CN102936521A - Diesel oil composition and method for improving biodiesel oxidation stability - Google Patents

Abstract

Translated fromChinese

本发明提供了一种柴油组合物，该柴油组合物含有基础柴油和添加剂，其中，所述基础柴油含有生物柴油，所述添加剂含有组分a，所述组分a为马来酸酐接枝油溶性聚合物的共聚物的胺化或氨解反应产物，所述添加剂还任选含有组分b，组分b为芳胺型抗氧剂和/或受阻酚型抗氧剂。本发明还提供了一种提高生物柴油氧化安定性的方法。本发明提供的柴油组合物，当以纯生物柴油作为基础柴油时，该柴油组合物具有较好的氧化安定性和低温流动性；当以含有生物柴油的调合燃料作为基础柴油时，该柴油组合物的稳定性和低温流动性较好。The invention provides a diesel oil composition, the diesel oil composition contains base diesel oil and additives, wherein, the base diesel oil contains biodiesel, the additive contains component a, and the component a is maleic anhydride grafted oil The amination or ammonolysis reaction product of a copolymer of a soluble polymer, the additive may also optionally contain component b, and component b is an aromatic amine antioxidant and/or a hindered phenol antioxidant. The invention also provides a method for improving the oxidation stability of biodiesel. The diesel oil composition provided by the present invention, when pure biodiesel is used as the base diesel oil, the diesel oil composition has good oxidation stability and low temperature fluidity; when the blended fuel containing biodiesel is used as the base diesel oil, the diesel oil composition Good stability and low temperature fluidity.

Description

Translated fromChinese

一种柴油组合物和提高生物柴油氧化安定性的方法A kind of diesel oil composition and the method for improving biodiesel oxidation stability

技术领域technical field

本发明是关于一种柴油组合物和提高生物柴油氧化安定性的方法。The invention relates to a diesel 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(Fatty Acid Methyl Ester)，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 (Fatty Acid Methyl Ester), is derived from 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, and animal fats, Waste cooking oil and other raw materials are obtained through transesterification with alcohols (methanol, ethanol). It 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EN 14214：2003、澳大利亚生物柴油标准(Draft2003)、新西兰生物柴油标准NZS 7500：2005、巴西生物柴油标准ANP255(2003)、印度生物柴油标准IS 15607：2005、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EN 14112：2003。European biodiesel standard EN 14214: 2003, Australian biodiesel standard (Draft2003), New Zealand biodiesel standard NZS 7500: 2005, Brazilian biodiesel standard ANP255 (2003), Indian biodiesel standard IS 15607: 2005, South African biodiesel standard SANS1935: Both 2004 and my country's national standard GB/T20828-2007 for biodiesel (BD100) for blending diesel engine fuels stipulate that the oxidation stability of biodiesel is not less than 6 hours at 110°C, and the measurement method is EN 14112:2003.

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，特引入石油柴油的概念)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和清净分散性比石油柴油要差。As we all know, non-hydrocarbon compounds such as olefins, diolefins, sulfides, and nitrogen compounds in petroleum diesel (that is, diesel oil in the usual sense, in order to distinguish it from biodiesel, are introduced here) are formed under the action of oxygen. A series of oxidized intermediates produce insoluble precipitates through condensation. 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 performance is that the stability and cleanness and dispersibility of the blended fuel containing biodiesel are 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和清净分散剂，以改善调合燃料的稳定性和清净分散性。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；清净分散剂可把喷嘴上已形成的积炭清洗下来，并在喷嘴表面形成保护膜，防止新的积炭产生，同时还可分散油中已形成的沉渣，改善滤清器和喷嘴堵塞，并改善尾气排放。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 harm of aging products; the other way is to add stabilizers and detergents and dispersants to petroleum diesel or blended fuels containing biodiesel, To improve the stability and clean dispersibility of blended fuels. Stabilizers can terminate, weaken, or interfere with various oxidation reactions to inhibit oil deterioration and improve its stability; detergents and dispersants can clean the carbon deposits formed on the nozzles and form a protective film on the surface of the nozzles to prevent new At the same time, it can also disperse the sediment formed in the oil, improve the clogging of filters and nozzles, and improve exhaust emissions.

CN 1742072A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％。CN 1742072A discloses a method for improving the storage stability of biodiesel, which method comprises adding the liquid stock solution containing 2,4-di-tert-butyl hydroxytoluene dissolved in biodiesel to the In the biodiesel to be stabilized, the concentration of 2,4-di-tert-butylhydroxytoluene reaches 0.005-2% by weight based on the total solution of biodiesel.

CN 1847368A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。CN 1847368A discloses a method for improving the oxidation stability of biodiesel, which method comprises bisphenol type antioxidant 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).

CN 1847369A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。CN 1847369A discloses a method for improving the oxidation stability of biodiesel, which method comprises adding the 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 said main antioxidant contains alkylphenol.

US 2007/113467A1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。US 2007/113467A1 discloses a fuel composition with improved oxidation stability 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.

CN101058774A公开了一种烃基取代的琥珀酸酰化剂与聚亚烷基胺的反应产物非必要地与2，5-二叔丁基氢醌的组合在防止或延迟液体组合物氧化中的用途，其中所述液体组合物含有至少2重量％的源自植物或动物的油。CN101058774A discloses the use of the reaction product of a hydrocarbyl-substituted succinic acylating agent and polyalkyleneamine optionally combined with 2,5-di-tert-butylhydroquinone in preventing or delaying the oxidation of a liquid composition, wherein the The liquid composition contains at least 2% by weight of oil of vegetable or animal origin.

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，但对于纯生物柴油基础柴油的氧化安定性提高效果不明显，对于生物柴油和其它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 effect on improving the oxidation stability of pure biodiesel base diesel is not obvious, and the stability of biodiesel and other diesel blended fuels The improvement effect 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以纯生物柴油为基础柴油的柴油组合物的氧化安定性较差以及以生物柴油与其它柴油的调合燃料为基础柴油的柴油组合物的稳定性较差的缺点，提供一种氧化安定性或者稳定性较好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 relatively poor oxidation stability of the diesel oil composition based on pure biodiesel and the relatively low stability of the diesel composition based on the blended fuel of biodiesel and other diesel oils in the prior art. To provide a diesel composition with better oxidation stability or stability and to provide a method for improving the oxidation stability of biodiesel.

本发明提供了一种柴油组合物，该柴油组合物含有基础柴油和添加剂，其中，所述基础柴油含有生物柴油，所述添加剂含有组分a，所述组分a为马来酸酐接枝油溶性聚合物的共聚物的胺化或氨解物。The invention provides a diesel oil composition, the diesel oil composition contains base diesel oil and additives, wherein, the base diesel oil contains biodiesel, the additive contains component a, and the component a is maleic anhydride grafted oil Amination or ammonolysis of copolymers of soluble polymers.

本发明同时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，所述添加剂含有组分a，所述组分a为马来酸酐接枝油溶性聚合物的共聚物的胺化或氨解物。The present invention also provides a method for improving the oxidation stability of biodiesel. The method includes adding an additive to the base diesel containing biodiesel. The additive contains component a, and the component a is maleic anhydride-linked Aminated or ammonolyzed copolymers of branched oil-soluble polymers.

本发明提供的柴油组合物，当以纯生物柴油作为基础柴油时，该柴油组合物具有较好的氧化安定性，当以含有生物柴油的调合燃料作为基础柴油时，该柴油组合物的稳定性较好。而且，本发明提供的柴油组合物的低温流动性也明显提高了。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，由于各添加剂之间令人惊异的出现协同效应，抗氧化效果比单独使用上述组分a、b时要好很多。在组分a与组分b混合使用时，组分a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b在生物柴油组合物中的量可以大大减少，尤其是在组分b特别昂贵或组分b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。The diesel oil composition provided by the present invention, when using pure biodiesel as base diesel oil, the diesel oil composition has better oxidation stability, when using the blended fuel containing biodiesel as base diesel oil, the stability of the diesel oil composition better. Moreover, the low-temperature fluidity of the diesel composition provided by the invention is also obviously improved. Especially according to the preferred embodiment provided by the present invention, when the additive contains component a and component b at the same time, due to the amazing synergistic effect between the additives, the antioxidant effect is higher than that of using the above components a and b alone much better. When component a and component b are used in combination, component a can be regarded as an auxiliary antioxidant, which can unexpectedly greatly enhance the effect of the antioxidant. Therefore, when achieving the same oxidation stability requirements, the amount of component b in the biodiesel composition can be greatly reduced, especially when component b is particularly expensive or component b has certain toxicity or corrosiveness, the reduction Its dosage is of great significance.

具体实施方式Detailed ways

根据本发明提供的柴油组合物，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500-5000ppm，优选为1000-3000ppm。According to the diesel composition provided by the present invention, the content of the additive can be selected within a wide range, for example, the content of the base diesel can be 500-5000ppm, preferably 1000-3000ppm.

组分aComponent a

所述组分a中的聚合物的数均分子量可以为500-100,000，优选为1000-50,000。所述组分a中的聚合物的接枝率为0.5-10，优选为1-5。The number average molecular weight of the polymer in the component a may be 500-100,000, preferably 1000-50,000. The graft ratio of the polymer in the component a is 0.5-10, preferably 1-5.

在本发明中，所述“马来酸酐接枝油溶性聚合物的共聚物的胺化或氨解物”是由马来酸酐接枝油溶性聚合物与含有-NH官能团的氨和/或有机胺通过缩合反应得到。马来酸酐接枝油溶性聚合物与含有-NH官能团的氨和/或有机胺发生缩合反应(也称羧酸衍生物的氨(胺)解反应或氨(胺)化反应)。In the present invention, the "aminated or ammolyzed product of a copolymer of maleic anhydride grafted oil-soluble polymer" is composed of maleic anhydride grafted oil-soluble polymer and ammonia and/or organic Amines are obtained by condensation reactions. Condensation reaction of maleic anhydride grafted oil-soluble polymer with ammonia and/or organic amine containing -NH functional group (also known as ammonia (amination) decomposition reaction or ammonia (amination) reaction of carboxylic acid derivatives).

在本发明中，所述“油溶性聚合物”的单体为烯键式不饱和单体，进一步优选为碳原子数为2-30的烯键式不饱和单体，更进一步优选为乙烯、丙烯、丁烯、丁二烯、丙烯腈、丙烯酸C1-C22烷基酯、甲基丙烯酸C1-C22烷基酯、丙烯酰胺、甲基丙烯酰胺、醋酸乙烯酯、苯乙烯、C6-C24的α-烯烃、马来酸酐、马来酸、马来酸酯、马来酰亚胺、富马酸酯、乙烯基吡啶、烷基乙烯醚中的一种或多种。所述油溶性聚合物可以是前述单体的均聚物、二元、三元或者多元共聚物。所述油溶性聚合物的数均分子量优选为500-100000，进一步优选为1000-50000。所述油溶性聚合物可以是现有的商品聚合物，例如为作为柴油流动改进剂的乙烯-醋酸乙烯酯共聚物(EVA)、丙烯酸酯均聚物、甲基丙烯酸酯均聚物、(甲基)丙烯酸酯-马来酸酰亚胺共聚物、(甲基)丙烯酸酯-马来酸酯共聚物；作为润滑油粘度指数改进剂的乙烯-丙烯共聚物、聚甲基丙烯酸酯、苯乙烯-双烯共聚物中的一种或多种；作为润滑油降凝剂的聚α-烯烃、聚(甲基)丙烯酸酯、醋酸乙烯酯-富马酸酯共聚物中的一种或多种；作为原油降凝剂的乙烯-醋酸乙烯酯共聚物(EVA)、(甲基)丙烯酸酯共聚物。符合上述条件的油溶性聚合物例如可以是中石化上海高桥石化分公司炼油厂生产的商品添加剂T602和北京有机化工厂生产的柴油商品降凝剂T1804C。In the present invention, the monomer of the "oil-soluble polymer" is an ethylenically unsaturated monomer, more preferably an ethylenically unsaturated monomer with 2-30 carbon atoms, more preferably ethylene, Alpha of propylene, butene, butadiene, acrylonitrile, C1-C22 alkyl acrylate, C1-C22 alkyl methacrylate, acrylamide, methacrylamide, vinyl acetate, styrene, C6-C24 - one or more of olefins, maleic anhydride, maleic acid, maleic acid esters, maleimides, fumaric acid esters, vinyl pyridines, alkyl vinyl ethers. The oil-soluble polymer may be a homopolymer, a binary, a ternary or a multi-polymer of the aforementioned monomers. The number average molecular weight of the oil-soluble polymer is preferably 500-100000, more preferably 1000-50000. The oil-soluble polymer can be an existing commodity polymer, such as ethylene-vinyl acetate copolymer (EVA), acrylate homopolymer, methacrylate homopolymer, (methacrylic acid ester homopolymer) as a diesel oil flow improver base) acrylate-maleimide copolymers, (meth)acrylate-maleate copolymers; ethylene-propylene copolymers, polymethacrylates, styrene as viscosity index improvers for lubricating oils - one or more of diene copolymers; one or more of polyalphaolefins, poly(meth)acrylates, vinyl acetate-fumarate copolymers as lubricating oil pour point depressants ; Ethylene-vinyl acetate copolymer (EVA), (meth)acrylate copolymer as crude oil point depressant. The oil-soluble polymer meeting the above conditions can be, for example, the commercial additive T602 produced by the refinery of Sinopec Shanghai Gaoqiao Petrochemical Company and the commercial diesel pour point depressant T1804C produced by Beijing Organic Chemical Plant.

马来酸酐接枝油溶性聚合物的共聚物是将马来酸酐与上述油溶性聚合物进行接枝聚合的产物。马来酸酐与上述油溶性聚合物进行接枝聚合时的物料质量比一般为0.005-0.2∶1，优选0.01-0.1∶1。对聚合物进行接枝聚合是本领域公知的技术，一般采用在溶液中加入引发剂从而引发接枝聚合反应。所述接枝聚合条件包括聚合温度为40-250℃，反应时间为1-10小时。所用引发剂可以是过氧化物或偶氮化物，如二叔丁基过氧化物、二月桂基过氧化物、过氧化苯甲酰、偶氮二异丁晴、过氧化十二酰、异丙苯过氧化氢、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯等；还可以用过硫酸钾、硫代硫酸盐等无机引发剂。引发剂的用量一般是反应物总重量的0.5-2％。所述溶剂可以是甲苯、二甲苯、乙苯、正己烷、环己烷等，也可以是芳烃稀释油，馏程为159-185℃，优选为馏程为159-185℃的芳烃稀释油。溶剂用量一般是单体物料总重的30-150％。引发剂的加料方式可以是一次全部加入，也可以分多次间隔一定时间加入。反应产物可以去除溶剂或不去除溶剂直接进行下步反应，优选为去除未反应马来酸酐的产物。去除未反应马来酸酐的方法可以为通过氮气吹扫或减压蒸馏，或者将聚合物在甲醇或丙酮中沉淀出来。反应产物更优选为去除未反应的马来酸酐后且含有50重量％左右溶剂的产物。The copolymer of maleic anhydride grafted oil-soluble polymer is the product of graft polymerization of maleic anhydride and the above-mentioned oil-soluble polymer. The mass ratio of maleic anhydride to the above-mentioned oil-soluble polymer during graft polymerization is generally 0.005-0.2:1, preferably 0.01-0.1:1. Graft polymerization of polymers is a well-known technique in the art, and an initiator is generally added to a solution to initiate the graft polymerization reaction. The graft polymerization conditions include a polymerization temperature of 40-250° C. and a reaction time of 1-10 hours. The initiator used can be a peroxide or an azo compound, such as di-tert-butyl peroxide, dilauryl peroxide, benzoyl peroxide, azobisisobutyroyl peroxide, lauryl peroxide, isopropyl Benzene hydroperoxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, etc.; inorganic initiators such as potassium persulfate and thiosulfate can also be used. The dosage of the initiator is generally 0.5-2% of the total weight of the reactants. The solvent may be toluene, xylene, ethylbenzene, n-hexane, cyclohexane, etc., or aromatic diluent oil with a distillation range of 159-185°C, preferably an aromatic diluent oil with a distillation range of 159-185°C. The amount of solvent used is generally 30-150% of the total weight of the monomer material. The feeding method of the initiator can be added all at once, or can be added several times at intervals of a certain time. The reaction product can directly carry out the next step reaction without removing the solvent, preferably the product obtained by removing unreacted maleic anhydride. Methods for removing unreacted maleic anhydride may be by nitrogen purge or distillation under reduced pressure, or by precipitating the polymer in methanol or acetone. The reaction product is more preferably a product containing about 50% by weight of a solvent after removing unreacted maleic anhydride.

所述马来酸酐接枝聚合物的胺化或氨解反应产物是指上述接枝共聚物与含有-NH官能团的氨和/或有机胺反应，可以得到铵盐、酰胺和酰亚胺中的一种或多种。The amination or ammonolysis reaction product of described maleic anhydride graft polymer refers to that above-mentioned graft copolymer reacts with ammonia and/or organic amine containing -NH functional group, can obtain ammonium salt, amide and imide one or more.

所述含有-NH官能团的氨和/或有机胺优选是含有-NH官能团的多胺化合物，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R₁HN-R₂-NHR₃的胺，这里的R₁和R₃可以是氢、碳数为1-30的烃基，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；“烃基”指烃取代基，即脂肪族、脂环族、芳族以及环式取代基中的一种或多种。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-丙二胺中的一种或多种。还可以是如下式1所示的聚醚二胺：The ammonia and/or organic amine containing -NH functional group is preferably a polyamine compound containing -NH functional group, where the polyamine refers to an amine containing two or more nitrogen atoms in the molecule, such as the structural formula R₁ HN- The amine of R₂ -NHR₃ , where R₁ and R₃ can be hydrogen, a hydrocarbon group with a carbon number of 1-30, and R₃ can be an alkylene group with a carbon number of 1-30, alkenyl, cycloalkyl, Aryl group or polyether group, etc.; "hydrocarbyl" refers to hydrocarbon substituents, that is, one or more of aliphatic, alicyclic, aromatic and cyclic substituents. For example, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyldiamine, decanediamine, coconut oil-based 1,3-propylenediamine, oleyl-1,3- One or more of propylenediamine and tallow 1,3-propylenediamine. It can also be polyether diamine shown in formula 1 below:

其中x1为1-50的整数，R₄可以是氢、碳数为1-30的烃基；R₅是氢或甲基。例如CAS号为9046-10-0、数均相对分子质量为400的聚醚胺。Wherein x1 is an integer of 1-50, R₄ can be hydrogen, a hydrocarbon group with a carbon number of 1-30; R₅ is hydrogen or methyl. For example, polyetheramine with a CAS number of 9046-10-0 and a number average relative molecular mass of 400.

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、四丙烯五胺和五丙烯六胺、六丙烯七胺、七丙烯八胺以及N-(2-氨基乙基)-1，3-丙二胺中的一种或多种。当R₆为碳数为1-30的烃基时，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，该烷基的例子包括正丁基、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。烯基的例子包括9-十八烯基。带有苯环的芳基的例子包括苯甲基(苄基)、苯乙基和苯丙基。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, tetrapropylenepentamine and pentapropylenehexamine, hexapropyleneheptamine, heptapropyleneoctamine and N-(2-aminoethyl)-1,3-propane One or more of diamines. When R₆ is a hydrocarbon group with a carbon number of 1-30, it is preferably 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. The alkyl group can be a straight chain normal alkyl group or an isomeric alkyl group with a side chain. Examples of the alkyl group include 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, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isodeca Tetradecyl, Isohexadecyl, Isooctadecyl and Isoeicosyl. Examples of alkenyl groups include 9-octadecenyl. Examples of aryl groups having a benzene ring include 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例如但不限于咪唑啉型、哌嗪型以及哌啶型的胺。The polyamines here may also be nitrogen-containing heterocyclic amines such as but not limited to imidazoline-type, piperazine-type and piperidine-type amines.

咪唑啉型多胺如下式2所示：The imidazoline polyamine is shown in formula 2 below:

其中y2为0到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，该烷基的例子包括正丁基、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。烯基的例子包括9-十八烯基。带有苯环的芳基的例子包括苯甲基(苄基)、苯乙基和苯丙基。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 from 0 to 5, and_R7 is a hydrocarbon group of C1-C24. It is preferably 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. The alkyl group can be a straight chain normal alkyl group or an isomeric alkyl group with a side chain. Examples of the alkyl group include 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, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isodeca Tetradecyl, Isohexadecyl, Isooctadecyl and Isoeicosyl. Examples of alkenyl groups include 9-octadecenyl. Examples of aryl groups having a benzene ring include 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3所示：The piperazine type polyamine is shown in the following formula 3:

其中R₈为H或C1-C24的烃基，x3为0到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 from 0 to 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，1-(2-氨乙基)哌啶等。Piperidine-type polyamines such as 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethylpiperidine, 1-(2- Aminoethyl) piperidine, etc.

这里的多胺还可以是如式4、5和6所示的含叔胺的多胺。The polyamine here may also be a polyamine containing a tertiary amine as shown in formulas 4, 5 and 6.

其中R₉、R₁₀为C1-C24的烃基，x4为0到10的整数。优选R₉、R₁₀为C1-C10的烃基，x4为1到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，3-二乙胺基丙胺(DEAPA)、3-二甲胺基丙胺(DMAPA)、3-(二丁氨基)丙胺(CAS号102-83-0)等。Wherein R₉ and R₁₀ are C1-C24 hydrocarbon groups, and x4 is an integer from 0 to 10. Preferably, R₉ and R₁₀ are C1-C10 hydrocarbon groups, and x4 is an integer from 1 to 8. For example, N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, N,N-dimethyl-1,4-butanediamine, N , N-diethyl-1,4-butanediamine, N,N-dimethyl-1,6-hexanediamine, 3-diethylaminopropylamine (DEAPA), 3-dimethylaminopropylamine ( DMAPA), 3-(dibutylamino)propylamine (CAS No. 102-83-0) and the like.

其中x5为1到10的整数，优选为2到6的整数，例如三(2-氨基乙基)胺。Where x5 is an integer from 1 to 10, preferably an integer from 2 to 6, such as tris(2-aminoethyl)amine.

其中R₁₁为C1-C24的烃基，x6为1到10的整数，优选为2到6的整数，例如N，N-双(3-氨丙基)甲胺。Wherein R₁₁ is a C1-C24 hydrocarbon group, x6 is an integer from 1 to 10, preferably an integer from 2 to 6, such as N, N-bis(3-aminopropyl)methylamine.

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、碳数为1-30的烃基。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 or 3, y1 can be an integer of 1-8, R can be hydrogen, and_a hydrocarbon group with a carbon number of 1-30.

本发明所述的有机胺除含有上述多胺外，还可再含有一元胺。这里的一元胺可以是伯胺，也可以是仲胺。优选伯胺。可以是碳原子数为1-30的脂肪胺，也可以是碳原子数为1-30的芳胺，优选脂肪胺，脂肪伯胺中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、正二十二胺及其混合物，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、异二十胺及其混合物。脂肪伯胺还可以是带有脂肪环的胺如环戊胺、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Primere 81R的叔碳伯胺。The organic amines described in the present invention may further contain monoamines in addition to the above-mentioned polyamines. The monoamine here can be a primary amine or a secondary amine. Primary amines are preferred. It can be an aliphatic amine with a carbon number of 1-30, or an aromatic amine with a carbon number of 1-30, preferably an aliphatic amine, and the aliphatic primary 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-dodecylamine and mixtures thereof, may also be primary fatty amines with branched chains, and these primary fatty amines with branched chains are the above-mentioned straight-chain primary fatty amines. Various isomers of amines, such as isopropylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, isohexylamine, isoheptylamine, isooctylamine (2-ethylhexylamine), isononylamine, iso Decylamine, Isododecylamine, Isotetradecylamine, Isohexadecylamine, Isostearylamine, Isoeicosylamine and mixtures thereof. Primary aliphatic amines can also be amines with aliphatic rings such as cyclopentylamine and cyclohexylamine. It can also be aliphatic primary amines containing unsaturated double bonds or triple bonds in the carbon chain, such as oleylamine (octadecenylamine), palm oilamine (hexadecenylamine), or tertiary carbon primary amines, such as those produced by Rohm&Haas The trade name of Primere 81R is a tertiary primary amine.

本发明所述的与马来酸酐接枝聚合物反应的有机胺优选含有多胺，进一步优选含至少一个伯胺基团的多胺，尤其优选多烯多胺。The organic amine reacted with the maleic anhydride graft polymer in the present invention preferably contains polyamines, more preferably polyamines containing at least one primary amine group, especially preferably polyene polyamines.

上述马来酸酐接枝聚合物含有-NH官能团的氨和/或有机胺反应已为本领域技术人员所公知，例如可以不用催化剂，将上述马来酸酐接枝聚合物与有机胺混合，在溶剂存在下回流分水或通过氮气吹扫除水或除甲醇、乙醇生成，或者在酸性或碱性催化剂作用下进行上述反应，酸性催化剂如硫酸、磷酸、对甲苯磺酸、酸性离子交换树脂、杂多酸、固体超强酸、酸性白土、酸性分子筛等，碱性催化剂如NaOH、KOH、Ca(OH)₂、Mg(OH)₂、甲醇钠、甲醇钾、有机胺等，具体在此不再赘述。Above-mentioned maleic anhydride graft polymer contains the reaction of ammonia and/or organic amine of -NH functional group known to those skilled in the art, for example can not use catalyst, above-mentioned maleic anhydride graft polymer is mixed with organic amine, in solvent In the presence of reflux for water separation or nitrogen purging to remove water or remove methanol and ethanol, or carry out the above reaction under the action of an acidic or basic catalyst, such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid, acidic ion exchange resin, heteropoly Acid, solid superacid, acid clay, acidic molecular sieve, etc., basic catalysts such as NaOH, KOH, Ca(OH)₂ , Mg(OH)₂ , sodium methoxide, potassium methoxide, organic amine, etc., details will not be repeated here.

所述马来酸酐与油溶性聚合物的接枝聚合物进行胺化或氨解反应时，马来酸酐与以-NH计的含有-NH官能团的氨和/或有机胺的摩尔比可以为1∶0.5-5。When the graft polymer of the maleic anhydride and the oil-soluble polymer undergoes amination or ammonolysis reaction, the molar ratio of maleic anhydride to the ammonia and/or organic amine containing the -NH functional group in terms of -NH can be 1 : 0.5-5.

本发明中，除非特别说明，所述组分a的含量以上述反应后所得产物不去除溶剂后优选经过去除马来酸酐的步骤的量为基准，也即上述溶剂的量也作为组分a的一部分。In the present invention, unless otherwise specified, the content of the component a is based on the amount of the product obtained after the above reaction without removing the solvent, preferably through the step of removing maleic anhydride, that is, the amount of the above solvent is also used as the amount of the component a part.

作为组分a的具体的接枝聚合物的例子有很多，但本发明的范围不受这些例子的限制：There are many examples of specific graft polymers as component a, but the scope of the present invention is not limited by these examples:

马来酸酐接枝聚(甲基)丙烯酸C6-C22烷基酯共聚物与含有多胺的有机胺的胺化反应产物；马来酸酐接枝C6-C24α-烯烃共聚物与含有多胺的有机胺的胺化反应产物；马来酸酐接枝聚苯乙烯共聚物与含有多胺的有机胺的胺化反应产物；马来酸酐接枝乙烯-醋酸乙烯酯共聚物与含多胺的有机胺的胺化反应产物。The amination reaction product of maleic anhydride grafted poly(meth)acrylate C6-C22 alkyl ester copolymer and organic amine containing polyamine; maleic anhydride grafted C6-C24α-olefin copolymer and organic polyamine containing polyamine The amination reaction product of amine; the amination reaction product of maleic anhydride grafted polystyrene copolymer and organic amine containing polyamine; the reaction product of maleic anhydride grafted ethylene-vinyl acetate copolymer and organic amine containing polyamine amination reaction product.

本发明所述添加剂除含有组分a之外，优选还含有组分b。组分b与组分a的重量比可以为0.01-10∶1，优选为0.05-5∶1。The additive according to the invention preferably also contains, in addition to component a, component b. The weight ratio of component b to component a may be 0.01-10:1, preferably 0.05-5:1.

组分bComponent b

组分b可以为芳胺型抗氧剂和/或受阻酚型抗氧剂。Component b may be an aromatic amine antioxidant and/or a hindered phenol antioxidant.

作为组分b的所述芳胺型抗氧剂可以选自萘胺衍生物、二苯胺衍生物、对苯二胺衍生物、喹啉衍生物中的至少一种。The aromatic amine antioxidant as component b may be selected from at least one of naphthylamine derivatives, diphenylamine derivatives, p-phenylenediamine derivatives, and quinoline derivatives.

其中萘胺衍生物包括但不限于下列物质中的一种或多种：Wherein the naphthylamine derivatives include but 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，萘胺衍生物优选苯基萘胺，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 naphthylamine derivative is preferably phenylnaphthylamine, such as one or more of phenyl-α-naphthylamine, phenyl-β-naphthylamine, and N-p-methoxyphenyl α-naphthylamine. Phenyl-α-naphthylamine is especially preferred.

其中二苯胺衍生物包括但不限于下列物质中的一种或多种：Wherein diphenylamine derivatives include but 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、壬基中的一种或多种，其工业产品的例子有美国Pennwalt公司商品名为Pennox A、Pennox A-“S”，美国National polychem公司商品名为Wytox ADP、ADP-X，美国Vanderbilt公司商品名为Agerite Stalite、Agerite Stalite S、Agerite Nepa、Agerite Gel，美国Uniroyal公司商品名为Polylite、Antioxidant 445、以及国内代号为T534的抗氧剂产品。And a mixture of alkylated diphenylamines, wherein the alkyl group can be one or more of heptyl, octyl, and nonyl. The examples of its industrial products have the trade names of Pennwalt Company in the United States, Pennox A, Pennox A-"S ", U.S. National polychem company trade name is Wytox ADP, ADP-X, U.S. Vanderbilt company trade name is Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, U.S. Uniroyal company trade name is Polylite, Antioxidant 445, and domestic code name is Antioxidant products of T534.

二苯胺衍生物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。Diphenylamine derivative 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.

其中对苯二胺衍生物型抗氧剂包括但不限于下列物质中的一种或多种：Wherein p-phenylenediamine derivative antioxidants include but 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;

对苯二胺衍生物型抗氧剂优选二烷基对苯二胺，尤其优选烷基碳原子数在4-10之间的二烷基对苯二胺，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。The p-phenylenediamine derivative antioxidant is preferably dialkyl-p-phenylenediamine, especially dialkyl-p-phenylenediamine with an alkyl carbon number between 4-10, such as: N, N'-diheptyl N,N'-di-sec-butyl-p-phenylenediamine; N,N'-dioctyl-p-phenylenediamine; N,N'-bis-(1-methylheptyl)-p-phenylenediamine One or more of diamines.

其中的喹啉衍生物包括但不限于：Among them, quinoline derivatives 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).

芳胺抗氧剂优选对苯二胺类芳胺抗氧剂。The aromatic amine antioxidant is preferably p-phenylenediamine aromatic amine antioxidant.

组分b中所述酚型抗氧剂可以是单酚、双酚或多酚，也可以是它们任意比例的混合物。The phenolic antioxidant in component b can be monophenol, bisphenol or polyphenol, or a mixture of them 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, methyl Oxy-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)中的一种或多种。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通过硫或碳原子相连的酚型抗氧剂，例如：Bisphenols refer to phenolic antioxidants that are connected by two monophenols through sulfur or carbon atoms, such as:

(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)(Nocrac 300)；4,4'-thiobis-(2,6-di-tert-butylphenol) (Nocrac 300);

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.

双酚型抗氧剂优选由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：Bisphenol antioxidants are preferably bisphenols that have at least one tert-butyl group in the ortho-position of the phenolic hydroxyl group through methylene or sulfur-linked bisphenols, such as:

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)(Nocrac 300)；4,4'-thiobis-(2,6-di-tert-butylphenol) (Nocrac 300);

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.

所述多酚抗氧剂指分子中由至少三个单酚基团的大分子抗氧剂优选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：The polyphenol antioxidant refers to a macromolecular antioxidant consisting of at least three monophenolic groups in the molecule, preferably a polyphenol consisting of a monophenolic group with at least one tert-butyl group in the ortho position of the phenolic hydroxyl group, especially preferably having Hindered polyphenols with two tert-butyl groups ortho to the phenolic hydroxyl group, for example:

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；以及中国专利申请号200810115581.8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 ammonia salt disclosed in Chinese Patent Application No. 200810115581.8. The polyphenolic antioxidant is preferably a gallic acid derivative, especially propyl gallate.

上述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，特别是通过亚甲基或硫相连的双酚型抗氧剂以及多酚抗氧剂中没食子酸酯、没食子酸酰胺或氨盐。The above-mentioned phenolic antioxidant preferably has at least one tert-butyl group in the bisphenolic antioxidant at the ortho position of the phenolic hydroxyl group, especially the bisphenolic antioxidant linked by methylene or sulfur and the gall in the polyphenolic antioxidant esters, gallic acid amides or ammonia salts.

组分b还可以是上述芳胺型抗氧剂与上述酚型抗氧剂的复合抗氧剂。本发明最优选所述组分b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)硫醚中的一种或多种。Component b can also be a composite antioxidant of the above-mentioned aromatic amine antioxidant and the above-mentioned phenolic antioxidant. In the present invention, the most preferred component b is N,N'-diheptyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-dioctyl-p-phenylenediamine, 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 Base-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-butyl One or more of phenol), bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide.

本发明人惊喜地发现，所述组分a与上述组分b复合后，出现明显的协同效应，对含生物柴油燃料氧化安定性的改善作用大大增强。The present inventors were surprised to find that after the component a is compounded with the above-mentioned component b, there is an obvious synergistic effect, and the improvement effect on the oxidation stability of the biodiesel-containing fuel is greatly enhanced.

根据使用需要，本发明提供的柴油组合物还可以含有其它添加剂，如金属钝化剂、清净分散剂、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多种。According to the needs of use, the diesel oil composition provided by the present invention can also contain other additives, such as metal deactivators, detergent dispersants, flow improvers, cetane number improvers, antistatic agents, preservatives, rust inhibitors, One or more of emulsions and the like.

所述金属钝化剂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多种。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多种。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多种。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多种。Described metal deactivator can be benzotriazole and derivative thereof, thiadiazole and derivative thereof, 8-hydroxyquinoline, ethylenediaminetetracarboxylic acid, hydrazide, β-diketone, β-ketoester, One or more of Schiff bases, organic polycarboxylic acids and derivatives thereof. 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 ammonium salts of benzotriazole and fatty amines and products obtained by Mannich reaction of benzotriazole, formaldehyde and fatty amines. 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, 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.

所述清净分散剂的例子可以包括丁二酰亚胺、曼尼西碱、聚异丁烯胺和聚醚胺；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分子量在500-3000的聚烯烃基丁二酸酐和/或丁二酸与胺的反应产物，如国产商品牌号为T151A(单丁二酰亚胺)、T151B(单丁二酰亚胺)、T152(双丁二酰亚胺)、T154(双丁二酰亚胺)、T155(多聚丁二酰亚胺)和/或T161(多聚丁二酰亚胺)等。进口添加剂如OLOA-1200、LZ894、Infineum C9238、9237、Hitec 644等。曼尼西碱型无灰分散剂例如数均分子量在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，尤其是多烯多胺。Examples of the detergent dispersant may include succinimide, Mannich base, polyisobutylene amine and polyether amine; The reaction product of polyolefin-based succinic anhydride and/or succinic acid and amine with an average molecular weight of 500-3000, such as domestic brand names T151A (monosuccinimide), T151B (monosuccinimide), T152 (bis-succinimide), T154 (bis-succinimide), T155 (polysuccinimide) and/or T161 (polysuccinimide), etc. Imported additives such as OLOA-1200, LZ894, Infineum C9238, 9237, Hitec 644, etc. Mannich base type ashless dispersants such as condensation products of polyolefin-based phenols with formaldehyde and amines with a number average molecular weight of 500-3000; said polyetheramine type ashless dispersants such as C8-C30 alkylphenols and ethylene oxide Or the product of condensation with amine after addition of propylene oxide or the product of condensation with amine after addition of C8-C30 alcohol with ethylene oxide or propylene oxide; the polyolefin amine type ashless dispersant such as chlorinated Polyolefin-based amines formed by reacting polyolefins with amines. The amines mentioned here are all preferably polyamines, especially polyene polyamines.

所述十六烷值改进剂的例子可以包括有机硝酸酯如硝酸异辛酯(T2201)、硝酸戊酯和过氧化物如二叔丁基过氧化物；所述消泡剂的例子可以包括商购的T901、T911、T921和T922；所述抗静电剂的例子可以包括商购的T1502、Stadis 425和Stadis 450。Examples of the cetane number improver can include organic nitrates such as isooctyl nitrate (T2201), amyl nitrate and peroxides such as di-tert-butyl peroxide; examples of the defoamer can include commercial commercially available T901, T911, T921 and T922; examples of the antistatic agent may include commercially available T1502, Stadis 425 and Stadis 450.

本发明提供的柴油组合物的制备简单，只需将组成柴油组合物的各组分混合均匀即可。可以直接将各添加剂成分与基础柴油混合，也可以先将各种添加剂成分混合均匀，得到添加剂后，再将所得添加剂与基础柴油混合。为了操作方便，在将各种添加剂成分混合均匀时，可以在溶剂存在下进行，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(THF)、二甲基亚砜(DMSO)、吡咯烷酮和甲基吡咯烷酮中的一种或多种。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 diesel composition provided by the invention is simple, and only needs to mix the components of the diesel composition uniformly. The various additive components can be directly mixed with the base diesel oil, or the various additive components can be mixed evenly first to obtain the additives, and then the obtained additives can be mixed with the base diesel oil. For the convenience of operation, when the various additive components are mixed uniformly, it can be carried out in the presence of a solvent, and the solvent here can be a polar solvent such as N, N-dimethylformamide (DMF), 1,4-dioxane One or more of ring, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), pyrrolidone and methylpyrrolidone. It can also be hydrocarbons, especially aromatics such as benzene, toluene, xylene, aromatics diluent oil and their mixtures, and biodiesel.

在本发明中，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 present invention, the base diesel oil can be pure biodiesel, and the biodiesel refers to fatty acid lower alcohol esters generated by transesterification (alcoholysis) reaction of oil and lower carbon alcohol (such as C1-C5 fatty alcohol) , generally fatty acid methyl ester, that is, the transesterification product 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、棕榈油、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(Tall Oil)、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 tree 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, oils of halo plants such as sea mallow, oil sand bean and other plants . 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多种，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 more, the volume ratio of 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GB 252-2000或车用柴油国家标准GB/T 19147-2003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 for light diesel oil GB 252-2000 or the national standard for vehicle diesel oil GB/T 19147-2003 as 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(Gas To Liquid)或CTL柴油(Coal To Liquid)，还可以是植物纤维经费-托合成方法而生产的BTL柴油(Biomass To Liquid)。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 (Gas To Liquid) or CTL diesel (Coal To Liquid) produced by the Fischer-Tropsch (F-T) synthesis method using natural gas or coal as raw material, and it can also be plant fiber by the Fischer-Tropsch synthesis method And the production of BTL diesel (Biomass To Liquid). 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 the second generation biodiesel, refers to the C8-C24 alkanes mainly composed of C8-C24 alkanes, especially C12-C20 n-paraffins, which are mainly composed of C8-C20 normal alkanes produced by animal and vegetable oils after hydrogenation and cracking reactions. The reaction product, this hydrocracking biodiesel has a high cetane number and extremely low sulfur and aromatic content, and can be used as diesel engine fuel or blending components to 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(Polyoxymethylene Dimethyl Ethers，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 specifications, usually alcohols and ethers or their mixtures, alcohols such as C1-C18 fats Alcohols, preferably C1-C12 monohydric fatty alcohols, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, lauryl alcohol and various isomer. 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 polyoxygen ether Vinyl ether, C6-C14 alkylphenol polyoxypropylene ether, polyoxymethylene dimethyl ether (Polyoxymethylene Dimethyl Ethers, CH3O(CH2O)xCH3, x=1-8), etc. and their mixtures.

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。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 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. 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 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，所述添加剂含有组分a以及组分b。The method for improving the oxidation stability of biodiesel provided by the invention includes adding an additive to the diesel component containing biodiesel, and the additive contains component a and component b.

所述添加剂的组分a、添加剂的组分b各自与上述柴油组合物中的组分a、组分b相同，其种类和用量已在前文描述，在此不再赘述。Component a and component b of the additive are respectively the same as component a and component b in the above-mentioned diesel oil composition, and their types and amounts have been described above, and will not be repeated here.

优选情况下，本发明提供的提高生物柴油氧化安定性的方法还包括在含有生物柴油的基础柴油中，加入其它添加剂，如清净分散剂、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多种。Preferably, the method for improving the oxidation stability of biodiesel provided by the present invention also includes adding other additives, such as detergent dispersant, flow improver, cetane number improver, antistatic agent, to the base diesel oil containing biodiesel , preservatives, rust inhibitors, demulsifiers, etc. in one or more.

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。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 diesel composition, for example, mixing can be at ambient temperature.

所述生物柴油既可以是前述纯的生物柴油，也可以是前述含生物柴油的调合燃料。The biodiesel can be the aforementioned pure biodiesel, or the aforementioned blended fuel containing biodiesel.

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.

以下实施例中，样品的接枝率采用酸碱滴定法测定，测试的方法具体为：准确称量提纯后的接枝聚合物样品0.5g左右，溶解于适量二甲苯中，回流15min后冷却至70℃，然后加入0.1mol/L的氢氧化钾-乙醇进行皂化回流，1h后，再用酚酞-百里酚酞混合指示剂，趁热用0.1mol/L的醋酸-二甲苯溶液反滴定至终点。接枝率的计算公式为：In the following examples, the grafting rate of the sample is measured by acid-base titration, and the method of testing is specifically: accurately weigh about 0.5 g of the grafted polymer sample after purification, dissolve it in an appropriate amount of xylene, and cool to 70°C, then add 0.1mol/L potassium hydroxide-ethanol for saponification and reflux, after 1h, use phenolphthalein-thymolphthalein mixed indicator, back titrate with 0.1mol/L acetic acid-xylene solution while hot to the end point . The formula for calculating the grafting rate is:

其中，M为马来酸酐分子质量(98.06)；N_HAC为醋酸-二甲苯溶液的浓度(mol/L)；V₀为空白滴定时所消耗醋酸-二甲苯溶液的体积(mL)；V为含有产物时滴定所消耗醋酸-二甲苯溶液的体积(mL)；W为试样的重量(g)。Wherein, M is maleic anhydride molecular weight (98.06); N_HAC is the concentration (mol/L) of acetic acid-xylene solution; V_O is the volume (mL) of acetic acid-xylene solution consumed when blank titration; V is The volume (mL) of the acetic acid-xylene solution consumed by titration when the product is contained; W is the weight (g) of the sample.

制备例1Preparation Example 1

将200g聚甲基丙烯酸酯(商品添加剂T602，中石化上海高桥石化分公司炼油厂生产)，20g马来酸酐和200g芳烃稀释油溶剂置于一装有电动搅拌器、温度计、回流冷凝管、滴液漏斗及氮气导入管的反应器中，通入氮气5-10分钟，并在反应过程中保持微弱的氮气流，加热搅拌升温至140-150℃，将2.2g二叔丁基过氧化物及20g芳烃稀释油混合物从滴液漏斗中分3次滴入反应器，1.5小时内滴完，保持温度140-150℃，回流反应3小时，加大氮气流量，在150℃通氮气2小时以除去未反应的马来酸酐，降温到50℃，加入丙酮析出产物，抽滤、洗涤后接着用丙酮洗提，在80℃时于真空干燥箱中干燥到恒重，得到马来酸酐-聚甲基丙烯酸酯接枝共聚物108.8g，接枝率为5.7。Put 200g polymethacrylate (commodity additive T602, produced by refinery of Sinopec Shanghai Gaoqiao Petrochemical Company), 20g maleic anhydride and 200g aromatic hydrocarbon diluting oil solvent in a tank equipped with electric stirrer, thermometer, reflux condenser, drop Into the reactor of the liquid funnel and the nitrogen introduction pipe, feed nitrogen for 5-10 minutes, and maintain a weak nitrogen flow during the reaction, heat and stir to raise the temperature to 140-150 ° C, and add 2.2 g of di-tert-butyl peroxide and 20g of aromatic hydrocarbon diluent oil mixture was dropped into the reactor in 3 times from the dropping funnel, and the dripping was completed within 1.5 hours. For unreacted maleic anhydride, cool down to 50°C, add acetone to precipitate the product, filter, wash and then elute with acetone, and dry it in a vacuum oven at 80°C to constant weight to obtain maleic anhydride-polymethyl Acrylate graft copolymer 108.8g, graft ratio 5.7.

制备例2Preparation example 2

将200g聚乙烯-醋酸乙烯酯(柴油商品降凝剂T1804C，北京有机化工厂生产)，12g马来酸酐和100g甲苯溶剂置于一装有电动搅拌器、温度计、回流冷凝管、滴液漏斗及氮气导入管的反应器中，通入氮气5-10分钟，并在反应过程中保持微弱的氮气流，加热搅拌升温至80℃，将3.0g过氧化苯甲酰及20g甲苯混合物从滴液漏斗中分3次滴加入反应器，1.5小时内滴完，保持温度85℃，反应4小时，减压蒸馏除去未反应的马来酸酐和溶剂，降温到50℃，加入甲醇析出产物，抽滤、洗涤后，在80℃时于真空干燥箱中干燥到恒重，得到马来酸酐-聚乙烯-醋酸乙烯酯接枝共聚物103.2g，接枝率为4.2。200g polyethylene-vinyl acetate (diesel commodity pour point depressant T1804C, produced by Beijing Organic Chemical Factory), 12g maleic anhydride and 100g toluene solvent are placed in an electric stirrer, thermometer, reflux condenser, dropping funnel and Into the reactor of the nitrogen gas introduction tube, feed nitrogen gas for 5-10 minutes, and maintain a weak nitrogen flow during the reaction, heat and stir to raise the temperature to 80°C, and pour the mixture of 3.0g benzoyl peroxide and 20g toluene from the dropping funnel Add it dropwise to the reactor in 3 times, finish the drop within 1.5 hours, keep the temperature at 85°C, react for 4 hours, remove unreacted maleic anhydride and solvent by distillation under reduced pressure, cool down to 50°C, add methanol to precipitate the product, filter with suction, After washing, it was dried to constant weight in a vacuum oven at 80° C. to obtain 103.2 g of maleic anhydride-polyethylene-vinyl acetate graft copolymer with a graft ratio of 4.2.

实施例1-2用于说明本发明所述组分a的合成。Examples 1-2 are used to illustrate the synthesis of component a of the present invention.

实施例1Example 1

实施例1是马来酸酐-聚甲基丙烯酸酯接枝共聚物与多胺的胺化产物。Example 1 is the amination product of maleic anhydride-polymethacrylate graft copolymer and polyamine.

将50g制备例1得到的马来酸酐-聚甲基丙烯酸酯接枝共聚物、65g二甲苯和6.5g的N-椰油基-1，3-丙撑二胺置于一装有电动搅拌器、温度计、回流冷凝管、分水器及氮气导入管的反应器中，在100℃反应2小时，再加入4.3g三乙烯四胺，通入氮气110℃分水反应3小时，得到红色油状液体118.5g，即为本发明所述的组分，有效浓度约为50％。The maleic anhydride-polymethacrylate graft copolymer that 50g preparation example 1 obtains, 65g xylene and 6.5g N-coco base-1,3-propylene diamine are placed in an electric stirrer , a thermometer, a reflux condenser, a water separator, and a nitrogen inlet pipe, react at 100°C for 2 hours, then add 4.3g of triethylenetetramine, feed nitrogen at 110°C for 3 hours, and obtain a red oily liquid 118.5g is the component of the present invention, and the effective concentration is about 50%.

实施例2Example 2

实施例2是马来酸酐聚乙烯-醋酸乙烯酯接枝共聚物和多胺的胺化产物。Example 2 is the amination product of maleic anhydride polyethylene-vinyl acetate graft copolymer and polyamine.

将50g制备例2制得的马来酸酐-聚乙烯-醋酸乙烯酯接枝共聚物、60g二甲苯和3.2g十二胺置于一装有电动搅拌器、温度计、回流冷凝管、分水器及氮气导入管的反应器中，在100℃反应1小时，再加入4.9g四乙烯五胺，通入氮气110℃分水反应4小时，得到红色油状液体108.4g，即为本发明所述的组分a，有效浓度约为50％。The maleic anhydride-polyethylene-vinyl acetate graft copolymer that 50g preparation example 2 makes, 60g dimethylbenzene and 3.2g dodecylamine are placed in a motor stirrer, thermometer, reflux condenser, water separator In the reactor with nitrogen inlet pipe, react at 100°C for 1 hour, then add 4.9g of tetraethylenepentamine, feed nitrogen at 110°C for water separation and reaction for 4 hours, and obtain 108.4g of red oily liquid, which is the compound of the present invention. Component a, the effective concentration is about 50%.

性能测试Performance Testing

以下测试中，所用地沟油生物柴油均由福建龙岩卓越新能源有限公司提供，酸化油生物柴油产品由中海油海南生物能源有限公司提供，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 waste oil biodiesel used was provided by Fujian Longyan Excellence New Energy Co., Ltd., the acidified oil biodiesel product was provided by CNOOC Hainan Bioenergy Co., Ltd., and the petroleum diesel was Jingbiao B diesel produced by Sinopec Yanshan Branch.

(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。采用SH/T 0248的方法测定冷滤点、ASTMD1500方法测定色度。其测试结果示表1和表2，添加量均以干剂计。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 method of SH/T 0248 is used to measure the cold filtration point, and the method of ASTMD1500 is used to measure the chromaticity. Its test results are shown in Table 1 and Table 2, and the additions are all in dry dose.

表1Table 1

表2Table 2

从表1和表2中的数据可以看出，加入本发明的组分a后，生物柴油的氧化安定性得到改善，诱导期增加，同时，冷滤点降低，说明生物柴油的低温流动性也得到一定程度的改善。对苯二胺类抗氧剂(如N，N’-二仲丁基对苯二胺、N，N’-二辛基对苯二胺)对生物柴油氧化安定性的改善作用比较好，但是其对生物柴油冷滤点无改善效果，同时这类化合物都有一定的毒性和染色性，以剂量大加入到生物柴油中会导致生物柴油颜色加深，十六烷值降低，例如表1中生物柴油加入1000mg/kg的N，N’-二仲丁基对苯二胺色度变为3.5，表2中生物柴油加入1500mg/kg的N，N’-二辛基对苯二胺色度变为4.0。尽管对苯二胺类抗氧剂、双酚型抗氧剂对生物柴油氧化安定性有一定改善，本发明所示的聚合物单独使用在添加量少时抗氧效果较弱，但将这两者复合使用后，效果出人意料的大大增强，即本发明另一实施方案出现明显协同效应，按照这一实施方案的生物柴油组合物具有更好的氧化安定性。实施例1、2制备的组分a与胺型或双酚型抗氧剂复合后协同的效应非常明显，对生物柴油颜色的影响也很小。制备1和2制得的接枝聚合物虽然有一定的降冷滤点作用，但对生物柴油氧化安定性的改善作用不大，同时作为组分a与胺型或双酚型抗氧剂复合后增效或者协同的效应也不明显。As can be seen from the data in Table 1 and Table 2, after adding the component a of the present invention, the oxidation stability of biodiesel is improved, and the induction period increases, and at the same time, the cold filter point decreases, indicating that the low temperature fluidity of biodiesel is also improved. improved to a certain extent. P-phenylenediamine antioxidants (such as N, N'-di-sec-butyl-p-phenylenediamine, N, N'-dioctyl-p-phenylenediamine) have a better effect on improving the oxidation stability of biodiesel, but It has no effect on improving the cold filter point of biodiesel. At the same time, these compounds have certain toxicity and dyeing properties. Adding large doses to biodiesel will cause the color of biodiesel to deepen and the cetane number to decrease. For example, the biodiesel in Table 1 Adding 1000mg/kg of N,N'-di-sec-butyl-p-phenylenediamine to the diesel oil will change the color to 3.5, and adding 1500mg/kg of N,N'-dioctyl-p-phenylenediamine to the biodiesel in Table 2 will change the color to is 4.0. Although p-phenylenediamine antioxidants and bisphenol antioxidants can improve the oxidation stability of biodiesel, the polymer shown in the present invention has a weak antioxidant effect when used alone in a small amount, but the combination of these two After they are used in combination, the effect is greatly enhanced unexpectedly, that is, another embodiment of the present invention has an obvious synergistic effect, and the biodiesel composition according to this embodiment has better oxidation stability. Component a prepared in Examples 1 and 2 has a very obvious synergistic effect after compounding with amine or bisphenol antioxidants, and has little effect on the color of biodiesel. Although the grafted polymers prepared in preparation 1 and 2 have a certain effect of lowering the cold filter point, they have little effect on improving the oxidation stability of biodiesel. Post-synergistic or synergistic effects are also not obvious.

(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、低温流动性的测试，所用生物柴油为地沟油生物柴油。(2) The oxidation resistance and low-temperature fluidity test of the blended diesel oil composition using a mixture of biodiesel and petroleum diesel as base diesel oil, and the biodiesel used is waste oil biodiesel.

采用EN 15751：2009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。采用SH/T 0248的方法测定冷滤点、GB/T510方法测定凝点。测试结果均示于表3中。The method of EN 15751:2009 was used to measure the induction period of each diesel oil 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 It shows that the oxidation resistance of the biodiesel composition is better, and on the contrary, the shorter the induction period is, the worse the oxidation resistance of the biodiesel composition is. The method of SH/T 0248 is used to determine the cold filtration point, and the method of GB/T510 is used to determine the freezing point. The test results are shown in Table 3.

表3table 3

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、低温流动性与石油柴油相比都变差。本发明所述组分a单独使用能改善生物柴油调合燃料的低温流动性和氧化安定性，将组分a与对苯二胺型抗氧剂复合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、低温流动性有更大程度的改善，其效果出现协同效应，比单独使用时效果明显增强。未进行胺化反应的接枝聚合物与抗氧剂复合后效果明显不如胺化反应后与抗氧剂复合效果好。It can be seen from the results in Table 3 that after adding biodiesel, the oxidation stability and low temperature fluidity of the blended fuel containing biodiesel are all worse than those of petroleum diesel. Component a of the present invention is used alone to improve the low-temperature fluidity and oxidation stability of biodiesel blended fuel, and the mixture of component a and p-phenylenediamine antioxidant is used as an additive to obtain the biological The oxidation stability and low-temperature fluidity of the diesel composition are improved to a greater extent, and the effect has a synergistic effect, which is obviously stronger than that when used alone. The composite effect of the graft polymer without amination reaction and antioxidant is obviously not as good as that of the composite with antioxidant after amination reaction.

Claims (28)

1. Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, described additive contains component a, and described component a is amination and/or the ammonolysis reaction product of the multipolymer of maleic anhydride graft oil-soluble polymers.

2. Dresel fuel compositions according to claim 1, wherein, described additive is 500-5000ppm with respect to the content of basic diesel oil.

3. Dresel fuel compositions according to claim 1, wherein, the number-average molecular weight of the polymkeric substance among the described component a is 500-100000, and the percentage of grafting of the polymkeric substance among the described component a is 0.5-10, and the number-average molecular weight of oil-soluble polymers is 1000-100000.

4. Dresel fuel compositions according to claim 1, wherein, described component a by the maleic anhydride graft oil-soluble polymers after with contain-ammonia and/or the organic amine of NH functional group obtain by condensation reaction.

5. Dresel fuel compositions according to claim 4, wherein, the mol ratio of described maleic anhydride and oil-soluble polymers is 0.005-0.2: 1.

6. the described Dresel fuel compositions of any one according to claim 1-5, wherein, the monomer of described oil-soluble polymers is ethylenically unsaturated monomers.

7. Dresel fuel compositions according to claim 6, wherein, the monomer of described oil-soluble polymers is one or more in the alpha-olefin, maleic anhydride, toxilic acid, maleic acid ester, maleimide, fumarate, vinyl pyridine, alkyl vinyl ether of ethene, propylene, butylene, divinyl, vinyl cyanide, vinylformic acid C1-C22 alkyl ester, methacrylic acid C1-C22 alkyl ester, acrylamide, Methacrylamide, vinyl acetate, vinylbenzene, C6-C24.

8. Dresel fuel compositions according to claim 4, wherein, the reaction conditions of described maleic anhydride graft oil-soluble polymers comprises that polymerization temperature is 40-250 ℃, polymerization time is 1-10 hour.

9. Dresel fuel compositions according to claim 4, wherein, maleic anhydride with take the containing of-NH-ammonia of NH functional group and/or the mol ratio of organic amine as 1: 0.5-5.

10. Dresel fuel compositions according to claim 1, wherein, described additive also contains components b, and described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and the weight ratio of components b and component a is 0.01-10: 1.

11. Dresel fuel compositions according to claim 10, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position one or more of a tertiary butyl at least.

12. Dresel fuel compositions according to claim 11, wherein, described components b be the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 with the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur in one or more.

13. Dresel fuel compositions according to claim 12, wherein, described components b is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.

14. Dresel fuel compositions according to claim 1, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.

15. method that improves oxidation stability of biodiesel, the method comprises, in containing the basic diesel oil of biofuel, adds additive, described additive contains component a, and described component a is amination or the ammonolysis reaction product of the multipolymer of maleic anhydride graft oil-soluble polymers.

16. method according to claim 15, wherein, described additive is 500-5000ppm with respect to the content of basic diesel oil.

17. method according to claim 15, wherein, the polymkeric substance number-average molecular weight among the described component a is 500-100000, and the percentage of grafting of the polymkeric substance among the described component a is 0.5-10, and the number-average molecular weight of oil-soluble polymers is 1000-100000.

18. the described method of any one according to claim 15-17, wherein, described component a by the maleic anhydride graft oil-soluble polymers after with contain-ammonia and/or the organic amine of NH functional group obtain by condensation reaction.

19. method according to claim 18, wherein, the mol ratio of described maleic anhydride and oil-soluble polymers is 0.005-0.2: 1.

20. method according to claim 18, wherein, the monomer of described oil-soluble polymers is ethylenically unsaturated monomers.

21. method according to claim 20, wherein, the monomer of described oil-soluble polymers is one or more in the alpha-olefin, maleic anhydride, toxilic acid, maleic acid ester, maleimide, fumarate, vinyl pyridine, alkyl vinyl ether of ethene, propylene, butylene, divinyl, vinyl cyanide, vinylformic acid C1-C22 alkyl ester, methacrylic acid C1-C22 alkyl ester, acrylamide, Methacrylamide, vinyl acetate, vinylbenzene, C6-C24.

22. method according to claim 15, wherein, the reaction conditions of described maleic anhydride graft oil-soluble polymers comprises that polymerization temperature is 40-250 ℃, and polymerization time is 1-10 hour.

23. method according to claim 15, wherein, described maleic anhydride with take the containing of-NH-ammonia of NH functional group and/or the mol ratio of organic amine as 1: 0.5-5.

24. method according to claim 15, wherein, described additive also contains components b, and described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and the weight ratio of components b and component a is 0.01-10: 1.

25. method according to claim 24, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position one or more of a tertiary butyl at least.

26. method according to claim 25, wherein, described components b be the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 with the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur in one or more.

27. method according to claim 26, wherein, described components b is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.

28. method according to claim 15, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.