度0-5℃，滴加完毕室温下搅拌反应2.5-6h，反应完毕后，离心，水洗，母液A收集回用，滤饼烘干后得到中间体1,6-双(N,N ,-二苯并噻唑氨基甲酰一硫)-己烷。
  7. 根据权利要求2-6任一项所述的方法，其特征在于：所述相转移催化剂为四丁基溴化铵或氯化三乙基苄铵，催化剂的用量为二苄胺质量的6-8％。
  8. 根据权利要求2-7任一项所述的方法，其特征在于：步骤(2)中反应温度为80-100℃，时间为6-8h，所述有机溶剂为甲苯、二甲苯或氯苯。
  9. 根据权利要求2-8任一项所述的方法，其特征在于，步骤(1)中滴加二硫化碳温度为3-5℃，滴加氢氧化钠水溶液温度为8-10℃。
  10. 根据权利要求5-8任一项所述的方法，其特征在于，步骤(1)中1,6-二氯己烷滴加温度3-5℃，滴加完毕后反应时间3-6h。
  11. 权利要求1所述的抗硫化返原剂1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷或权利要求2-10任一项所述的方法制备的1,6-双(N,N ,-二苯并噻唑氨基甲酰二硫)-己烷作为橡胶抗硫化返原剂的应用。
PCT/CN2018/113797 2018-08-22 2018-11-02 一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法 WO2020037831A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810962402.8A CN109233035B (zh) 2018-08-22 2018-08-22 一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法
CN201810962402.8 2018-08-22

Publications (1)

Publication Number Publication Date
WO2020037831A1 true WO2020037831A1 (zh) 2020-02-27

Family

ID=65068769

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/113797 WO2020037831A1 (zh) 2018-08-22 2018-11-02 一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法

Country Status (2)

Country Link
CN (1) CN109233035B (zh)
WO (1) WO2020037831A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3869435A (en) * 1971-11-19 1975-03-04 Monsanto Co Method for cross-linking rubber
CA2289434A1 (en) * 1998-11-16 2000-05-16 Bayer Aktiengesellschaft Vulcanizable rubber compounds containing styrenebutadiene and butadiene rubbers
CN103922982A (zh) * 2014-04-25 2014-07-16 江苏麒祥高新材料有限公司 一种二硫代氨基甲酸类硫化交联剂的制备方法
CN105503677A (zh) * 2015-12-04 2016-04-20 山东阳谷华泰化工股份有限公司 一种环保、高效硫化交联剂1,6-二（n,n-二苄基氨基甲酰二硫）己烷的制备方法
CN108424552A (zh) * 2018-04-08 2018-08-21 贾中将 一种高抗硫化返原性能的橡胶减震器

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1007811B (zh) * 1984-02-16 1990-05-02 国营火药炸药公司 氨基甲酸衍生物制备工艺
EP1600439B1 (de) * 2004-05-26 2016-02-03 LANXESS Deutschland GmbH Herstellung von derivatisierten Dithiolen
JP2012153785A (ja) * 2011-01-25 2012-08-16 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物及び空気入りタイヤ
JP2013121997A (ja) * 2011-12-09 2013-06-20 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物及び空気入りタイヤ
CN104449462B (zh) * 2013-09-13 2019-03-15 湖北回天新材料股份有限公司 一种耐湿热性能优异的汽车折边胶
CN103613523B (zh) * 2013-12-16 2016-04-06 北京彤程创展科技有限公司 一种硫代氨基甲酸衍生物及其制备方法
CN105152997A (zh) * 2015-08-01 2015-12-16 江苏麒祥高新材料有限公司 二硫代氨基甲酸类硫化交联剂的制备方法
CN106832448B (zh) * 2017-02-22 2019-02-26 双钱集团上海轮胎研究所有限公司 一种用于制备高性能轮胎的胎面胶
CN107759843A (zh) * 2017-09-25 2018-03-06 上海豪元橡胶制品有限公司 全钢子午线轮胎胎肩垫胶组合物及其制备方法
CN107778548A (zh) * 2017-09-25 2018-03-09 上海豪元橡胶制品有限公司 全钢子午线轮胎胎面胶组合物及其制备方法
CN107746483A (zh) * 2017-10-16 2018-03-02 山东恒宇科技有限公司 缺气保用轮胎胎侧支撑胶及制备方法
CN108395393A (zh) * 2018-05-15 2018-08-14 清华大学 一种秋兰姆类橡胶硫化促进剂的绿色合成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3869435A (en) * 1971-11-19 1975-03-04 Monsanto Co Method for cross-linking rubber
CA2289434A1 (en) * 1998-11-16 2000-05-16 Bayer Aktiengesellschaft Vulcanizable rubber compounds containing styrenebutadiene and butadiene rubbers
CN103922982A (zh) * 2014-04-25 2014-07-16 江苏麒祥高新材料有限公司 一种二硫代氨基甲酸类硫化交联剂的制备方法
CN105503677A (zh) * 2015-12-04 2016-04-20 山东阳谷华泰化工股份有限公司 一种环保、高效硫化交联剂1,6-二（n,n-二苄基氨基甲酰二硫）己烷的制备方法
CN108424552A (zh) * 2018-04-08 2018-08-21 贾中将 一种高抗硫化返原性能的橡胶减震器

Also Published As

Publication number Publication date
CN109233035A (zh) 2019-01-18
CN109233035B (zh) 2020-10-23

Similar Documents

Publication Publication Date Title
CN109835937A (zh) 金属有机骨架化合物衍生的金属硫化物纳米片及其制备
AU765081B2 (en) Telmisartan polymorphs, methods for producing same and their use in the preparation of a medicament
CN1212321C (zh) 工业合成雷尼酸锶盐及其水合物的新方法
CN103613523B (zh) 一种硫代氨基甲酸衍生物及其制备方法
CN102295592A (zh) 橡胶硫化促进剂二甲基二硫代氨基甲酸锌的制备方法
CN106750299B (zh) 一种低成本聚苯硫醚的制备方法
CN105037295A (zh) 一种生产次磺酰胺类橡胶硫化促进剂的方法
CN101318942A (zh) 新型循环水系统降温生产橡胶硫化促进剂dz的方法
CN106946230B (zh) 一种不溶性硫磺的连续生产方法
CN108586295A (zh) 一种硫化促进剂dpg的连续化生产方法
WO2020037831A1 (zh) 一种粒径为40-100μm的橡胶用抗硫化返原剂及其合成新方法
CN105413711A (zh) 负载型铜铋催化剂的再生制备方法
CN106316906B (zh) 一种合成促进剂dptu的方法
CN102093253A (zh) 苄氧胺盐酸盐类化合物的制备方法
CN106083679A (zh) 一种二烷氧基黄原酸酯多硫化物的制备方法
CN105837615B (zh) 一种低压、双组份溶剂、双催化剂合成硅烷偶联剂Si-75的方法
CN105037215B (zh) 一种高收率氧气氧化法合成促进剂dpg的环保方法
CN109225647B (zh) 叔丁氧基乙基二硫代碳酸盐及其制备方法和应用
CN108383087B (zh) 一种is90不溶性硫磺的制备方法
CN105503677A (zh) 一种环保、高效硫化交联剂1,6-二（n,n-二苄基氨基甲酰二硫）己烷的制备方法
CN106672920B (zh) 一种常温液相制备硒硫固溶体的方法
CN112645900B (zh) 促进剂dcbs的合成方法
CN102504160A (zh) 利用合成阿司匹林废液制备混凝土高效减水剂方法
CN111013665B (zh) 一种基于Fe3O4的磁性固体酸催化剂及其制备方法、应用
CN104557728B (zh) 以邻苯二胺的精馏残渣制备多菌灵的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18931117

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18931117

Country of ref document: EP

Kind code of ref document: A1