Rubber plasticizer for petroleum-based environment-friendly reclaimed rubber and preparation method thereof
阅读说明：本技术 一种石油系环保型再生胶用橡胶增塑剂及其制备方法 (Rubber plasticizer for petroleum-based environment-friendly reclaimed rubber and preparation method thereof ) 是由 冯涛 李军 于恩强 武光照 马志远 王瑞瑞 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种石油系环保型再生胶用橡胶增塑剂及其制备方法。它的制备方法,包括如下步骤：(1)将减压渣油进行馏分切割,得到特定馏分段的窄馏分；(2)对所述窄馏分进行脱芳反应,脱除部分多环芳烃,得到脱芳油；(3)对所述得到脱芳油进行改性反应,得到石油系环保型再生胶用橡胶增塑剂。该橡胶增塑剂具有芳烃含量高,与橡胶具有良好的相容性；应用性能好,可很好的解决传统的非环保煤质沥青制备的再生胶油品迁移以及门尼粘度反弹大等问题；满足欧盟环保要求,苯并芘的含量小于1mg/kg、18种多环芳烃的总含量小于50mg/kg,为环保型产品；产品原料采用一般市售减压渣油,来源丰富,可以保证稳定生产。(The invention discloses a rubber plasticizer for petroleum-based environment-friendly reclaimed rubber and a preparation method thereof. The preparation method comprises the following steps: (1) carrying out fraction cutting on vacuum residue to obtain narrow fraction of a specific fraction section; (2) performing dearomatization reaction on the narrow fraction to remove part of polycyclic aromatic hydrocarbon to obtain dearomatized oil; (3) and carrying out modification reaction on the obtained dearomatized oil to obtain the rubber plasticizer for the petroleum environment-friendly reclaimed rubber. The rubber plasticizer has high aromatic hydrocarbon content and good compatibility with rubber; the application performance is good, and the problems of oil product migration, large Mooney viscosity rebound and the like of the reclaimed rubber prepared by the traditional non-environment-friendly coal asphalt can be well solved; meets the requirement of European Union on for environmental protection, the content of benzopyrene is less than 1mg/kg, the total content of 18 polycyclic aromatic hydrocarbons is less than 50mg/kg, and the product is an environment-friendly product; the raw materials of the product are common commercial vacuum residue oil, the sources are rich, and the stable production can be ensured.)
1. A method of preparing a rubber plasticizer comprising:
1) carrying out fraction cutting on the vacuum residue to obtain narrow fraction;
2) performing dearomatization reaction on the narrow fraction to obtain dearomatized oil;
3) and carrying out modification reaction on the dearomatized oil to obtain the rubber plasticizer.
2. The method of claim 1, wherein: the crude oil of the vacuum residue belongs to at least one of intermediate base crude oil and naphthenic base crude oil; the characteristic factor of the intermediate base crude oil is 11.5-12.1;
the kinematic viscosity of the vacuum residue at 100 ℃ is 180-280 mm2The distillation range is > 450 ℃.
3. The method according to claim 1 or 2, characterized in that: the vacuum residue is selected from vacuum distillate oil obtained by vacuum distillation of crude oil.
4. A method according to any one of claims 1 to 3, wherein: the distillation range of the narrow distillate obtained in the distillate cutting step is as follows: 450 to 600 ℃.
5. The method according to any one of claims 1 to 4, wherein: in the dearomatization reaction in the step 2), the addition amount of the dearomatization agent is 0.1-5% of the mass of the narrow fraction;
the adding amount of the catalyst is 0-8% of the mass of the narrow fraction;
the dearomatization agent is a polymer with reducibility; specifically at least one selected from polyethylene glycol, unsaturated polyester and trioxymethylene; the molecular weight of the polyethylene glycol is 150-300; the unsaturated polyester is specifically selected from at least one of styrene/butadiene copolymer, maleic anhydride/propylene glycol copolymer and phthalic anhydride/propylene glycol copolymer;
the catalyst is a polymer capable of providing a specific acidic environment; specifically at least one selected from polyphosphoric acid and polyurethane;
the molecular weight of the polyphosphoric acid is 200-600; more particularly from H5P3O10、H7P5O16And H9P7O22At least one of (1);
the molecular weight of the polyurethane is 2000-10000.
6. The method according to any one of claims 1 to 5, wherein: in the dearomatization reaction in the step 2), the temperature is 80-250 ℃;
the time is 20-60 min.
7. The method of any one of claims 1-6, wherein: in the modification reaction in the step 3), the addition amount of the modifier is 0.5-5% of the mass of the dearomatized oil;
the modifier is a compound with reducibility; specifically at least one of stearic acid, zinc stearate, lignin, friedel-crafts olefin, oligomeric ester, anti-aging agent 1314 and white carbon black;
in the step of modification reaction, the temperature is 80-250 ℃;
the time is 20-60 min.
8. A rubber plasticizer prepared by the method of any of claims 1 to 7.
9. A rubber plasticizer according to claim 8, characterized in that: the performance parameters of the rubber plasticizer are as follows:
the kinematic viscosity at 100 ℃ is 80-250 mm2/s；
The aromatic hydrocarbon content is 35-60%;
the content of benzopyrene is less than 1 mg/kg;
the content of 18 polycyclic aromatic hydrocarbons is less than 50 mg/kg;
the 18 polycyclic aromatic hydrocarbons are specifically selected from at least one of benzo (a) pyrene, benzo (e) pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzo (a, h) anthracene, indeno (1,2,3-cd) pyrene, benzo (g, h, i) pyrene, naphthalene, acenaphthene, acenaphthylene, fluorene, anthracene, fluoranthene, phenanthrene and pyrene.
10. Use of the rubber plasticizer according to claim 8 or 9 for the plasticization of reclaimed rubber or petroleum-based environment-friendly reclaimed rubber.
Technical Field
The invention relates to a rubber plasticizer for petroleum-based environment-friendly reclaimed rubber and a preparation method thereof, belonging to the field of petrochemical product processing.
Background
Rubber is used as strategic material and needs to be imported in large quantity every year, but waste rubber is generated more and more at the same time. The rubber resources in China are in short supply, so that the reclaimed rubber prepared from the waste rubber is used as a rubber substitute material, accords with the national conditions of China, and is a main way for rubber regeneration and reutilization. In order to improve the processing and use performance of reclaimed rubber, a specific rubber plasticizer is usually added for achieving the purpose. The rubber plasticizer is added into the rubber, so that the acting force between rubber molecular chains can be reduced, and the powdery compounding agent and the rubber powder are well infiltrated, thereby improving the mixing process; meanwhile, the plasticity, the fluidity and the adhesiveness of the rubber material can be increased, and the process operations such as calendering, extrusion, molding and the like are facilitated.
At present, coal tar is mostly used as a plasticizer in the production process of reclaimed rubber in the reclaimed rubber industry. However, the content of 18 specific polycyclic aromatic hydrocarbons in the reclaimed rubber produced by using coal tar as a plasticizer far exceeds the relevant regulatory requirements of developed countries such as Europe and America, and the reclaimed rubber belongs to toxic and harmful pollution type products, and rubber products prepared by using the reclaimed rubber are difficult to export. The reclaimed rubber industry faces severe transformation and upgrading pressure, and the use of environment-friendly raw materials becomes a consensus of the reclaimed rubber industry. The development of the rubber plasticizer for petroleum-based environment-friendly reclaimed rubber meeting the environmental protection requirement of the European Union is beneficial to the development of the whole reclaimed rubber industry.
Disclosure of Invention
The invention aims to provide a rubber plasticizer for petroleum-based environment-friendly reclaimed rubber and a preparation method thereof. The rubber plasticizer has high aromatic hydrocarbon content, good compatibility with rubber and no migration; the processability of the reclaimed rubber can be effectively improved, and the prepared reclaimed rubber has good Mooney stability; the content of 18 polycyclic aromatic hydrocarbons meets the environmental protection requirement of European Union; the preparation process is simple and economical.
The invention provides a method for preparing a rubber plasticizer, which comprises the following steps:
1) carrying out fraction cutting on the vacuum residue to obtain narrow fraction;
2) performing dearomatization reaction on the narrow fraction to obtain dearomatized oil;
3) and carrying out modification reaction on the dearomatized oil to obtain the rubber plasticizer.
In the above process, the crude oil of the vacuum residue is at least one selected from the group consisting of a medium base crude oil and a naphthenic base crude oil; the characteristic factor of the intermediate base crude oil is 11.5-12.1;
the kinematic viscosity of the vacuum residue at 100 ℃ is 180-280 mm2The distillation range is > 450 ℃.
The vacuum residue is vacuum distillate oil obtained by vacuum distillation of crude oil; more specifically, vacuum residuum as shown in table 1 properties.
The distillation range of the narrow distillate obtained in the distillate cutting step is as follows: 450-600 ℃;
the fraction is finely cut into cut light fraction of 5-20%, 5-15% or 8-20%.
In the dearomatization reaction in the step 2), the addition amount of the dearomatization agent is 0.1-5% of the mass of the narrow fraction; specifically, 0.5%, 1%, 2%, 3% or 0.5% -5%;
the adding amount of the catalyst is 0-8% of the mass of the narrow fraction, and specifically can be 0.1%, 3%, 5% or 3-8%;
the dearomatization agent is a polymer with reducibility; specifically at least one selected from polyethylene glycol, unsaturated polyester and trioxymethylene; the polyethylene glycol is liquid at normal temperature and has a molecular formula of HO (CH)2CH2O)nH, molecular weight is 150-300; the unsaturated polyester is specifically selected from at least one of styrene/butadiene copolymer, maleic anhydride/propylene glycol copolymer and phthalic anhydride/propylene glycol copolymer;
the catalyst is a polymer capable of providing a specific acidic environment; specifically at least one selected from polyphosphoric acid and polyurethane;
the polyphosphoric acid is colorless transparent viscous liquid with a molecular formula (H)n+2(P)n(O)3n+1Molecular weight is 200-600; more particularly from H5P3O10、H7P5O16And H9P7O22At least one of (1);
the molecular weight of the polyurethane is 2000-10000; specifically, a polyurethane for rubber.
In the dearomatization reaction in the step 2), the temperature is 80-250 ℃; specifically, the temperature can be 120 ℃, 150 ℃, 180 ℃ or 220-250 ℃;
the time is 20-60 min; specifically, it can be 20min, 30min, 40min or 40-60 min.
In the modification reaction in the step 3), the addition amount of the modifier is 0.5-5% of the mass of the dearomatized oil; specifically, 0.5%, 1%, 2%, 3%, 4% or 0.5% -5%;
the modifier is a compound with reducibility; specifically at least one of stearic acid, zinc stearate, lignin, friedel-crafts olefin, oligomeric ester, anti-aging agent 1314 and white carbon black;
in the step of modification reaction, the temperature is 80-250 ℃; specifically, the temperature can be 120 ℃, 150 ℃, 180 ℃ or 220-250 ℃;
the time is 20-60 min; specifically, it can be 20min, 30min, 40min or 40-60 min.
In addition, the rubber plasticizer prepared by the method and the application of the rubber plasticizer in the plasticization of reclaimed rubber or petroleum environment-friendly reclaimed rubber also belong to the protection scope of the invention.
Specifically, the performance parameters of the rubber plasticizer are as follows:
the kinematic viscosity at 100 ℃ is 80-250 mm2/s；
The aromatic hydrocarbon content is 35-60%;
the content of benzopyrene is less than 1 mg/kg;
the content of 18 polycyclic aromatic hydrocarbons is less than 50 mg/kg;
the 18 polycyclic aromatic hydrocarbons are specifically selected from at least one of benzo (a) pyrene, benzo (e) pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzo (a, h) anthracene, indeno (1,2,3-cd) pyrene, benzo (g, h, i) pyrene, naphthalene, acenaphthene, acenaphthylene, fluorene, anthracene, fluoranthene, phenanthrene and pyrene.
In the present invention, the benzo (a) pyrene, benzo (e) pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzo (a, h) anthracene, indeno (1,2,3-cd) pyrene, benzo (g, h, i) pyrene, naphthalene, acenaphthene, acenaphthylene, fluorene, anthracene, fluoranthene, phenanthrene and pyrene are abbreviated as BaP, BeP, BaA, CHR, BbFA, BjFA, BkFA, DBA, IPy, BPE, NAP, ANA, ANY, FLU, ANT, FLT, PHE and PYR, respectively.
The method comprises the following steps of cutting the raw materials into proper fractions to obtain narrow fractions of specific distillation sections, wherein the distillation sections are relatively single in composition, most polycyclic aromatic hydrocarbons in the raw materials are cut off, and more monocyclic and bicyclic aromatic hydrocarbons are reserved; in order to further reduce the content of polycyclic aromatic hydrocarbon in distillate oil, a small amount of polycyclic aromatic hydrocarbon is removed by using a dearomatization agent, and the performance of the dearomatization agent is improved by using a modifier, so that the petroleum-series environment-friendly rubber plasticizer for reclaimed rubber is produced. The product of the invention has higher aromatic hydrocarbon content, better compatibility with the regenerated rubber powder and good application performance. Compared with the common coal tar rubber plasticizer, the product provided by the invention meets the environmental protection requirements of European Union, and can solve the application problems of migration, unstable Mooney performance and the like of coal tar in the use process.
The rubber plasticizer for the petroleum-based environment-friendly reclaimed rubber has the following advantages:
1. the aromatic hydrocarbon content is high. The aromatic hydrocarbon content of the product is more than 35 percent, the product has good compatibility with rubber, and the product can fully play the role of a rubber plasticizer when used in the manufacturing process of a reclaimed rubber product, and improve the processing and using performance of the rubber product.
2. The application performance is good. Compared with the traditional application of the coal tar product in reclaimed rubber, the product of the invention can well solve the problems of migration, large Mooney viscosity rebound and the like of the prepared reclaimed rubber.
3. Meets the environmental protection requirement of European Union and is an environmental protection product. The product of the invention meets the limited conditions in the European Union REACH regulation: the content of benzopyrene is less than 1mg/kg, the content of 18 polycyclic aromatic hydrocarbons is less than 50mg/kg, and the product is environment-friendly.
4. Rich resources and stable production. The product of the invention adopts general distillate oil on the market, has rich sources, and can ensure the stable production of the rubber plasticizer for the petroleum environment-friendly reclaimed rubber.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The molecular weight of the polyethylene glycol used in the following examples is 150-300; the molecular weight of the polyphosphoric acid is 200-600; the molecular weight of the polyurethane used is 2000-; specifically, a polyurethane for rubber. The feedstocks used in the examples below were either a medium or a naphthenic vacuum residue, all commercially available, and the properties are shown in table 1.
TABLE 1 vacuum residuum Properties
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