技术领域technical field
本发明是关于一种添加剂组合物、含有该添加剂组合物的柴油组合物和提高生物柴油氧化安定性的方法。The invention relates to an additive composition, a diesel composition containing the additive composition and a method for improving the oxidation stability of biodiesel.
背景技术Background technique
随着世界范围内车辆柴油化趋势的加快，柴油的需求量会愈来愈大，而石油资源的日益枯竭和人们环保意识的提高，大大促进了世界各国加快柴油替代燃料的开发步伐，生物柴油以其优越的环保性能和可再生性受到了各国的重视。With the acceleration of dieselization of vehicles worldwide, the demand for diesel will increase. The depletion of petroleum resources and the improvement of people's awareness of environmental protection have greatly promoted the development of diesel alternative fuels in countries around the world. Biodiesel It has been valued by various countries for its superior environmental protection performance and renewability.
生物柴油(BD100)又称脂肪酸甲酯(FattyAcidMethylEster)，是以大豆和油菜籽等油料作物、油棕和黄连木等油料林木果实、工程微藻等油料水生植物的油脂以及动物油脂、废餐饮油等作原料，与醇类(甲醇、乙醇)经酯交换反应获得，是一种洁净的生物燃料。生物柴油具有可再生、清洁和安全三大优势，对我国农业结构调整、能源安全和生态环境综合治理有十分重大的战略意义。而我国目前是一个石油净进口国，石油储量又很有限，大量进口石油对我国的能源安全造成威胁；因此，生物柴油的研究和生产对我国有着重要的现实意义。Biodiesel (BD100), also known as fatty acid methyl ester (FattyAcidMethylEster), is based on oil crops such as soybeans and rapeseeds, oil-bearing forest fruits such as oil palm and pistachio, engineering microalgae and other oil-bearing aquatic plants, animal fats, and waste cooking oil. etc. as raw materials, obtained through transesterification with alcohols (methanol, ethanol), and is a clean biofuel. Biodiesel has the three major advantages of being renewable, clean and safe, and is of great strategic significance to the adjustment of my country's agricultural structure, energy security and comprehensive management of the ecological environment. But our country is a net importer of oil at present, and the oil reserves are very limited. Importing a large amount of oil poses a threat to our energy security; therefore, the research and production of biodiesel has important practical significance to our country.
但是，由于原料和加工工艺的原因，有些生物柴油的氧化安定性很差，对生物柴油的使用和贮存都造成很大的困难。氧化安定性差的生物柴油易生成如下老化产物：1)不溶性聚合物(胶质和油泥)，这会造成发动机滤网堵塞和喷射泵结焦，并导致排烟增大、启动困难；2)可溶性聚合物，其可在发动机中形成树脂状物质，可能会导致熄火和启动困难；3)老化酸，这会造成发动机金属部件腐蚀；4)过氧化物，这会造成橡胶部件的老化变脆而导致燃料泄漏等。However, due to raw materials and processing techniques, some biodiesel has poor oxidation stability, which causes great difficulties in the use and storage of biodiesel. Biodiesel with poor oxidation stability is prone to produce the following aging products: 1) insoluble polymers (colloids and sludge), which will cause engine filter blockage and injection pump coking, and lead to increased smoke exhaust and difficulty in starting; 2) soluble polymers 3) aging acids, which can cause corrosion of metal parts in the engine; 4) peroxides, which can cause aging of rubber parts to become brittle and cause Fuel leaks, etc.
欧洲生物柴油标准EN14214：2003、澳大利亚生物柴油标准(Draft2003)、新西兰生物柴油标准NZS7500：2005、巴西生物柴油标准ANP255(2003)、印度生物柴油标准IS15607：2005、南非生物柴油标准SANS1935：2004以及我国柴油机燃料调合用生物柴油(BD100)国家标准GB/T20828-2007都规定生物柴油的氧化安定性为110℃下的诱导期不低于6小时，测定方法为EN14112：2003。European biodiesel standard EN14214: 2003, Australian biodiesel standard (Draft2003), New Zealand biodiesel standard NZS7500: 2005, Brazilian biodiesel standard ANP255 (2003), Indian biodiesel standard IS15607: 2005, South African biodiesel standard SANS1935: 2004 and my country The national standard GB/T20828-2007 of biodiesel (BD100) for diesel fuel blending stipulates that the oxidation stability of biodiesel is not less than 6 hours at 110°C, and the measurement method is EN14112:2003.
众所周知，石油柴油(即通常意义的柴油，此处为了与生物柴油相区分，特引入石油柴油)中的烯烃、双烯烃以及硫化物、氮化物等非烃化合物在氧的作用下，生成一系列的氧化中间产物，并经缩合作用产生不溶性的沉淀。这些在石油柴油储存过程中生成的不溶性颗粒会影响到燃料的使用性能，造成过滤系统堵塞，引起燃油系统部件故障，影响喷油雾化，导致不完全燃烧，甚至在发动机中形成过多积炭，使喷嘴堵塞。而生物柴油由于氧化安定性比石油柴油差，与石油柴油调合后会加重上述问题。最为明显的表现是含生物柴油的调合燃料的稳定性比石油柴油要差。As we all know, non-hydrocarbon compounds such as olefins, diolefins, sulfides, and nitrogen compounds in petroleum diesel oil (that is, diesel oil in the usual sense, here in order to distinguish it from biodiesel), generate a series of Oxidation intermediates, and condensation produces insoluble precipitates. These insoluble particles generated during the storage of petroleum diesel will affect the performance of the fuel, cause blockage of the filter system, cause failure of fuel system components, affect fuel injection atomization, cause incomplete combustion, and even form excessive carbon deposits in the engine , causing the nozzle to clog. Since biodiesel has poorer oxidation stability than petroleum diesel, blending with petroleum diesel will aggravate the above problems. The most obvious manifestation is that the stability of blended fuel containing biodiesel is worse than that of petroleum diesel.
上述问题可通过加入添加剂解决或缓解。一种方式是向纯生物柴油中加入抗氧剂以减缓其氧化，从而缓解老化产物的危害；另一种方式是向石油柴油或含生物柴油的调合燃料中加入稳定剂以改善调合燃料的稳定性。稳定剂可终止、减弱、或干扰各种氧化反应，以抑制油品变质，改善其安定性。The above problems can be solved or alleviated by adding additives. One way is to add antioxidants to pure biodiesel to slow down its oxidation, thereby alleviating the hazards of aging products; the other way is to add stabilizers to petroleum diesel or blended fuels containing biodiesel to improve blended fuels stability. Stabilizers can terminate, weaken, or interfere with various oxidation reactions to inhibit oil deterioration and improve its stability.
CN1742072A公开了一种提高生物柴油储存稳定性的方法，该方法包括将含有以原液计为15-60重量％的溶于生物柴油的2，4-二叔丁基羟甲苯的液态原液加入到待稳定化的生物柴油中，直至以生物柴油的总溶液计，2，4-二叔丁基羟甲苯的浓度达到0.005-2重量％。CN1742072A discloses a method for improving the storage stability of biodiesel, which method includes adding a liquid stock solution containing 15-60% by weight of 2,4-di-tert-butylhydroxytoluene dissolved in biodiesel to the In the stabilized biodiesel, the concentration of 2,4-di-tert-butylhydroxytoluene reaches 0.005-2% by weight based on the total solution of biodiesel.
CN1847368A公开了一种提高生物柴油的氧化稳定性的方法，该方法包括将双酚型抗氧剂如4，4`-亚甲基二[2，6-二叔丁基苯酚]、2，2`-亚甲基二[6-叔丁基-4-甲基苯酚]以10-20000ppm(w/w)的量加入到待稳定的生物柴油中。CN1847368A discloses a method for improving the oxidation stability of biodiesel, which method comprises bisphenol type antioxidants such as 4,4'-methylene bis[2,6-di-tert-butylphenol], 2,2 `-Methylenebis[6-tert-butyl-4-methylphenol] is added to the biodiesel to be stabilized in an amount of 10-20000ppm (w/w).
CN1847369A公开了一种提高生物柴油的氧化稳定性的方法，该方法包括将熔点小于或等于40℃的主抗氧化剂以10-20000ppm(w/w)的量加入到待稳定的生物柴油中，其中所述主抗氧化剂含有烷基酚。CN1847369A discloses a method for improving the oxidation stability of biodiesel, which method includes adding a primary antioxidant with a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of 10-20000ppm (w/w), wherein The primary antioxidant contains alkylphenols.
US2007/113467A1公开了一种具有改进的氧化稳定性的燃料组合物，该组合物含有生物柴油和至少一种抗氧剂，所述抗氧剂选自没食子酸丙酯、1，2，3-三羟基苯、2，6-二叔丁基对甲基苯酚、丁基化羟基茴香醚、硫代二丙酸月桂酯、生育酚、喹啉衍生物中的一种。US2007/113467A1 discloses a fuel composition having improved oxidation stability, the composition comprising biodiesel and at least one antioxidant selected from the group consisting of propyl gallate, 1,2,3- One of trihydroxybenzene, 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, lauryl thiodipropionate, tocopherol, and quinoline derivatives.
以上使用传统的抗氧剂来提高生物柴油氧化安定性的方法虽然有一定效果，但用量都较大，同时对含生物柴油的调合燃料的稳定性的改善效果也不太好。Although the above methods of using traditional antioxidants to improve the oxidation stability of biodiesel have certain effects, the dosage is relatively large, and the improvement effect on the stability of the blended fuel containing biodiesel is not very good.
发明内容Contents of the invention
本发明的目的是为了克服上述现有技术的抗氧剂用量大以及含生物柴油的调合燃料的稳定性改善效果较差的缺点，提供一种能够提高生物柴油氧化安定性或者稳定性较好的添加剂组合物和含有该添加剂组合物的柴油组合物以及提供一种提高生物柴油氧化安定性的方法。The purpose of the present invention is to overcome the shortcomings of the large amount of antioxidants in the prior art and the relatively poor stability improvement effect of the blended fuel containing biodiesel, and to provide a biodiesel that can improve the oxidation stability or stability of biodiesel. The additive composition and the diesel composition containing the additive composition and a method for improving the oxidation stability of biodiesel are provided.
本发明提供了一种添加剂组合物，所述添加剂组合物含有组分a和组分b，所述组分a为芳胺型抗氧剂和/或受阻酚型抗氧剂；所述组分b是氨与C-C6醛的缩合反应产物和/或胺与C1-C6醛的缩合反应产物。The invention provides an additive composition, the additive composition contains component a and component b, the component a is aromatic amine antioxidant and/or hindered phenol antioxidant; the component b is the condensation reaction product of ammonia with C-C6 aldehydes and/or the condensation reaction product of amines with C1-C6 aldehydes.
本发明还提供了一种柴油组合物，所述柴油组合物含有基础柴油和添加剂，其特征在于，所述基础柴油含有生物柴油，所述添加剂为本发明提供的添加剂组合物。The present invention also provides a diesel oil composition, which contains base diesel oil and additives, characterized in that the base diesel oil contains biodiesel, and the additive is the additive composition provided by the present invention.
本发明还提供一种提高生物柴油氧化安定性的方法，该方法包括，在含有生物柴油的基础柴油中，加入添加剂，其中，所述添加剂为本发明提供的添加剂组合物。The present invention also provides a method for improving the oxidation stability of biodiesel, which includes adding an additive to the base diesel containing biodiesel, wherein the additive is the additive composition provided by the present invention.
本发明提供的添加剂组合物，当与纯生物柴油作为基础柴油配合得到柴油组合物时，该柴油组合物具有较好的氧化安定性，组分a与组分b之间令人惊异的出现协同效应，抗氧化效果比单独使用抗氧剂要好很多。组分b可以看作是辅助抗氧剂，其可以使抗氧剂的效果出人意料地大大增强。因此，在达到相同的氧化安定性要求时，组分a在生物柴油组合物中的量可以大大减少，尤其是组分a特别昂贵或组分a有一定毒性或腐蚀性的情况下，减少了其用量具有很大意义。当该添加剂组合物与以含有生物柴油的调合燃料作为基础柴油配合得到柴油组合物时，该柴油组合物的稳定性较好。特别是根据本发明提供的优选实施方式，当所述添加剂同时含有组分a、组分b和组分c时，由于各添加剂之间明显的协同效应，本发明提供的柴油组合物的抗氧性明显提高。The additive composition provided by the present invention, when blended with pure biodiesel as base diesel oil to obtain a diesel composition, the diesel composition has better oxidation stability, and there is surprising synergy between component a and component b Effect, the antioxidant effect is much better than using antioxidants alone. Component b can be regarded as a secondary antioxidant, which can unexpectedly greatly enhance the effect of antioxidants. Therefore, when achieving the same oxidation stability requirements, the amount of component a in the biodiesel composition can be greatly reduced, especially when component a is particularly expensive or component a has certain toxicity or corrosiveness. Its dosage is of great significance. When the additive composition is mixed with the blended fuel containing biodiesel as base diesel to obtain a diesel composition, the stability of the diesel composition is better. Especially according to the preferred embodiment provided by the present invention, when the additive contains component a, component b and component c at the same time, due to the obvious synergistic effect between the additives, the oxidation resistance of the diesel composition provided by the present invention Significantly improved sex.
具体实施方式detailed description
根据本发明提供的柴油组合物中，所述添加剂的含量可以在较大范围内选择，例如相对于基础柴油的含量可以为50-10000ppm，优选80-8000ppm，进一步优选为100-5000ppm。In the diesel composition provided by the present invention, the content of the additive can be selected in a wide range, for example, the content of the base diesel can be 50-10000ppm, preferably 80-8000ppm, more preferably 100-5000ppm.
所述组分b与组分a的重量比可以为0.01-100∶1，优选为0.02-50∶1，进一步优选为0.05-10∶1，更进一步优选为0.2-5∶1。The weight ratio of component b to component a may be 0.01-100:1, preferably 0.02-50:1, more preferably 0.05-10:1, even more preferably 0.2-5:1.
组分aComponent a
所述组分a为芳胺型抗氧剂和/或受阻酚型抗氧剂，所述芳胺型抗氧剂可以选自取代的萘胺、取代的二苯胺、取代的对苯二胺、取代的喹啉中的至少一种，所述受阻酚型抗氧剂为双酚型抗氧剂和/或分子中至少含有三个酚羟基的多酚型抗氧剂。The component a is an aromatic amine antioxidant and/or a hindered phenol antioxidant, and the aromatic amine antioxidant can be selected from substituted naphthylamine, substituted diphenylamine, substituted p-phenylenediamine, At least one of substituted quinolines, the hindered phenolic antioxidant is a bisphenolic antioxidant and/or a polyphenolic antioxidant with at least three phenolic hydroxyl groups in its molecule.
其中取代的萘胺包括但不限于下列物质中的一种或多种：Wherein the substituted naphthylamines include but are not limited to one or more of the following substances:
苯基-α-萘胺(抗氧剂T531，防老剂甲)；Phenyl-α-naphthylamine (antioxidant T531, antioxidant A);
苯基-β-萘胺(防老剂丁)；Phenyl-β-naphthylamine (antiaging agent D);
N-对甲氧基苯基α-萘胺(防老剂102)；N-p-methoxyphenyl α-naphthylamine (antiaging agent 102);
对羟苯基-β-萘胺(防老剂D-OH)；p-Hydroxyphenyl-β-naphthylamine (antiaging agent D-OH);
丁间醇醛-α-萘胺(防老剂AP)Aldol-α-Naphthylamine (Antioxidant AP)
2-羟基-1，3-双[对(β-萘胺)苯氧基]丙烷(防老剂C-49)；2-Hydroxy-1,3-bis[p-(β-naphthylamine)phenoxy]propane (antiaging agent C-49);
二甲基双[对(β-萘胺)苯氧基]硅烷(防老剂C-41)；Dimethylbis[p-(β-naphthylamine)phenoxy]silane (antiaging agent C-41);
二乙基双[对(β-萘胺)苯氧基]硅烷(防老剂C-41-乙基)；Diethylbis[p-(β-naphthylamine)phenoxy]silane (antiaging agent C-41-ethyl);
2，2’-双[对(β-萘胺)苯氧基]二乙醚(防老剂C-41-乙醚)。2,2'-bis[p-(β-naphthylamine)phenoxy]diethyl ether (antiaging agent C-41-ethyl ether).
其中，取代的萘胺优选苯基萘胺，例如苯基-α-萘胺、苯基-β-萘胺、N-对甲氧基苯基α-萘胺中的一种或多种。尤其优选苯基-α-萘胺。Among them, the substituted naphthylamine is preferably phenylnaphthylamine, such as one or more of phenyl-α-naphthylamine, phenyl-β-naphthylamine, and N-p-methoxyphenylα-naphthylamine. Phenyl-α-naphthylamine is especially preferred.
其中取代的二苯胺包括但不限于下列物质中的一种或多种：The substituted diphenylamines include but are not limited to one or more of the following substances:
4，4’-二氨基二苯胺(防老剂APA)；4,4'-diaminodiphenylamine (antiaging agent APA);
对，对’-二甲氧基二苯胺；p, p'-dimethoxydiphenylamine;
N，N，N’，N’-四苯基二胺甲烷(防老剂350)；N, N, N', N'-tetraphenyldiaminemethane (antiaging agent 350);
N，N’-二苯基乙二胺；N,N'-diphenylethylenediamine;
N，N’-二苯基丙二胺；N,N'-diphenylpropylenediamine;
N，N’-二邻甲苯基乙二胺；N,N'-di-o-tolylethylenediamine;
2-羟基-1，3-双-(对苯胺苯氧基)丙烷(防老剂C-47)；2-Hydroxy-1,3-bis-(p-anilinephenoxy)propane (antiaging agent C-47);
2，2’-双(对苯胺苯氧基)-二乙醚(防老剂H-1)；2,2'-bis(p-anilinephenoxy)-diethyl ether (antiaging agent H-1);
二甲基双(对苯胺-苯氧基)-硅烷(防老剂C-1)；Dimethylbis(p-aniline-phenoxy)-silane (antiaging agent C-1);
对异丙氧基二苯胺(防老剂ISO)；p-isopropoxy diphenylamine (antiaging agent ISO);
对，对’-二异丙氧基二苯胺(防老剂DISO)；Right, right'-diisopropoxy diphenylamine (antiaging agent DISO);
4，4’-双(α，α’-二甲基苄基)二苯胺(防老剂KY-405)；4,4'-bis(α,α'-dimethylbenzyl)diphenylamine (antiaging agent KY-405);
对羟基二苯胺(防老剂AO3920)；p-Hydroxydiphenylamine (antiaging agent AO3920);
二-(1，1，3，3-四甲基乙基)二苯胺(防老剂ODA)；Di-(1,1,3,3-tetramethylethyl)diphenylamine (antiaging agent ODA);
4，4’-二辛基二苯胺；4,4'-Dioctyldiphenylamine;
4，4’-二异辛基二苯胺；4,4'-Diisooctyldiphenylamine;
4，4’-二庚基二苯胺；4,4'-Diheptyldiphenylamine;
4，4’-二壬基二苯胺；4,4'-Dinonyldiphenylamine;
辛基化二苯胺(一辛基化二苯胺和二辛基化二苯胺的混合物，防老剂OD)；Octylated diphenylamine (a mixture of monooctylated diphenylamine and dioctylated diphenylamine, antioxidant OD);
辛基/丁基二苯胺(抗氧剂L-57)；Octyl/butyl diphenylamine (antioxidant L-57);
苯乙烯化二苯胺(防老剂DFL，DFC-34)；Styrenated diphenylamine (antiaging agent DFL, DFC-34);
以及烷基化二苯胺的混合物，其中烷基可以为庚基、辛基、壬基中的一种或几种，其工业产品的例子有美国Pennwalt公司商品名为PennoxA、PennoxA-“S”，美国Nationalpolychem公司商品名为WytoxADP、ADP-X，美国Vanderbilt公司商品名为AgeriteStalite、AgeriteStaliteS、AgeriteNepa、AgeriteGel，美国Uniroyal公司商品名为Polylite、Antioxidant445、以及国内代号为T534的抗氧剂产品。And the mixture of alkylated diphenylamine, wherein alkyl can be one or more in heptyl, octyl, nonyl, the example of its industrial product has U.S. Pennwalt company trade name to be PennoxA, PennoxA-"S", U.S. Nationalpolychem company trade name is WytoxADP, ADP-X, U.S. Vanderbilt company trade name is AgeriteStalite, AgeriteStaliteS, AgeriteNepa, AgeriteGel, U.S. Uniroyal company trade name is Polylite, Antioxidant445, and domestic code name is the antioxidant product of T534.
取代的二苯胺型抗氧剂优选烷基化二苯胺及其混合物，尤其优选烷基碳原子数在4-10之间的烷基化二苯胺及其混合物，如：4，4’-二辛基二苯胺、4，4’-二异辛基二苯胺、4，4’-二庚基二苯胺、4，4’-二壬基二苯胺、辛基化二苯胺(一辛基化二苯胺和二辛基化二苯胺的混合物)、辛基/丁基二苯胺、商品抗氧剂T534中的一种或多种。Substituted diphenylamine antioxidants are preferably alkylated diphenylamines and mixtures thereof, especially alkylated diphenylamines with alkyl carbon atoms between 4-10 and mixtures thereof, such as: 4,4'-dioctyl Diphenylamine, 4,4'-diisooctyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dinonyldiphenylamine, octylated diphenylamine (one-octylated diphenylamine One or more of the mixture of dioctylated diphenylamine), octyl/butyl diphenylamine, commercial antioxidant T534.
其中所述取代的对苯二胺型抗氧剂可以是对苯二胺的胺基(-NH2)中的氢原子被一个或多个烷基、芳基、芳烷基、烷基芳基、烃基酰基、烃基磺酰基、烃基酰氧基中的一种或几种取代后的产物，当胺基中的两个氢原子被取代时，可以是取代同一个胺基上的氢原子，也可以是取代两个胺基上的氢原子，且为两个以上取代基时，各取代基之间可以相同，也可以不同。也就是说，所述取代的对苯二胺型抗氧剂可以是单烷基取代的对苯二胺、单芳基取代的对苯二胺、单烷基芳基取代的对苯二胺、单芳基烷基取代的对苯二胺、单烃基酰基取代的对苯二胺、单烃基磺酰基取代的对苯二胺、单烃基酰氧基取代的对苯二胺、N-烷基-N’-烷基取代的对苯二胺、N-芳基-N’-烷基取代的对苯二胺、N-烷基-N’-烷基芳基取代的对苯二胺、N-芳基-N’-烷基取代的对苯二胺、N-芳基烷基-N’-烷基取代的对苯二胺、N-芳基烷基-N’-芳基取代的对苯二胺、N-芳基烷基-N’-烃基酰基取代的对苯二胺、N-芳基烷基-N’-烃基磺酰基取代的对苯二胺、N-芳基烷基-N’-烃基酰氧基取代的对苯二胺、N-芳基-N’-烃基酰基取代的对苯二胺、N-烷基-N’-烃基磺酰基取代的对苯二胺、N-烷基-N’-烃基酰氧基取代的对苯二胺N-芳基-N’-烃基酰基取代的对苯二胺、N-烷基-N’-烃基磺酰基取代的对苯二胺、N-烷基-N’-烃基酰氧基取代的对苯二胺、N-烷基芳基-N’-烃基酰基取代的对苯二胺、N-烷基芳基-N’-烃基磺酰基取代的对苯二胺、N-烷基芳基-N’-烃基酰氧基取代的对苯二胺、N，N-双烷基取代的对苯二胺、N，N-双芳基取代的对苯二胺、N，N-双烷基芳基取代的对苯二胺、N，N-双芳基烷基取代的对苯二胺、N，N-双烃基磺酰基取代的对苯二胺、N，N-双烃基酰基取代的对苯二胺、N，N-双烃基酰氧基取代的对苯二胺中的一种或几种。每个取代基的碳原子数优选为1-20，对于烷基取代基，优选碳原子数为4-10。Wherein the substituted p-phenylenediamine type antioxidant can be that the hydrogen atom in the amine group (-NH2 ) of p-phenylenediamine is replaced by one or more alkyl, aryl, aralkyl, alkylaryl , hydrocarbyl acyl, hydrocarbyl sulfonyl, hydrocarbyl acyloxy one or more substituted products, when two hydrogen atoms in the amine group are substituted, it can replace the hydrogen atom on the same amine group, or The hydrogen atoms on two amine groups may be substituted, and when there are two or more substituents, the substituents may be the same or different. That is to say, the substituted p-phenylenediamine antioxidant can be monoalkyl substituted p-phenylenediamine, monoaryl substituted p-phenylenediamine, monoalkylaryl substituted p-phenylenediamine, Monoarylalkyl substituted p-phenylenediamine, monohydrocarbyl acyl substituted p-phenylenediamine, monohydrocarbylsulfonyl substituted p-phenylenediamine, monohydrocarbyl acyloxy substituted p-phenylenediamine, N-alkyl- N'-alkyl substituted p-phenylenediamine, N-aryl-N'-alkyl substituted p-phenylenediamine, N-alkyl-N'-alkylaryl substituted p-phenylenediamine, N- Aryl-N'-alkyl substituted p-phenylenediamine, N-arylalkyl-N'-alkyl substituted p-phenylenediamine, N-arylalkyl-N'-aryl substituted p-phenylenediamine Diamine, N-arylalkyl-N'-hydrocarbyl acyl substituted p-phenylenediamine, N-arylalkyl-N'-hydrocarbylsulfonyl substituted p-phenylenediamine, N-arylalkyl-N '-hydrocarbyl acyloxy substituted p-phenylenediamine, N-aryl-N'-hydrocarbyl acyl substituted p-phenylenediamine, N-alkyl-N'-hydrocarbylsulfonyl substituted p-phenylenediamine, N- Alkyl-N'-hydrocarbyl acyloxy substituted p-phenylenediamine N-aryl-N'-hydrocarbyl acyl substituted p-phenylenediamine, N-alkyl-N'-hydrocarbylsulfonyl substituted p-phenylenediamine , N-alkyl-N'-hydrocarbyl acyloxy substituted p-phenylenediamine, N-alkylaryl-N'-hydrocarbyl acyl substituted p-phenylenediamine, N-alkylaryl-N'-hydrocarbyl Sulfonyl substituted p-phenylenediamine, N-alkylaryl-N'-hydrocarbyl acyloxy substituted p-phenylenediamine, N,N-dialkyl substituted p-phenylenediamine, N,N-bisaryl substituted p-phenylenediamine, N,N-dialkylaryl substituted p-phenylenediamine, N,N-bisarylalkyl substituted p-phenylenediamine, N,N-dialkylsulfonyl substituted One or more of p-phenylenediamine, N,N-dihydrocarbyl acyl substituted p-phenylenediamine, N,N-dihydrocarbyl acyloxy substituted p-phenylenediamine. The number of carbon atoms per substituent is preferably 1-20, and for an alkyl substituent, the number of carbon atoms is preferably 4-10.
具体的，所述取代的对苯二胺型抗氧剂包括但不限于下列物质中的一种或多种：Specifically, the substituted p-phenylenediamine antioxidants include but are not limited to one or more of the following substances:
N苯基-N’-环己基对苯二胺(防老剂4010)；N-phenyl-N'-cyclohexyl-p-phenylenediamine (antiaging agent 4010);
N，N-(1，3-二甲基丁基)-N’-苯基对苯二胺(防老剂4020)；N, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (antiaging agent 4020);
N，N’-双-(1，4-二甲基戊基)对苯二胺(防老剂4030)；N, N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine (antiaging agent 4030);
N-对甲苯基-N’-(1，3-二甲基丁基)对苯二胺(防老剂4040)；N-p-tolyl-N'-(1,3-dimethylbutyl) p-phenylenediamine (antiaging agent 4040);
N，N’-二庚基对苯二胺(防老剂788)；N, N'-diheptyl-p-phenylenediamine (antiaging agent 788);
N-异丙基-N’-苯基对苯二胺(防老剂4010NA)；N-isopropyl-N'-phenyl-p-phenylenediamine (antiaging agent 4010NA);
N-异丙基-N’-对甲基苯基对苯二胺(防老剂甲基4010NA)；N-isopropyl-N'-p-methylphenyl-p-phenylenediamine (antiaging agent methyl 4010NA);
N，N’-二甲苯基对苯二胺(防老剂PPD-A)；N, N'-xylyl-p-phenylenediamine (antiaging agent PPD-A);
N，N’-二苯基对苯二胺(防老剂H)；N, N'-diphenyl-p-phenylenediamine (antiaging agent H);
N，N’-二-(β-萘基)对苯二胺(防老剂DNP)；N, N'-di-(β-naphthyl)-p-phenylenediamine (antiaging agent DNP);
N，N’-二仲丁基对苯二胺(防老剂U-5)；N, N'-di-sec-butyl-p-phenylenediamine (antiaging agent U-5);
N，N’-二辛基对苯二胺(防老剂88)；N, N'-dioctyl-p-phenylenediamine (antiaging agent 88);
N，N’-双-(1-甲基庚基)对苯二胺(防老剂288)；N, N'-bis-(1-methylheptyl)-p-phenylenediamine (antiaging agent 288);
N，N’-双-(1-乙基-3-甲基戊基)对苯二胺(防老剂8L)；N, N'-bis-(1-ethyl-3-methylpentyl) p-phenylenediamine (antiaging agent 8L);
N，N’-双-(1，4-二甲基丁基)对苯二胺(防老剂66)；N, N'-bis-(1,4-dimethylbutyl)-p-phenylenediamine (antioxidant 66);
N-辛基-N’-苯基对苯二胺(防老剂688)；N-octyl-N'-phenyl-p-phenylenediamine (antiaging agent 688);
N-异丁基-N’-苯基对苯二胺(防老剂5L)；N-isobutyl-N'-phenyl-p-phenylenediamine (anti-aging agent 5L);
N，N’-二甲基-N，N’-双-(1-甲丙基)对苯二胺(防老剂32)；N, N'-dimethyl-N, N'-bis-(1-methylpropyl)-p-phenylenediamine (antiaging agent 32);
N-(对甲苯基磺酰基)-N’-苯基对苯二胺(防老剂TPPD)；N-(p-tolylsulfonyl)-N'-phenyl-p-phenylenediamine (anti-aging agent TPPD);
N-(3-甲基丙烯基酰氧代-2-羟基丙基)-N’-苯基对苯二胺(防老剂G-1)；N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine (antiaging agent G-1);
N-(3-苯胺基苯基)甲基丙烯酰胺；N-(3-anilinophenyl)methacrylamide;
N-己基-N’-苯基对苯二胺；N-hexyl-N'-phenyl-p-phenylenediamine;
本发明中，取代的对苯二胺型抗氧剂优选为对苯二胺的胺基中的氢原子被两个烷基或两个芳基或者一个烷基一个芳基取代的二烷基对苯二胺中的一种或几种，尤其优选对苯二胺的两个胺基分别被一个碳原子数在4-10之间的烷基或碳原子数为6-15的芳基取代的对苯二胺中的一种或几种取代的二烷基对苯二胺中的一种或几种，如：N，N’-二庚基对苯二胺；N，N’-二仲丁基对苯二胺；N，N’-二辛基对苯二胺；N，N’-双-(1-甲基庚基)对苯二胺中的一种或多种。In the present invention, the substituted p-phenylenediamine antioxidant is preferably a dialkyl pair in which the hydrogen atoms in the amine groups of p-phenylenediamine are substituted by two alkyl groups or two aryl groups or one alkyl group and one aryl group. One or more of phenylenediamines, especially preferably the two amine groups of p-phenylenediamine are respectively substituted by an alkyl group with 4-10 carbon atoms or an aryl group with 6-15 carbon atoms One or more of one or more substituted dialkyl-p-phenylenediamines in p-phenylenediamine, such as: N, N'-diheptyl-p-phenylenediamine; N, N'-disecondary One or more of butyl-p-phenylenediamine; N,N'-dioctyl-p-phenylenediamine; N,N'-bis-(1-methylheptyl)-p-phenylenediamine.
其中的取代的喹啉型抗氧剂包括但不限于：The substituted quinoline antioxidants include but are not limited to:
6-乙氧基-2，2，4-三甲基-1，2-二氢化喹啉(防老剂AW)；6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (antiaging agent AW);
6-苯基-2，2，4-三甲基-1，2-二氢化喹啉(防老剂PMQ)；6-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline (antiaging agent PMQ);
6-十二烷基-2，2，4-三甲基-1，2-二氢化喹啉(防老剂DD)；6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline (antiaging agent DD);
2，2，4-三甲基-1，2-二氢化喹啉聚合体(防老剂RD、防老剂124)；2,2,4-trimethyl-1,2-dihydroquinoline polymer (antiaging agent RD, antiaging agent 124);
二苯胺与丙酮低温反应产物(防老剂BAS)；Low temperature reaction product of diphenylamine and acetone (antiaging agent BAS);
二苯胺与丙酮高温反应产物(防老剂BLE)；High temperature reaction product of diphenylamine and acetone (antiaging agent BLE);
二苯胺与丙酮和醛的反应产物(防老剂BXA)；The reaction product of diphenylamine with acetone and aldehyde (antiaging agent BXA);
苯基-β-萘胺与丙酮的反应产物(防老剂APN、防老剂AM)。The reaction product of phenyl-β-naphthylamine and acetone (antiaging agent APN, antiaging agent AM).
芳胺抗氧剂优选取代的对苯二胺型芳胺抗氧剂。The aromatic amine antioxidant is preferably a substituted p-phenylenediamine type aromatic amine antioxidant.
本发明中，所述酚型抗氧剂可以是单酚、二酚、双酚或多酚，也可以是它们任意比例的混合物。In the present invention, the phenolic antioxidant may be monophenol, diphenol, bisphenol or polyphenol, or a mixture thereof in any proportion.
其中单酚是有一个苯环/并且苯环上有一个羟基的取代的苯酚，而且取代基中至少有一个是叔丁基，其它取代基可以是烃基或含有杂原子的取代基，其中的烃基选自C1-C10烷基，例如甲基、乙基、烯丙基、正丁基、仲丁基、壬基等，含有杂原子的取代基选自含氧的取代基如甲氧基、甲氧基取代的甲基、羟甲基，含氮的取代基如α-二甲胺基甲基。例如可以是下面结构的单酚：邻叔丁基苯酚、对叔丁基苯酚、2-叔丁基-4-甲基苯酚、6-叔丁基-2-甲基苯酚、6-叔丁基-3-甲基苯酚；4-叔丁基-2，6-二甲基苯酚、6-叔丁基-2，4-二甲基苯酚；2，4-二叔丁基苯酚、2，5-二叔丁基苯酚、2，6-二叔丁基苯酚；2，5-二叔丁基-4-甲基苯酚、2，6-二叔丁基-4-甲基苯酚(BHT，抗氧剂T501)、4，6-二叔丁基-2-甲基苯酚；2，4，6-三叔丁基苯酚、2-烯丙基-4-甲基-6-叔丁基苯酚、2-仲丁基-4-叔丁基苯酚、4-仲丁基-2，6-二叔丁基苯酚、4-壬基-2，6-二叔丁基苯酚、2，6-二叔丁基-4-乙基苯酚(抗氧剂DBEP)、2，6-二叔丁基-4-正丁基苯酚(抗氧剂678)；叔丁基羟基茴香醚(BHA)、2，6-二叔丁基-α-甲氧基-对甲酚(BHT-MO)、4-羟甲基-2，6-二叔丁基苯酚(抗氧剂754)、2，6-二叔丁基-α-二甲氨基-对甲酚(抗氧剂703)、各种3，5-二叔丁基-4-羟基苯基丙酸酯和3，5-二叔丁基-4-羟基苯基丙酸酰胺等。Among them, the monophenol is a substituted phenol with a benzene ring/and a hydroxyl group on the benzene ring, and at least one of the substituents is a tert-butyl group, and other substituents can be hydrocarbon groups or substituents containing heteroatoms, wherein the hydrocarbon group Selected from C1 -C10 alkyl groups, such as methyl, ethyl, allyl, n-butyl, sec-butyl, nonyl, etc., and the substituents containing heteroatoms are selected from oxygen-containing substituents such as methoxy , methoxy-substituted methyl, hydroxymethyl, nitrogen-containing substituents such as α-dimethylaminomethyl. For example, it can be a monophenol of the following structure: o-tert-butylphenol, p-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 6-tert-butyl -3-methylphenol; 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol; 2,4-di-tert-butylphenol, 2,5 -Di-tert-butylphenol, 2,6-di-tert-butylphenol; 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol (BHT, anti Oxygen T501), 4,6-di-tert-butyl-2-methylphenol; 2,4,6-tri-tert-butylphenol, 2-allyl-4-methyl-6-tert-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylphenol Butyl-4-ethylphenol (antioxidant DBEP), 2,6-di-tert-butyl-4-n-butylphenol (antioxidant 678); tert-butylhydroxyanisole (BHA), 2,6 -Di-tert-butyl-α-methoxy-p-cresol (BHT-MO), 4-hydroxymethyl-2,6-di-tert-butylphenol (antioxidant 754), 2,6-di-tert-butyl Base-α-dimethylamino-p-cresol (antioxidant 703), various 3,5-di-tert-butyl-4-hydroxyphenylpropionates and 3,5-di-tert-butyl-4-hydroxy Phenylpropionamide, etc.
其中单酚抗氧剂优选至少有一个叔丁基在酚羟基邻位的受阻单酚，如：Wherein the monophenol antioxidant preferably has at least one tert-butyl hindered monophenol at the ortho position of the phenolic hydroxyl group, such as:
2-叔丁基-4-甲基苯酚、6-叔丁基-2，4-二甲基苯酚、2，6-二叔丁基苯酚、2，6-二叔丁基-4-甲基苯酚(BHT，抗氧剂T501)、2，4，6-三叔丁基苯酚、4-仲丁基-2，6-二叔丁基苯酚、4-壬基-2，6-二叔丁基苯酚、2，6-二叔丁基-4-乙基苯酚(抗氧剂DBEP)、叔丁基羟基茴香醚(BHA)、2，6-二叔丁基-α-甲氧基-对甲酚(BHT-MO)、4-羟甲基-2，6-二叔丁基苯酚(抗氧剂754)、2，6-二叔丁基-α-二甲氨基-对甲酚(抗氧剂703)中的一种或几种。2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol Phenol (BHT, antioxidant T501), 2,4,6-tri-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butyl 2,6-di-tert-butyl-4-ethylphenol (antioxidant DBEP), tert-butylhydroxyanisole (BHA), 2,6-di-tert-butyl-α-methoxy-p Cresol (BHT-MO), 4-hydroxymethyl-2,6-di-tert-butylphenol (antioxidant 754), 2,6-di-tert-butyl-α-dimethylamino-p-cresol (antioxidant Oxygen agent 703) in one or more.
双酚是指由两个单酚相连形成的双酚，优选是指由两个单酚通过硫或碳原子相连的双酚型抗氧剂。所述由两个单酚通过硫或碳原子相连的双酚型抗氧剂可以是下述中的一种或几种：Bisphenols refer to bisphenols formed by linking two monophenols, and preferably refer to bisphenol antioxidants in which two monophenols are linked through sulfur or carbon atoms. The bisphenol type antioxidant linked by two monophenols through sulfur or carbon atoms can be one or more of the following:
(1)由碳原子相连的双酚(1) Bisphenol linked by carbon atoms
4，4’-异丙叉双酚(双酚A)；4,4'-isopropylidene bisphenol (bisphenol A);
2，2’-双-(3-甲基-4羟基苯基)丙烷(双酚C)；2,2'-bis-(3-methyl-4-hydroxyphenyl)propane (bisphenol C);
4，4’-二羟基联苯(抗氧剂DOD)；4,4'-dihydroxybiphenyl (antioxidant DOD);
4，4’-二羟基-3，3’，5，5’-四-叔丁基联苯(抗氧剂712)；4,4'-dihydroxy-3,3',5,5'-tetra-tert-butylbiphenyl (antioxidant 712);
2，2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)(抗氧剂双酚2246)；2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) (antioxidant bisphenol 2246);
4，4’-亚甲基-双-(2-甲基-6-叔丁基苯酚)(抗氧剂甲叉736)；4,4'-methylene-bis-(2-methyl-6-tert-butylphenol) (antioxidant methylene 736);
2，2’-亚甲基-双-(4-乙基-6-叔丁基苯酚)(抗氧剂425)；2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol) (antioxidant 425);
2，2’-亚甲基-双-(4-甲基-6-环己基苯酚)(抗氧剂ZKF)；2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol) (antioxidant ZKF);
2，2’-亚甲基-双[4-甲基-6-(α-甲基环己基)苯酚](抗氧剂WSP)；2,2'-methylene-bis[4-methyl-6-(α-methylcyclohexyl)phenol] (antioxidant WSP);
2，2’-亚甲基-双-(6-α-甲基苄基对甲酚)；2,2'-methylene-bis-(6-α-methylbenzyl-p-cresol);
4，4’-亚甲基-双-(2，6-二叔丁基苯酚)(抗氧剂T511)；4,4'-methylene-bis-(2,6-di-tert-butylphenol) (antioxidant T511);
4，4’-亚甲基-双-(2-叔丁基苯酚)(抗氧剂702)；4,4'-methylene-bis-(2-tert-butylphenol) (antioxidant 702);
2，2’-亚乙基-双-(4-甲基-6-叔丁基苯酚)；2,2'-Ethylene-bis-(4-methyl-6-tert-butylphenol);
4，4’-亚乙基-双-(2-甲基-6-叔丁基苯酚)；4,4'-Ethylene-bis-(2-methyl-6-tert-butylphenol);
4，4’-亚乙基-双-(2，6-二叔丁基苯酚)；4,4'-Ethylene-bis-(2,6-di-tert-butylphenol);
4，4’-亚丁基-双-(6-叔丁基-间甲酚)(抗氧剂BBM、抗氧剂TCA)；4,4'-butylene-bis-(6-tert-butyl-m-cresol) (antioxidant BBM, antioxidant TCA);
4，4’-亚异丁基-双-(2，6-二叔丁基苯酚)等。4,4'-isobutylene-bis-(2,6-di-tert-butylphenol), etc.
(2)由硫原子相连的双酚(2) bisphenols connected by sulfur atoms
4，4’-硫代双-(3-甲基-6-叔丁基苯酚)(抗氧剂300或AO-1)；4,4'-thiobis-(3-methyl-6-tert-butylphenol) (antioxidant 300 or AO-1);
2，2’-硫代双-(4-甲基-6-叔丁基苯酚)(抗氧剂2246-S)；2,2'-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4，4’-硫代双-(2-甲基-6-叔丁基苯酚)(抗氧剂736)；4,4'-thiobis-(2-methyl-6-tert-butylphenol) (antioxidant 736);
4，4’-硫代双-(5-甲基-2-叔丁基苯酚)；4,4'-thiobis-(5-methyl-2-tert-butylphenol);
4，4’-硫代双-(2，6-二叔丁基苯酚)(Nocrac300)；4,4'-thiobis-(2,6-di-tert-butylphenol) (Nocrac300);
2，2’-硫代双-(4-辛基苯酚)等。2,2'-thiobis-(4-octylphenol), etc.
(3)由碳原子相连但含有杂原子的双酚(3) Bisphenols connected by carbon atoms but containing heteroatoms
N，N’-六甲撑双-(3，5-二叔丁基-4-羟基苯丙酰胺)(抗氧剂1098)；N, N'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyphenylpropanamide) (antioxidant 1098);
己二醇双[β-(3，5-二叔丁基-4-羟基苯基)丙酸酯](抗氧剂259)；Hexylene glycol bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 259);
双-(3，5-二叔丁基-4-羟基苯基丙酸丙酰)联氨(抗氧剂BPP)；Bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl propionyl) hydrazine (antioxidant BPP);
双-(3，5-二叔丁基-4-羟基苄基)硫醚(抗氧剂甲叉4426-S)；Bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide (antioxidant methylene 4426-S);
2，2’-亚硫基乙二醇双[β-(3，5-二叔丁基-4-羟基苯基)丙酸酯](抗氧剂1035)；2,2'-thioethylene glycol bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1035);
三甘醇双-3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯(抗氧剂245)等。Triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245), etc.
双酚型抗氧剂优选至少有一个叔丁基在酚羟基邻位的双酚型抗氧剂，进一步优选由两个至少有一个叔丁基在酚羟基邻位的单酚通过亚甲基或硫相连的双酚，例如下述物质中的一种或几种：The bisphenol type antioxidant preferably has at least one tert-butyl group in the bisphenol type antioxidant at the ortho position of the phenolic hydroxyl group, and is further preferably composed of two monophenols with at least one tert-butyl group at the ortho position of the phenolic hydroxyl group through methylene or Sulfur-linked bisphenols, such as one or more of the following:
2，2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)(抗氧剂2246)；2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) (antioxidant 2246);
4，4’-亚甲基-双-(2-甲基-6-叔丁基苯酚)(抗氧剂甲叉736)；4,4'-methylene-bis-(2-methyl-6-tert-butylphenol) (antioxidant methylene 736);
4，4’-亚甲基-双-(2，6-二叔丁基苯酚)(抗氧剂T511)；4,4'-methylene-bis-(2,6-di-tert-butylphenol) (antioxidant T511);
4，4’-亚甲基-双-(2-叔丁基苯酚)(抗氧剂702)；4,4'-methylene-bis-(2-tert-butylphenol) (antioxidant 702);
4，4’-硫代双-(3-甲基-6-叔丁基苯酚)(抗氧剂300或AO-1)；4,4'-thiobis-(3-methyl-6-tert-butylphenol) (antioxidant 300 or AO-1);
2，2’-硫代双-(4-甲基-6-叔丁基苯酚)(抗氧剂2246-S)；2,2'-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4，4’-硫代双-(2-甲基-6-叔丁基苯酚)(抗氧剂736)；4,4'-thiobis-(2-methyl-6-tert-butylphenol) (antioxidant 736);
4，4’-硫代双-(2，6-二叔丁基苯酚)(Nocrac300)；4,4'-thiobis-(2,6-di-tert-butylphenol) (Nocrac300);
双-(3，5-二叔丁基-4-羟基苄基)硫醚(抗氧剂甲叉4426-S)等。Bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide (antioxidant methylene 4426-S), etc.
酚型抗氧剂还可以是二酚型抗氧剂，这里的“二酚”是指一个苯环上有两个羟基的酚型抗氧剂，可以是下面结构的二酚：对苯二酚、叔丁基对苯二酚(TBHQ)、2，5-二叔丁基对苯二酚、2，5-二叔戊基对苯二酚中的一种或几种。The phenolic antioxidant can also be a diphenolic antioxidant. The "diphenol" here refers to a phenolic antioxidant with two hydroxyl groups on a benzene ring, which can be a diphenol with the following structure: hydroquinone , tert-butylhydroquinone (TBHQ), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone or one or more of them.
所述多酚型抗氧剂是指同一个酚型抗氧剂分子中含有多个酚羟基的酚，酚羟基的个数为三个或三个以上，多个酚羟基可以位于同一个苯环上，也可以位于不同苯环上，本发明优选所述多酚型抗氧剂为分子中含有至少三个单酚基团的大分子抗氧剂，即一个酚型抗氧剂中至少含有三个苯环，且至少有三个苯环上各自具有至少一个酚羟基，优选所述多酚型抗氧剂为由至少有一个叔丁基在酚羟基邻位的单酚基团组成的多酚，尤其优选有两个叔丁基在酚羟基邻位的受阻多酚，例如下述物质中的一种或几种：The polyphenolic antioxidant refers to the phenol containing multiple phenolic hydroxyl groups in the same phenolic antioxidant molecule. The number of phenolic hydroxyl groups is three or more, and multiple phenolic hydroxyl groups can be located in the same benzene ring. It can also be located on different benzene rings. In the present invention, the polyphenolic antioxidant is preferably a macromolecular antioxidant containing at least three monophenolic groups in the molecule, that is, a phenolic antioxidant contains at least three benzene rings, and at least three benzene rings each have at least one phenolic hydroxyl group, preferably the polyphenolic antioxidant is a polyphenol consisting of a monophenolic group with at least one tert-butyl group at the ortho position of the phenolic hydroxyl group, Especially preferred are hindered polyphenols with two tert-butyl groups at the ortho-position of the phenolic hydroxyl group, such as one or more of the following substances:
1，3，5-三甲基-2，4，6-三-(4’-羟基-3’，5’-二叔丁基)苯(抗氧剂330)；1,3,5-Trimethyl-2,4,6-tri-(4'-hydroxy-3',5'-di-tert-butyl)benzene (antioxidant 330);
三[2-(3，5-二叔丁基-4-羟基苯基)丙酰基氧乙基]异氰酸酯(抗氧剂3125)；Tris[2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanate (antioxidant 3125);
四(3，5-二叔丁基-4-羟基苯基丙酸)季戊四醇酯(抗氧剂1010)；Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) pentaerythritol ester (antioxidant 1010);
1，3，5-三(3，5-二叔丁基-4-羟基苄基)均三嗪-2，4，6-(1H，3H，5H)(抗氧剂3114)；1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H) (antioxidant 3114);
1，1，3-三-(2-甲基-4-羟基-5-叔丁基苯基)丁烷(抗氧剂CA)；1,1,3-tri-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA);
1，3，5-三(2，6-二甲基-4-叔丁基-3-羟基苄基)均三嗪-2，4，6-(1H，3H，5H)(抗氧剂1790)；1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H) (antioxidant 1790 );
双[3，3-双-(3’-叔丁基-4’-羟基苄基)丁酸]乙二醇酯等。Bis[3,3-bis-(3'-tert-butyl-4'-hydroxybenzyl)butanoic acid]ethylene glycol ester, etc.
这里的多酚还可以是苯环中带有三个羟基的酚，例如焦性没食子酸、没食子酸酯如没食子酸甲酯、没食子酸乙酯、没食子酸丙酯、没食子酸丁酯、没食子酸戊酯、没食子酸己酯、没食子酸庚酯、没食子酸辛酯、没食子酸壬酯、没食子酸癸酯、没食子酸十二酯、没食子酸十四酯、没食子酸十六酯、没食子酸十八酯、没食子酸十八烯酯等；以及CN200810115581.8所公开的没食子酸酰胺或氨盐。多酚型抗氧剂优选没食子酸衍生物如没食子酸的酯化产物尤其是没食子酸丙酯。The polyphenols here can also be phenols with three hydroxyl groups in the benzene ring, such as pyrogallic acid, gallic acid esters such as methyl gallate, ethyl gallate, propyl gallate, butyl gallate, pentyl gallate ester, hexyl gallate, heptyl gallate, octyl gallate, nonyl gallate, decyl gallate, lauryl gallate, tetradecyl gallate, cetyl gallate, octadecyl gallate, Octadecenyl gallate, etc.; and gallic acid amide or ammonium salt disclosed in CN200810115581.8. The polyphenolic antioxidant is preferably a gallic acid derivative such as an esterification product of gallic acid, especially propyl gallate.
本发明所述酚型抗氧剂优选由两个单酚通过硫或碳原子相连的双酚型抗氧剂和有两个叔丁基在酚羟基邻位的受阻多酚中的一种或几种。本发明最优选所述酚型抗氧剂选自2，2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)、4，4’-亚甲基-双-(2-甲基-6-叔丁基苯酚)、4，4’-亚甲基-双-(2，6-二叔丁基苯酚)、4，4’-亚甲基-双-(2-叔丁基苯酚)、4，4’-硫代双-(3-甲基-6-叔丁基苯酚)、2，2’-硫代双-(4-甲基-6-叔丁基苯酚)、4，4’-硫代双-(2-甲基-6-叔丁基苯酚)、4，4’-硫代双-(2，6-二叔丁基苯酚)、双-(3，5-二叔丁基-4-羟基苄基)硫醚中的一种或几种。The phenolic antioxidant of the present invention is preferably composed of two monophenolic bisphenolic antioxidants linked by sulfur or carbon atoms and one or more of the hindered polyphenols with two tert-butyl groups in the ortho position of the phenolic hydroxyl group. kind. The most preferred phenolic antioxidant of the present invention is selected from 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 4,4'-methylene-bis-( 2-methyl-6-tert-butylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 4,4'-methylene-bis-(2- tert-butylphenol), 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2'-thiobis-(4-methyl-6-tert-butylphenol ), 4,4'-thiobis-(2-methyl-6-tert-butylphenol), 4,4'-thiobis-(2,6-di-tert-butylphenol), bis-(3 , One or more of 5-di-tert-butyl-4-hydroxybenzyl) sulfides.
组分a还可以是所述酚型抗氧剂与芳胺型抗氧剂的复合抗氧剂，所述酚型抗氧剂与芳胺型抗氧剂的重量比优选为0-10∶1，进一步优选为0.2-5∶1。Component a can also be a composite antioxidant of the phenolic antioxidant and the arylamine antioxidant, and the weight ratio of the phenolic antioxidant to the arylamine antioxidant is preferably 0-10:1 , more preferably 0.2-5:1.
本发明中，最优选所述组分a为N，N’-二庚基对苯二胺、N，N’-二仲丁基对苯二胺、N，N’-二辛基对苯二胺、N，N’-双-(1-甲基庚基)对苯二胺、2，2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)、4，4’-亚甲基-双-(2-甲基-6-叔丁基苯酚)、4，4’-亚甲基-双-(2，6-二叔丁基苯酚)、4，4’-亚甲基-双-(2-叔丁基苯酚)、4，4’-硫代双-(3-甲基-6-叔丁基苯酚)、2，2’-硫代双-(4-甲基-6-叔丁基苯酚)、4，4’-硫代双-(2-甲基-6-叔丁基苯酚)、4，4’-硫代双-(2，6-二叔丁基苯酚)、双-(3，5-二叔丁基-4-羟基苄基)硫醚中的一种或几种。In the present invention, the most preferred component a is N,N'-diheptyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-dioctyl-p-phenylenediamine Amine, N,N'-bis-(1-methylheptyl)-p-phenylenediamine, 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 4,4 '-Methylene-bis-(2-methyl-6-tert-butylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 4,4'- Methylene-bis-(2-tert-butylphenol), 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2'-thiobis-(4- Methyl-6-tert-butylphenol), 4,4'-thiobis-(2-methyl-6-tert-butylphenol), 4,4'-thiobis-(2,6-di-tert One or more of butylphenol), bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide.
组分bComponent b
所述组分b是氨与C-C6醛的缩合反应产物和/或胺与C1-C6的醛的缩合反应产物。氨和胺与醛的缩合反应属于本领域已经公知的技术，其产物主要为取代三嗪或取代甲烷，反应的条件一般包括所述氨和胺的总量与C1-C6的醛的比例可以为摩尔比1∶(0.1-10)，优选1∶0.2-5，更优选1∶0.3-3；反应可以不用溶剂也可以加入烃类溶剂如己烷、庚烷、甲苯、二甲苯等回流分水反应；反应的温度一般为80-150℃；反应的时间以反应不再出水为基准，一般为30分钟至10小时。The component b is a condensation reaction product of ammonia and C-C6 aldehydes and/or a condensation reaction product of amines and C1-C6 aldehydes. The condensation reaction of ammonia and amines and aldehydes belongs to the known technology in the art, and its products are mainly substituted triazines or substituted methanes. The conditions of the reaction generally include that the ratio of the total amount of ammonia and amines to C1-C6 aldehydes can be The molar ratio is 1: (0.1-10), preferably 1: 0.2-5, more preferably 1: 0.3-3; the reaction can be done without a solvent or by adding a hydrocarbon solvent such as hexane, heptane, toluene, xylene, etc. to reflux and divide water Reaction; the reaction temperature is generally 80-150°C; the reaction time is based on the fact that the reaction no longer produces water, generally 30 minutes to 10 hours.
本发明中，所述胺可以是如式B3所示的有机胺，In the present invention, the amine can be an organic amine as shown in formula B3,
其中，R1和R2各自可以为碳原子数为1-30的烃基或带杂原子的基团，或者R1和R2其中之一为H，另一个为碳原子数为1-30的烃基或带杂原子的基团，所述带杂原子的基团可以是含有羰基、羟基、羧基、酯基、酰基、烷氧基、硝基、氰基、卤基、胺基或者氨基的基团。即B3可以是伯胺，还可以是仲胺，也可以是氨、伯胺和仲胺中一种或几种的混合物。“烃基”指烃取代基，即脂肪族、脂环族、芳族以及杂环取代基。脂肪族烃基可以是饱和的也可以是不饱和的带双键或三键的烃基。Wherein , each of R1 and R2 can be a hydrocarbon group with1-30 carbon atoms or a group with aheteroatom , orone of R1 and R2 is H, and the other is a hydrocarbon group with 1-30 carbon atoms A hydrocarbon group or a group with a heteroatom, and the group with a heteroatom can be a group containing a carbonyl group, a hydroxyl group, a carboxyl group, an ester group, an acyl group, an alkoxy group, a nitro group, a cyano group, a halogen group, an amino group or an amino group group. That is, B3 can be a primary amine, a secondary amine, or a mixture of one or more of ammonia, primary amine and secondary amine. "Hydrocarbyl" refers to hydrocarbon substituents, ie, aliphatic, cycloaliphatic, aromatic and heterocyclic substituents. Aliphatic hydrocarbon groups can be saturated or unsaturated hydrocarbon groups with double or triple bonds.
(1)当R1和R2其中之一为H，另一个为碳原子数为1-30的烃基的伯胺时，该伯胺可以是碳原子数为1-30的脂肪胺，也可以是碳原子数为6-30的芳胺，优选碳原子数为1-24的脂肪胺，脂肪伯胺可以是直链的脂肪胺，如甲胺、乙胺、正丙胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一胺、正十二胺(月桂胺)、正十四胺、正十六胺、正十八胺、正二十胺、正二十二胺中的一种或几种，也可以是带有支链的脂肪伯胺，这些带有支链的脂肪伯胺是上述直链脂肪伯胺的各种异构体，例如异丙胺、异丁胺、叔丁胺、异戊胺、新戊胺、异己胺、异庚胺、异辛胺(2-乙基己胺)、异壬胺、异癸胺、异十二胺、异十四胺、异十六胺、异十八胺、异二十胺中的一种或几种。脂肪伯胺还可以是带有脂肪环的胺，如环戊胺和/或环己胺，也可以是碳链中含有不饱和双键或三键的脂肪伯胺，如油胺(十八烯胺)、棕榈油胺(十六烯胺)，还可以是叔碳伯胺，例如Rohm&Haas公司生产的商品牌号为Primere81R的叔碳伯胺。(1) When one of R and R is H, and the other is a primary amine of a hydrocarbon group with 1-30 carbon atoms, the primary amine can be an aliphatic amine with 1-30 carbon atoms, or It is an aromatic amine with a carbon number of 6-30, preferably an aliphatic amine with a carbon number of 1-24. The primary aliphatic amine can be a straight-chain aliphatic amine, such as methylamine, ethylamine, n-propylamine, n-butylamine, n- Pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine (laurylamine), n-tetradecylamine, n-hexadecylamine, n-octadecylamine , n-eicosylamine, n-docosylamine, or one or more kinds of fatty primary amines with branched chains. These primary fatty amines with branched chains are all kinds of the above-mentioned straight chain primary fatty amines Isomers such as isopropylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, isohexylamine, isoheptylamine, isooctylamine (2-ethylhexylamine), isononylamine, isodecylamine, One or more of dodecylamine, isotetradecylamine, isohexadecylamine, isostearylamine, and isoeicosylamine. Primary aliphatic amines can also be amines with aliphatic rings, such as cyclopentylamine and/or cyclohexylamine, or primary aliphatic amines containing unsaturated double bonds or triple bonds in the carbon chain, such as oleylamine (octadecene amine), palm oil amine (hexadecenylamine), can also be tertiary carbon primary amine, such as the trade mark that Rohm&Haas company produces is the tertiary carbon primary amine of Primere81R.
如果是仲胺，其中R1、R2可以相同，也可以不同，优选各自可以是碳原子数为1-24的正构烷基，如甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基(月桂基)、正十四烷基、正十六烷基、正十八烷基、正二十烷基或正二十二烷基，也可以是带有支链的碳原子数为1-24的异构烷基，如异丙基、异丁基、叔丁基、异戊基、新戊基、异己基、异庚基、异辛基(2-乙基己基)、异壬基、异癸基、异十二烷基、异十四烷基、异十六烷基、异十八烷基或异二十烷基。If it is a secondary amine, wherein R1 and R2 can be the same or different, preferably each can be a normal alkyl group with 1-24 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl (lauryl), n-tetradecyl, n-hexadecyl , n-octadecyl, n-eicosyl or n-docosyl, also can be isomeric alkyl with branched carbon number of 1-24, such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isotetradecyl, Isohexadecyl, isostearyl or isoeicosyl.
(2)R1、R2至少一个是碳原子数为1-30的带杂原子的基团，另一个为H或碳原子数为1-30的烃基。(2) At least one of R1 and R2 is a heteroatom-bearing group with 1-30 carbon atoms, and the other is H or a hydrocarbon group with 1-30 carbon atoms.
其中含有羟基的胺可以是醇胺或氨基酚，例如乙醇胺、二乙醇胺、N-烷基乙醇胺、N-烯基乙醇胺、N-烷基异丙醇胺、N-烯基异丙醇胺、异丙醇胺、二异丙醇胺、三羟甲基氨基甲烷、3-氨基-1，2-丙二醇、2-氨基-1，3-丙二醇、3-氨基丙醇、4-氨基-1-丁醇、5-氨基-1-戊醇、6-氨基-1-己醇、4-氨基苯酚中的-种或几种。The amines containing hydroxyl groups can be alcoholamines or aminophenols, such as ethanolamines, diethanolamines, N-alkylethanolamines, N-alkenyl ethanolamines, N-alkylisopropanolamines, N-alkenylisopropanolamines, iso Propanolamine, Diisopropanolamine, Trishydroxymethylaminomethane, 3-Amino-1,2-Propanediol, 2-Amino-1,3-Propanediol, 3-Aminopropanol, 4-Amino-1-Butane One or more of alcohol, 5-amino-1-pentanol, 6-amino-1-hexanol, and 4-aminophenol.
R1、R2至少一个是胺基或氨基的胺为多胺化合物，这里的多胺指分子中含有两个或两个以上氮原子的胺，如结构式为H2N-R3-NHR4的胺，这里的R3可以是碳数为1-30的亚烷基，烯基、环烷基、芳基或聚醚基等；R4可以是氢、碳数为1-30的烃基。例如乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺、癸二胺、椰子油基1，3-丙二胺、油基1，3-丙二胺、牛脂基1，3-丙二胺。还可以是如下式B4所示的聚醚二胺：R1 , R2 at least one of which is an amino group or an amino group is a polyamine compound, where the polyamine refers to an amine containing two or more nitrogen atoms in the molecule, such as an amine with a structural formula of H2 NR3 -NHR4 , whereR3 can be an alkylene group with a carbon number of 1-30, an alkenyl group, a cycloalkyl group, an aryl group or a polyether group, etc.;R4 can be hydrogen or a hydrocarbon group with a carbon number of 1-30. For example, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyldiamine, decanediamine, coconut oil-based 1,3-propylenediamine, oleyl-1,3- Propylenediamine, tallow 1,3-propanediamine. Can also be the polyether diamine shown in following formula B4:
其中x1为1-5的整数，R4可以是氢、碳数为1-30的烃基；R5是氢或甲基。Wherein x1 is an integer of 1-5, R4 can be hydrogen, a hydrocarbon group with a carbon number of 1-30; R5 is hydrogen or methyl.
多胺还可以是多烯多胺，多烯多胺的结构式为H2N[(CH2)x2NH]y1R6，其中，x2可以为2-4的整数，优选为2或3，y1可以为1-8的整数，R6可以是氢、碳数为1-30的烃基。例如，当R6为H时，所述多烯多胺可以为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、六乙烯七胺、七乙烯八胺、丙二胺、二丙烯三胺、三丙烯四胺、四丙烯五胺、五丙烯六胺、六丙烯七胺、七丙烯八胺中的一种或几种。当R6为碳原子数为1-30的烃基时，优选为碳原子数为4-22的烃基。该烃基可以是饱和的烷基，也可以是带有双键的烯基或带有苯环的芳基。烷基可以是直链正构烷基，也可以是带有侧链的异构烷基，该烷基可以是正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、正二十烷基、正二十二烷基；异丁基、叔丁基、异戊基、新戊基，异己基、异庚基、异辛基(2-乙基己基)、异壬基、异癸基、异十二烷基、异十四烷基、异十六烷基、异十八烷基和异二十烷基中的一种或几种。烯基的例子包括9-十八烯基。带有苯环的芳基可以是苯甲基(苄基)、苯乙基和苯丙基中的一种或几种。其中，更优选C6-C20的烷基。The polyene polyamine can also be polyene polyamine, the structural formula of polyene polyamine is H2 N[(CH2 )x2 NH]y1 R6 , wherein, x2 can be an integer of 2-4, preferably 2 or 3, y1 Can be an integer of 1-8,R6 can be hydrogen, a hydrocarbon group with a carbon number of 1-30. For example, when R is H, the polyene polyamine can be ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine,heptaethyleneoctamine , propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentaamine, pentapropylenehexamine, hexapropyleneheptamine, heptapropyleneoctamine, or one or more of them. When R6 is a hydrocarbon group with 1-30 carbon atoms, it is preferably a hydrocarbon group with 4-22 carbon atoms. The hydrocarbon group may be a saturated alkyl group, an alkenyl group with a double bond or an aryl group with a benzene ring. Alkyl can be straight chain normal alkyl or isomeric alkyl with side chain, the alkyl can be n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl; isobutyl Base, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isotetradecyl One or more of isohexadecyl, isoctadecyl and isoeicosyl. Examples of alkenyl include 9-octadecenyl. The aryl group with a benzene ring can be one or more of benzyl (benzyl), phenethyl and phenylpropyl. Among them, a C6-C20 alkyl group is more preferred.
这里的多胺还可以是含氮杂环的胺，包括但不限于咪唑啉型、哌嗪型和哌啶型的胺中的一种或几种。The polyamine here can also be a nitrogen-containing heterocyclic amine, including but not limited to one or more of imidazoline-type, piperazine-type and piperidine-type amines.
咪唑啉型多胺如下式B5所示：The imidazoline polyamine is shown in the following formula B5:
其中y2为0-5的整数，R7为C1-C24的烃基。优选为C4-C22的烃基。该烃基可以是饱和的烷基，也可以是带有双键的烯基或带有苯环的芳基。烷基可以是直链正构烷基，也可以是带有侧链的异构烷基，该烷基可以是正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、正二十烷基、正二十二烷基、异丁基、叔丁基、异戊基、新戊基、异己基、异庚基、异辛基(2-乙基己基)、异壬基、异癸基、异十二烷基、异十四烷基、异十六烷基、异十八烷基和异二十烷基中的一种或几种。烯基的例子包括9-十八烯基。带有苯环的芳基可以是苯甲基(苄基)、苯乙基和苯丙基中的一种或几种。其中，进一步优选y2为1-3的整数，R7为C6-C20的烷基或烯基。Wherein y2 is an integer of 0-5, and R7 is a C1 -C24 hydrocarbon group. Preferably it is a C4 -C22 hydrocarbon group. The hydrocarbon group may be a saturated alkyl group, an alkenyl group with a double bond or an aryl group with a benzene ring. Alkyl can be straight chain normal alkyl or isomeric alkyl with side chain, the alkyl can be n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-dodecyl, isobutyl Base, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isotetradecyl One or more of isohexadecyl, isoctadecyl and isoeicosyl. Examples of alkenyl include 9-octadecenyl. The aryl group with a benzene ring can be one or more of benzyl (benzyl), phenethyl and phenylpropyl. Among them, it is further preferred that y2 is an integer of 1-3, and R7 is a C6 -C20 alkyl or alkenyl group.
哌嗪型多胺如下式B6所示：Piperazine type polyamine is shown in following formula B6:
其中R8为H或C1-C24的烃基，x3为0-5的整数。优选典型的哌嗪型多胺为N-(2-氨基乙基)哌嗪。Wherein R8 is H or a C1 -C24 hydrocarbon group, and x3 is an integer of 0-5. A preferred typical piperazine-type polyamine is N-(2-aminoethyl)piperazine.
哌啶型的多胺如4-氨基-2，2，6，6-四甲基哌啶、4-氨基-1，2，2，6，6-五甲基哌啶等。Piperidine type polyamines such as 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethylpiperidine and the like.
这里的多胺还可以是如式B7、B8所示的含叔胺的多胺。The polyamine here can also be a polyamine containing a tertiary amine as shown in formulas B7 and B8.
其中R9、R10为或C1-C24的烃基，x4为0-10的整数。优选R9、R10为C1-C10的烃基，x4为1-8的整数。例如N，N-二甲基-1，3-丙二胺、N，N-二乙基-1，3-丙二胺、N，N-二甲基-1，4-丁二胺、N，N-二乙基-1，4-丁二胺、N，N-二甲基-1，6-己二胺中的一种或几种。Wherein R9 and R10 are C1 -C24 hydrocarbon groups, and x4 is an integer of 0-10. Preferably, R9 and R10 are C1-C10 hydrocarbon groups, and x4 is an integer of 1-8. For example, N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, N,N-dimethyl-1,4-butanediamine, N , one or more of N-diethyl-1,4-butanediamine, N,N-dimethyl-1,6-hexanediamine.
其中x5为1-10的整数，优选为2-6的整数，例如三(2-氨基乙基)胺。Where x5 is an integer of 1-10, preferably an integer of 2-6, such as tris(2-aminoethyl)amine.
多胺还可以是结构式为H2N[(CH2)x2NH]y1R6的多烯多胺与环氧乙烷、环氧丙烷的缩合物。其中，x2可以为2-4的整数，优选为2或3，y1可以为1-8的整数，R6可以是氢或碳数为1-30的烃基，优选为氢或碳数为C4-C22的烷基或烯基。The polyamine can also be a condensation product of polyene polyamine with structural formula H2 N[(CH2 )x2 NH]y1 R6 and ethylene oxide or propylene oxide. Wherein, x2 can be an integer of 2-4, preferably 2 or3 , y1 can be an integer of 1-8, R6 can be hydrogen or a hydrocarbon group with a carbon number of 1-30, preferably hydrogen or a carbon number ofC4 -C22 alkyl or alkenyl.
所述胺还可以是下述高分子胺型无灰分散剂，这些无灰分散剂包括烯基丁二酰亚胺和/或烯基丁二酸酰胺、曼尼西碱型无灰分散剂、聚醚胺型无灰分散剂和聚烯烃胺型无灰分散剂。所述烯基丁二酰亚胺和/或基丁二酸酰胺无灰分散剂例如数均相对分子质量在500-3000的聚烯烃基丁二酸酐和/或数均相对分子质量在500-3000的聚烯烃基丁二酸与胺的反应产物；曼尼西碱型无灰分散剂例如数均相对分子质量在500-3000的聚烯烃基苯酚与甲醛和胺的缩合产物；所述聚醚胺型无灰分散剂例如C8-C30烷基酚与环氧乙烷或环氧丙烷加合后再与胺缩合的产物或者是C8-C30醇与环氧乙烷或环氧丙烷加合后再与胺缩合的产物；所述聚烯烃胺型无灰分散剂例如氯化聚烯烃与胺反应生成的聚烯烃基胺。这里所说的胺都优选多胺，尤其是如上文所说的多烯多胺。The amine can also be the following high molecular weight amine type ashless dispersant, these ashless dispersants include alkenyl succinimide and/or alkenyl succinic acid amide, Mannich base type ashless dispersant, polyether amine Type ashless dispersant and polyolefin amine type ashless dispersant. The alkenyl succinimide and/or succinic acid amide ashless dispersant such as polyalkenyl succinic anhydride with a number average relative molecular mass of 500-3000 and/or a polyalkenyl succinic anhydride with a number average relative molecular mass of 500-3000 The reaction product of polyolefin-based succinic acid and amine; Mannich base type ashless dispersant, such as the condensation product of polyolefin-based phenol with formaldehyde and amine in the number average relative molecular weight of 500-3000; the polyetheramine-type ashless dispersant Ash dispersants such as C8-C30 alkylphenols are added to ethylene oxide or propylene oxide and then condensed with amines, or C8-C30 alcohols are added to ethylene oxide or propylene oxide and then condensed with amines Product; said polyolefin amine type ashless dispersant, such as polyolefin-based amine produced by the reaction of chlorinated polyolefin and amine. The amines mentioned here are all preferably polyamines, especially polyene polyamines as mentioned above.
本发明组分b中所述的胺可以是上述胺的复合胺。The amine described in component b of the present invention may be a complex amine of the above-mentioned amines.
本发明B3所述的胺优选为多胺，进一步优选含至少一个伯胺基团的多胺，尤其优选上述多烯多胺、咪唑啉型、哌嗪型和哌啶型的胺中的一种或几种，特别优选多烯多胺和哌嗪型多胺中的一种或几种。The amine described in B3 of the present invention is preferably a polyamine, more preferably a polyamine containing at least one primary amino group, especially preferably one of the above-mentioned polyene polyamines, imidazoline type, piperazine type and piperidine type amines or several, particularly preferably one or more of polyene polyamines and piperazine polyamines.
本发明组分b中所述的胺优选含多胺，进一步优选含至少一个伯胺基团的多胺，尤其优选含多烯多胺的胺。The amines mentioned in component b of the present invention are preferably polyamine-containing, further preferably polyamine-containing at least one primary amino group, especially preferably polyene-polyamine-containing amines.
所述C1-C6的醛可以是甲醛、乙醛、丙醛、环己醛中的一种或几种，优选为甲醛、多聚甲醛和甲醛溶液如福尔马林中的一种或几种。The C1-C6 aldehyde can be one or more of formaldehyde, acetaldehyde, propionaldehyde and cyclohexanal, preferably one or more of formaldehyde, paraformaldehyde and formaldehyde solution such as formalin.
组分ccomponent c
优选情况下，本发明提供的添加剂组合物还含有组分c，所述组分c可以为各种能与金属表面反应的金属减活剂和/或与金属或金属离子反应或者结合的金属螯合剂。所述组分a与组分c的重量比可以为1∶0-1，优选所述组分a与所述组分c的重量比为1∶0.01-1，进一步优选为1∶0.01-0.5，更进一步优选为1∶0.02-0.2。Preferably, the additive composition provided by the present invention also contains component c, which can be various metal deactivators that can react with metal surfaces and/or metal chelates that can react or combine with metals or metal ions mixture. The weight ratio of component a to component c may be 1:0-1, preferably the weight ratio of component a to component c is 1:0.01-1, more preferably 1:0.01-0.5 , more preferably 1:0.02-0.2.
具体的，所述组分c可以为苯三唑及其衍生物、噻二唑及其衍生物、8-羟基喹啉、乙二胺四羧酸、酰肼、β-二酮、β-酮酯、席夫碱(Schiffbases)、有机多元羧酸及其衍生物中的一种或几种。由于苯三唑本身在生物柴油中的溶解性并不非常优异，因此，为了增加其在生物柴油中的溶解性，通常对苯三唑进行改性，改性的方法主要通过在苯三唑中引入油溶性基团如长链烃基。因此，所述苯三唑衍生物可以是各种在生物柴油中的溶解性较苯三唑本身好的各种衍生物。具体的，所述苯三唑衍生物可以是苯三唑与脂肪胺形成的铵盐以及苯三唑、甲醛与脂肪胺通过曼尼西反应得到的产物中的一种或几种。所述乙二胺四羧酸可以是乙二胺四乙酸(EDTA)，所述酰肼可以是N-水杨叉-N’-水杨酰肼和/或N，N’-二乙酰基己二酰基二酰肼。所述β-二酮如乙酰丙酮，所述β-酮酯如乙酰乙酸辛酯。所述席夫碱可以是N，N’-二水杨叉-1，2-乙二胺、N，N’-二水杨叉-1，2-丙二胺、N，N’-二水杨叉-1，2-环己二胺、N，N’-二水杨叉-N’-甲基二丙烯三胺中的一种或几种。所述有机多元羧酸及其衍生物例如可以是柠檬酸、酒石酸、苹果酸、琥珀酸(丁二酸)、马来酸、植酸等及其衍生物中的一种或几种。Specifically, the component c can be benzotriazole and its derivatives, thiadiazole and its derivatives, 8-hydroxyquinoline, ethylenediaminetetracarboxylic acid, hydrazide, β-diketone, β-ketone One or more of esters, Schiff bases, organic polycarboxylic acids and their derivatives. Since the solubility of benzotriazole itself in biodiesel is not very excellent, in order to increase its solubility in biodiesel, benzotriazole is usually modified, and the method of modification is mainly through Introduce oil-soluble groups such as long-chain hydrocarbon groups. Therefore, the benzotriazole derivatives may be various derivatives with better solubility in biodiesel than benzotriazole itself. Specifically, the benzotriazole derivatives may be one or more of the ammonium salts of benzotriazole and fatty amines and the products of benzotriazole, formaldehyde and fatty amines through Mannich reaction. The ethylenediaminetetracarboxylic acid can be ethylenediaminetetraacetic acid (EDTA), and the hydrazide can be N-salicylidene-N'-salicylhydrazide and/or N, N'-diacetyladipyl Dihydrazide. The β-diketone is such as acetylacetone, and the β-ketoester is such as octyl acetoacetate. The Schiff base can be N, N'-disalicylidene-1,2-ethylenediamine, N,N'-disalicylidene-1,2-propylenediamine, N,N'-dihydrate One or more of salicylidene-1,2-cyclohexanediamine and N,N'-disalicylidene-N'-methyldipropylenetriamine. The organic polycarboxylic acid and its derivatives can be, for example, one or more of citric acid, tartaric acid, malic acid, succinic acid (succinic acid), maleic acid, phytic acid, etc. and their derivatives.
本发明中，优选所述组分c为苯三唑与脂肪胺形成的铵盐，苯三唑、甲醛与脂肪胺通过曼尼西反应得到的产物(例如商品名为T551的商品添加剂)，席夫碱和有机多元羧酸及其与脂肪胺、或脂肪醇的缩合反应产物(即有机多元羧酸的酰胺类、酯类衍生物)中的一种或几种。In the present invention, it is preferred that the component c is an ammonium salt formed by benzotriazole and fatty amine, a product obtained by Mannich reaction of benzotriazole, formaldehyde and fatty amine (such as a commercial additive with a trade name of T551). One or more of the alkali and organic polycarboxylic acid and its condensation reaction product with aliphatic amine or fatty alcohol (i.e. amides and ester derivatives of organic polycarboxylic acid).
根据使用需要，本发明提供的添加剂组合物还可以含有其它添加剂，如流动改进剂、十六烷值改进剂、抗静电剂、防腐剂、防锈剂、破乳剂等中的一种或几种。According to the needs of use, the additive composition provided by the present invention can also contain other additives, such as one or more of flow improvers, cetane number improvers, antistatic agents, preservatives, rust inhibitors, demulsifiers, etc. .
本发明提供的添加剂组合物的制备简单，只需将组成添加剂组合物的各组分混合均匀即可。这些组分可以直接混合，也可以在溶剂存在下进行混合，这里的溶剂可以是极性溶剂如N，N-二甲基甲酰胺(DMF)、1，4-二氧六环、四氢呋喃(DHF)、二甲基亚砜(DMSO)、吡咯烷酮和甲基吡咯烷酮中的一种或几种。也可以是烃类尤其是芳烃如苯、甲苯、二甲苯、芳烃稀释油及其混合物，还可以是生物柴油。The preparation of the additive composition provided by the invention is simple, and it only needs to mix the components constituting the additive composition uniformly. These components can be mixed directly or mixed in the presence of a solvent, where the solvent can be a polar solvent such as N,N-dimethylformamide (DMF), 1,4-dioxane, tetrahydrofuran (DHF ), dimethylsulfoxide (DMSO), pyrrolidone and methylpyrrolidone or one or more. It can also be hydrocarbons, especially aromatics such as benzene, toluene, xylene, aromatics diluent oil and their mixtures, and biodiesel.
在本发明提供的柴油组合物中，所述基础柴油可以为纯生物柴油，所述生物柴油是指油脂与低碳醇(如C1-C5脂肪醇)经酯交换(醇解)反应而生成的脂肪酸低碳醇酯，一般为脂肪酸甲酯，即油脂与甲醇的酯交换产物。In the diesel oil composition provided by the present invention, the base diesel oil can be pure biodiesel, and the biodiesel refers to the reaction of oil and low-carbon alcohol (such as C1 -C5 fatty alcohol) through transesterification (alcoholysis) The fatty acid lower alcohol esters produced are generally fatty acid methyl esters, that is, the transesterification products of oil and methanol.
所述的酯交换反应工艺可以是任何已知或未知的通过油脂与低碳醇的酯交换反应得到生物柴油的工艺方法，例如酸催化法、碱催化法、酶催化法、超临界法，等等。具体可参考CN1473907A、DE3444893、CN1472280A、CN1142993C、CN1111591C、CN1594504A等文献。The transesterification process can be any known or unknown process for obtaining biodiesel through transesterification of oils and low-carbon alcohols, such as acid catalysis, alkali catalysis, enzyme catalysis, supercritical method, etc. Wait. For details, reference can be made to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, and CN1594504A.
所述的油脂具有本领域公知的一般含义，是油和脂的总称，主要成分是脂肪酸甘油三酯。一般常温为液体的称为油，常温为固体或半固体的称为脂肪(简称脂)。所述油脂包括植物油以及动物油，另外，还包括来自微生物、藻类等物质中的油料，甚至还可以是废油脂，例如餐饮废油、地沟油、泔水油、油脂厂的酸化油等使用过的油脂或变质的油脂。所述植物油可以是草本植物油也可以是木本植物油，如花生油、玉米油、棉籽油、菜子油、大豆油、棕桐油、红花油、亚麻籽油、椰子油、橡树油、杏仁油、核桃油、蓖麻油、芝麻油、橄榄油、妥尔油(TallOil)、向日葵油、麻风树油、桐油、文冠果油、黄连木油、盐土植物如海滨锦葵、油莎豆等植物的油。所述动物油可以是猪油、鸡油、鸭油、鹅油、羊油、马油、牛油、鲸鱼油、鲨鱼油等。The fat has a general meaning known in the art, which is a general term for oil and fat, and its main component is fatty acid triglyceride. Generally, what is liquid at room temperature is called oil, and what is solid or semi-solid at room temperature is called fat (referred to as fat). The oils include vegetable oils and animal oils. In addition, oils from microorganisms, algae, etc. can even be waste oils, such as used oils such as waste catering oil, waste oil, swill oil, acidified oil from oil factories, etc. or spoiled grease. Described vegetable oil can be herbaceous vegetable oil also can be woody vegetable oil, as peanut oil, corn oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, safflower oil, linseed oil, coconut oil, oak oil, almond oil, walnut oil, castor oil, sesame oil, olive oil, tall oil (Tall Oil), sunflower oil, jatropha oil, tung oil, sorbetia oil, pistachio oil, saline plants such as sea mallow, oil sand beans and other plant oils. The animal oil may be lard, chicken oil, duck oil, goose oil, suet oil, horse oil, tallow, whale oil, shark oil, etc.
在本发明的生物柴油组合物中，所述基础柴油也可以含有其它柴油，所述其它柴油为石油柴油、费-托合成柴油、加氢裂化生物柴油、含氧柴油调合物中的一种或几种，所述生物柴油与其它柴油的体积比优选为1∶2-99。In the biodiesel composition of the present invention, the base diesel oil may also contain other diesel oils, and the other diesel oils are one of petroleum diesel, Fischer-Tropsch synthetic diesel oil, hydrocracking biodiesel, and oxygenated diesel blends or several, the volume ratio of the biodiesel to other diesel is preferably 1:2-99.
其中石油柴油是指原油(石油)经炼油厂的各种炼制工艺如常减压、催化裂化、催化重整、焦化、加氢精制、加氢裂化等装置处理后的馏程在160-380℃之间的馏分，并经过调配而成的满足轻柴油国家标准GB252或车用柴油国家标准GB19147的压燃式内燃机用燃料。Among them, petroleum diesel refers to crude oil (petroleum) with a distillation range of 160-380°C after being treated by various refining processes in refineries, such as atmospheric and vacuum, catalytic cracking, catalytic reforming, coking, hydrofining, and hydrocracking. The fractions between them are blended to meet the national standard GB252 for light diesel oil or the national standard GB19147 for automotive diesel fuel for compression ignition internal combustion engines.
费-托合成柴油主要指以天然气或煤为原料经费-托(F-T)合成方法而生产的GTL柴油(GasToLiquid)或CTL柴油(CoalToLiquid)，还可以是植物纤维经费-托合成方法而生产的BTL柴油(BiomassToLiquid)。费-托合成柴油基本上不含硫和芳烃，是非常洁净的燃料，但其润滑性却极差，与生物柴油调合后润滑性大大改善，但调合油的氧化安定性有可能变差，因此含生物柴油的调合燃料也需要加入抗氧剂。Fischer-Tropsch synthetic diesel mainly refers to GTL diesel (GasToLiquid) or CTL diesel (CoalToLiquid) produced by using natural gas or coal as a raw material through the Fischer-Tropsch (F-T) synthesis method, and it can also be BTL produced by plant fiber through the Fischer-Tropsch synthesis method Diesel (BiomassToLiquid). Fischer-Tropsch synthetic diesel basically does not contain sulfur and aromatics, and is a very clean fuel, but its lubricity is extremely poor. After blending with biodiesel, the lubricity is greatly improved, but the oxidation stability of the blended oil may deteriorate , so blended fuels containing biodiesel also need to add antioxidants.
加氢裂化生物柴油也称为第二代生物柴油，是指由动植物油脂经过加氢和裂化反应后生成的以C8-C24烷烃为主，尤其是以C12-C20正构烷烃为主要成分的反应产物，这种加氢裂化生物柴油十六烷值高，硫和芳烃含量极低，作为柴油发动机燃料或调合组分可大大降低柴油机污染物的排放。Hydrocracking biodiesel, also known as second-generation biodiesel, refers to C8 -C24 alkanes, especially C12 -C20 normal alkanes, produced by hydrogenation and cracking reactions of animal and vegetable oils As the reaction product of the main component, this hydrocracking biodiesel has a high cetane number and extremely low sulfur and aromatic content. As a diesel engine fuel or a blending component, it can greatly reduce the emission of diesel engine pollutants.
含氧柴油调合组分是指可与各种柴油机燃料调配成符合一定规范要求的含氧化合物或含氧化合物的混合物，通常是醇类和醚类或其混合物，醇类例如C1-C18脂肪醇、优选C1-C12一元脂肪醇，如甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、十一碳醇、月桂醇及其各种异构体。醚类可以是二甲醚、甲基叔丁基醚、乙基叔丁基醚、C6-C14脂肪醇聚氧乙烯醚、C6-C14脂肪醇聚氧丙烯醚、C6-C14烷基酚聚氧乙烯醚、C6-C14烷基酚聚氧丙烯醚、聚氧化亚甲基二甲醚(PolyoxymethyleneDimethylEthers，CH3O(CH2O)xCH3，x＝1-8)等及其混合物。Oxygenated diesel blending components refer to oxygenated compounds or mixtures of oxygenated compounds that can be blended with various diesel fuels to meet certain specification requirements, usually alcohols and ethers or their mixtures, alcohols such as C1 -C18 Fatty alcohols, preferably C1 -C12 monohydric fatty alcohols, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, lauryl alcohol and its various isomers. Ethers can be dimethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, C6 -C14 fatty alcohol polyoxyethylene ether, C6 -C14 fatty alcohol polyoxypropylene ether, C6 -C14 Alkylphenol polyoxyethylene ethers, C6 -C14 alkylphenol polyoxypropylene ethers, polyoxymethylene dimethyl ethers (PolyoxymethyleneDimethylEthers, CH3 O(CH2 O)x CH3 , x=1-8 ), etc. and mixtures thereof.
本发明中，所述基础柴油为含生物柴油的调合燃料时，所述柴油组合物可以通过将所述添加剂、生物柴油和其它柴油直接混合而得到，也可以先将所述添加剂与生物柴油混合，然后再与其它柴油调合而得到。可以将添加剂的各种组分直接与基础柴油的各种成分混合，也可以先将添加剂的各种组分预先混合，得到添加剂混合物后再与基础柴油或者基础柴油的各种成分混合。对添加剂的各种组分以及生物柴油和其它柴油的混合顺序没有特别限定，可以以各种顺序混合。混合的条件可以在各种不对添加剂组合物和柴油组合物造成不利影响的条件下进行，例如，可以在环境温度下混合。In the present invention, when the base diesel oil is a blended fuel containing biodiesel, the diesel oil composition can be obtained by directly mixing the additive, biodiesel and other diesel oils, or can first mix the additive with biodiesel Mixed, and then blended with other diesel obtained. The various components of the additive can be directly mixed with the various components of the base diesel, or the various components of the additive can be pre-mixed to obtain the additive mixture and then mixed with the base diesel or various components of the base diesel. The mixing order of the various components of the additive and biodiesel and other diesel is not particularly limited, and may be mixed in various orders. The mixing conditions can be carried out under various conditions that do not adversely affect the additive composition and the diesel composition, for example, mixing can be at ambient temperature.
本发明提供的提高生物柴油氧化安定性的方法包括，在含有生物柴油的柴油组分中，加入添加剂，其中，所述添加剂为本发明提供的上述添加剂组合物。The method for improving the oxidation stability of biodiesel provided by the present invention includes adding an additive to the diesel component containing biodiesel, wherein the additive is the above-mentioned additive composition provided by the present invention.
下面的实施例将对本发明做进一步的说明。The following examples will further illustrate the present invention.
制备例1-4用于说明组分b的合成。Preparations 1-4 are used to illustrate the synthesis of component b.
制备例1Preparation Example 1
在一500ml的三颈瓶中，加入56.7g四乙烯五胺(0.3mol)和38.7gN-(2-氨基乙基)哌嗪(0.3mol)以及100g甲苯，加热搅拌回流，将42.0g的浓度为36重量％的甲醛溶液(0.5mol)在2小时内滴加到三颈瓶中，回流分水至不再出水(约2小时)，减压蒸馏除去甲苯后，得101g残留物，再加入105g馏程为159-185℃芳烃稀释油配成稀释液，该稀释液直接用作组分b。In a 500ml three-necked flask, add 56.7g tetraethylenepentamine (0.3mol) and 38.7g N-(2-aminoethyl) piperazine (0.3mol) and 100g toluene, heat and stir to reflux, the concentration of 42.0g A 36% by weight formaldehyde solution (0.5mol) was added dropwise in a three-necked flask within 2 hours, refluxed to separate water until no more water came out (about 2 hours), and after the toluene was removed by distillation under reduced pressure, 101g of residue was obtained, and then added 105g of aromatic diluent oil with a distillation range of 159-185°C was prepared as a diluent, which was directly used as component b.
制备例2Preparation example 2
在一500ml的三颈瓶中，加入69.6g五乙烯六胺(0.3mol)和9.0多聚甲醛(0.3mol甲醛)以及80g甲苯，加热搅拌回流分水反应至不再出水(5小时)，减压蒸馏除去甲苯后，得73g残留物，再加入73g馏程为159-185℃芳烃稀释油配成稀释液，该稀释液直接用作组分b。In a 500ml three-necked flask, add 69.6g of pentaethylenehexamine (0.3mol) and 9.0g of paraformaldehyde (0.3mol formaldehyde) and 80g of toluene, heat and stir to reflux and divide water until no more water is produced (5 hours), reduce After the toluene was removed by pressure distillation, 73g of residue was obtained, and 73g of aromatic hydrocarbon diluent oil with a distillation range of 159-185°C was added to prepare a diluent, which was directly used as component b.
制备例3Preparation example 3
在一500ml的三颈瓶中，加入43.8g三乙烯四胺(0.3mol)、72.6g的N-十二烷基-1，3-丙二胺(0.3mol)和18.0g多聚甲醛(0.6mol甲醛)以及125g甲苯，加热搅拌回流分水反应至不再出水(5小时)，减压蒸馏除去甲苯后，得124g残留物，再加入120g馏程为159-185℃的芳烃稀释油配成稀释液，该稀释液直接用作组分b。In a 500ml three-necked flask, add 43.8g triethylenetetramine (0.3mol), 72.6g N-dodecyl-1,3-propylenediamine (0.3mol) and 18.0g paraformaldehyde (0.6 mol formaldehyde) and 125g of toluene, heated, stirred, refluxed, and reacted until no more water came out (5 hours). After the toluene was removed by distillation under reduced pressure, 124g of residue was obtained, and 120g of aromatic hydrocarbon diluent oil with a distillation range of 159-185°C was added to prepare diluent, which is used directly as component b.
制备例4Preparation Example 4
在一500ml的三颈瓶中，加入56.7g四乙烯五胺(0.3mol)和126g的T151A(聚异丁烯单丁二酰亚胺，聚异丁烯数均相对分子质量为1000，锦州康泰润滑油添加剂有限公司工业产品)以及110g甲苯，加热搅拌回流，将29.2g浓度为36重量％的甲醛溶液(0.35mol)在2小时内滴加到三颈瓶中，回流分水反应至不再出水(约3小时)，减压蒸馏除去甲苯后，得185g残留物，再加入66g馏程为159-185℃芳烃稀释油配成稀释液，该稀释液直接用作组分b。In a 500ml three-necked bottle, add 56.7g of tetraethylenepentamine (0.3mol) and 126g of T151A (polyisobutylene monosuccinimide, polyisobutylene number average relative molecular weight is 1000, Jinzhou Kangtai Lubricating Oil Additive Co., Ltd. Company industrial product) and 110g toluene, heated and stirred and refluxed, 29.2g concentration was that the formaldehyde solution (0.35mol) of 36% by weight was added dropwise in the three-necked bottle within 2 hours, and the reflux water separation reaction was no longer water-out (about 3 hours), after removing the toluene by distillation under reduced pressure, 185g of residue was obtained, and then 66g of aromatic hydrocarbon diluent oil with a distillation range of 159-185°C was added to make a diluent, which was directly used as component b.
实施例1-11Examples 1-11
实施例1-11用于说明本发明添加剂组合物的制备。Examples 1-11 illustrate the preparation of additive compositions of the present invention.
将组分a和组分b以及组分c按照表1所示的重量比混合。Component a, component b and component c were mixed according to the weight ratio shown in Table 1.
表1Table 1
性能测试Performance Testing
以下测试中，所用棉籽油生物柴油是中石化石家庄炼化分公司提供的生物柴油产品，所用酸化油生物柴油均由福建龙岩卓越新能源有限公司提供，石油柴油均为中石化燕山分公司生产的京标B柴油。In the following tests, the cottonseed oil biodiesel used is the biodiesel product provided by Sinopec Shijiazhuang Refining and Chemical Branch, the acidified oil biodiesel used is provided by Fujian Longyan Excellence New Energy Co., Ltd., and the petroleum diesel is Beijing standard produced by Sinopec Yanshan Branch B diesel.
(1)纯生物柴油作为基础柴油的生物柴油组合物的氧化安定性测试(1) Oxidation stability test of biodiesel composition with pure biodiesel as base diesel
用EN14112：2003方法(Racimat法)测定110℃下的诱导期来评定生物柴油氧化安定性，使用仪器为瑞士万通公司的743型油脂氧化稳定性测定仪，其中，诱导期越长则说明柴油组合物的抗氧化性越好，反之诱导期越短则说明柴油组合物的抗氧化性越差。其测试结果示于表2中。Use the EN14112:2003 method (Racimat method) to measure the induction period at 110°C to evaluate the oxidation stability of biodiesel. The instrument used is Metrohm's 743 oil oxidation stability tester. The longer the induction period, the higher the oxidation stability of diesel oil. The better the oxidation resistance of the composition, on the contrary the shorter the induction period, the worse the oxidation resistance of the diesel oil composition. The test results are shown in Table 2.
表2Table 2
表2(续)Table 2 (continued)
从表2中的数据可以看出，组分a是常见的抗氧剂，对生物柴油氧化安定性有一定改善，组分b单独使用对生物柴油的抗氧作用没有任何改进，本发明提供的生物柴油组合物具有明显更好的氧化安定性。组分a与组分b配合作用后，生物柴油组合物的氧化安定性比单独使用组分a、组分b的效果之和要好很多，由此可见组分a、b之间令人惊奇地出现了很明显的协同作用。As can be seen from the data in Table 2, component a is a common antioxidant, which improves the oxidation stability of biodiesel to a certain extent, and component b alone does not have any improvement to the antioxidant effect of biodiesel. The invention provides Biodiesel compositions have significantly better oxidation stability. After the combination of component a and component b, the oxidation stability of the biodiesel composition is much better than the sum of the effects of using component a and component b alone, so it can be seen that there is a surprising difference between component a and b A clear synergy emerged.
实施例4与实施例5相比可以看出，选用任选的组分c后，所得生物柴油组合物的氧化安定性进一步增强。Comparing Example 4 with Example 5, it can be seen that after the optional component c is selected, the oxidation stability of the obtained biodiesel composition is further enhanced.
实施例1与实施例7相比可以看出，对苯二胺类抗氧剂作为组分a效果远优于二苯胺类抗氧剂；实施例6与实施例8相比可以看出，双酚型抗氧剂作为组分a效果远优于单酚类抗氧剂。Compared with Example 7, it can be seen that the effect of p-phenylenediamine antioxidant is far superior to that of diphenylamine antioxidant as component a; compared with Example 8, it can be seen that the double The effect of phenolic antioxidant as component a is much better than that of monophenolic antioxidant.
实施例4与实施例9相比可以看出，组分a为芳胺型抗氧剂和受阻酚型抗氧剂的混合物时，所得生物柴油组合物的氧化安定性进一步提高。Comparing Example 4 with Example 9, it can be seen that when component a is a mixture of aromatic amine antioxidant and hindered phenol antioxidant, the oxidation stability of the obtained biodiesel composition is further improved.
实施例4与实施例10和实施例11相比可以看出，组分a为二烷基对苯二胺的效果优于组分a为其它对苯二胺型抗氧剂。Comparing Example 4 with Example 10 and Example 11, it can be seen that the effect of component a being dialkyl-p-phenylenediamine is better than that of component a being other p-phenylenediamine antioxidants.
(2)以生物柴油和石油柴油的混合物作为基础柴油的调合柴油组合物的抗氧化性、稳定性和清净分散性的测试，所用生物柴油为酸化油生物柴油。(2) The oxidation resistance, stability and clean dispersibility of the blended diesel oil composition using the mixture of biodiesel and petroleum diesel as the base diesel oil. The biodiesel used is acidified oil biodiesel.
采用PrEN15751：2008的方法分别测定各柴油组合物、石油柴油和调合柴油在110℃下的诱导期，使用仪器为瑞士万通公司的743型油脂氧化稳定性测定仪，诱导期越长则说明生物柴油组合物的抗氧化性越好，反之诱导期越短则说明生物柴油组合物的抗氧化性越差。其测试结果示于表3中。The method of PrEN15751:2008 was used to measure the induction period of each diesel composition, petroleum diesel and blended diesel oil at 110°C. The instrument used was Metrohm’s 743 oil oxidation stability tester. The longer the induction period, the more The better the oxidation resistance of the biodiesel composition, on the contrary the shorter the induction period, the worse the oxidation resistance of the biodiesel composition. The test results are shown in Table 3.
采用SH/T0175的方法测定各种调合柴油组合物总不溶物的量(单位：mg/100mL)，从而评定它们的稳定性。总不溶物的量越大则稳定性越差，反之若总不溶物的量越小则稳定性越好，其测试结果示于表3中。The method of SH/T0175 was used to measure the amount of total insoluble matter (unit: mg/100mL) of various blended diesel oil compositions, so as to evaluate their stability. The greater the amount of total insolubles, the poorer the stability; on the contrary, the smaller the amount of total insolubles, the better the stability. The test results are shown in Table 3.
表3table 3
*表示用加入600mg/kg实施例4对应的添加剂后的生物柴油与石油柴油按照体积比15∶85调合而成，计算出调合燃料添加剂含量为90mg/kg。* indicates that biodiesel and petroleum diesel are blended according to the volume ratio of 15:85 after adding 600mg/kg of the additive corresponding to Example 4, and the content of the blended fuel additive is calculated to be 90mg/kg.
由表3的结果可以看出，加入生物柴油后，含生物柴油的调合燃料的氧化安定性、稳定性与石油柴油相比都变差。含有组分a和组分b的混合物作为添加剂而得到的本发明的生物柴油组合物的氧化安定性、稳定性都有很大程度的改善，组分a和组分b效果出现协同效应，其效果比单独使用时效果明显增强。It can be seen from the results in Table 3 that after adding biodiesel, the oxidation stability and stability of the blended fuel containing biodiesel are worse than those of petroleum diesel. The oxidation stability and stability of the biodiesel composition of the present invention obtained by containing the mixture of component a and component b as additives are greatly improved, and the effects of component a and component b have a synergistic effect, which The effect is significantly stronger than when used alone.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910090512.0ACN101993744B (en) | 2009-08-19 | 2009-08-19 | The method of biodiesel composition and raising oxidation stability of biodiesel |
| EP10791159.6AEP2447344B1 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process for improving oxidation stability of biodiesel |
| ES10791159TES2749879T3 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process to improve oxidation stability of biodiesel |
| US13/380,334US20120124896A1 (en) | 2009-06-26 | 2010-06-25 | Diesel Composition and Method of Increasing Biodiesel Oxidation Stability |
| PCT/CN2010/000950WO2010148652A1 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process for improving oxidation stability of biodiesel |
| BRPI1012681-3ABRPI1012681B1 (en) | 2009-06-26 | 2010-06-25 | DIESEL COMPOSITION AND METHOD OF INCREASING BIODIESEL OXIDATION STABILITY |
| Application Number | Priority Date | Filing Date | Title |
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| CN200910090512.0ACN101993744B (en) | 2009-08-19 | 2009-08-19 | The method of biodiesel composition and raising oxidation stability of biodiesel |
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