CN103012650B - A kind of copolymer type pour depressant for lubricating oil - Google Patents

A kind of copolymer type pour depressant for lubricating oil Download PDF

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CN103012650B
CN103012650B CN201210520712.7A CN201210520712A CN103012650B CN 103012650 B CN103012650 B CN 103012650B CN 201210520712 A CN201210520712 A CN 201210520712A CN 103012650 B CN103012650 B CN 103012650B
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pour point
lubricating oil
point depressant
terpolymer
fumaric acid
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CN103012650A (en
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周光远
雷金化
张丽
王小波
曹旭
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Shenzhen Hairunde Additive Co ltd
Changchun Institute of Applied Chemistry of CAS
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SHENZHEN HIGHT LUBRICANTS Ltd
Changchun Institute of Applied Chemistry of CAS
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Abstract

一种共聚物型润滑油降凝剂,进一步提高了现有降凝剂的降凝效果。该共聚物型润滑油降凝剂为一种三嵌段共聚物或多种三嵌段共聚物的混合物,所述的三嵌段共聚物的结构式如下:式中,n为7-17的整数,a、b、c分别为1-1000的整数,三嵌段共聚物的粘均分子量为10000-500000。本发明还提供上述三嵌段共聚物的制备方法。本发明的降凝剂具有优异的降凝效果,可达到32℃。

A copolymer type lubricating oil pour point depressant further improves the pour point depressant effect of the existing pour point depressant. The copolymer type lubricating oil pour point depressant is a mixture of a triblock copolymer or a plurality of triblock copolymers, and the structural formula of the triblock copolymer is as follows: In the formula, n is an integer of 7-17, a, b, and c are respectively an integer of 1-1000, and the viscosity-average molecular weight of the triblock copolymer is 10,000-500,000. The present invention also provides a preparation method of the above-mentioned tri-block copolymer. The pour point depressant of the invention has an excellent pour point depressant effect, which can reach 32°C.

Description

一种共聚物型润滑油降凝剂A copolymer type lubricating oil pour point depressant

技术领域technical field

本发明涉及一种共聚物型润滑油降凝剂,属于润滑油添加剂技术领域。The invention relates to a copolymer type lubricating oil pour point depressant, which belongs to the technical field of lubricating oil additives.

技术背景technical background

我国所产原油多为高蜡原油,特别是随着石油资源的日益殆尽,新产原油的含蜡量越来越高,这类原油凝点高、低温流动性差。解决的办法有脱蜡、加氢、加降凝剂等,从降低能耗和生产成本、增加企业经济效益的角度来看,向含蜡原油中添加具有一定功能的高分子降凝剂是简单有效的方法。Most of the crude oil produced in my country is high-wax crude oil, especially with the increasing depletion of oil resources, the wax content of newly produced crude oil is getting higher and higher. This kind of crude oil has a high freezing point and poor low-temperature fluidity. The solutions include dewaxing, hydrogenation, adding point depressants, etc. From the perspective of reducing energy consumption and production costs and increasing the economic benefits of enterprises, it is simple to add polymer point depressants with certain functions to waxy crude oil. effective method.

降凝剂技术始于上世纪三十年代初,主要是用于润滑油领域,1929年Davis用氯化石蜡和萘通过Fride-Craft缩合反应得到了人类最早的降凝剂,即Paraflow。1931年商品名为山驼普尔的降凝剂问世,它是氯化石蜡和酚的缩合物,结构与Paraflow相似。1938-1948年出现了新的降凝剂聚异丁烯。从20世纪50年代起,人们一方面继续开发新型降凝剂,另一方面采用共混及共聚等手段对已有的降凝剂进行改性。20世纪60年代到80年代,随着世界高蜡原油产量的日益增多,为解决生产中的问题,相继研制出适用于不同产地原油性质的降凝剂,并运用在原油输送管道上。The pour point depressant technology began in the early 1930s and was mainly used in the field of lubricating oil. In 1929, Davis obtained the earliest pour point depressant, Paraflow, by using chlorinated paraffin and naphthalene through the Fride-Craft condensation reaction. In 1931, the pour point depressant named Camel Pool came out. It is a condensation product of chlorinated paraffin and phenol, and its structure is similar to Paraflow. From 1938 to 1948, a new pour point depressant, polyisobutylene, appeared. Since the 1950s, people have continued to develop new type of pour point depressants on the one hand, and modified existing pour point depressants by means of blending and copolymerization on the other hand. From the 1960s to the 1980s, with the increasing production of high-wax crude oil in the world, in order to solve the problems in production, pour point depressants suitable for the properties of crude oil from different origins were successively developed and used in crude oil pipelines.

自20世纪80年代以来,随着原油输送方法的增多及人们对低硫高蜡原油需求的逐渐增加,对降凝剂的要求越来越高。世界上一些主要公司不再着重于合成或开发新型降凝剂,而是对某些原有的产品进行了改性或复配。雪弗龙公司利用复合技术,开发出由烯基丁酰二胺酸与聚乙烯-醋酸乙烯酯、聚乙烯-丙烯酸酯组合的复合剂,生产出性能良好的复合降凝剂。Since the 1980s, with the increase of crude oil transportation methods and the gradual increase of people's demand for low-sulfur high-wax crude oil, the requirements for pour point depressants have become higher and higher. Some major companies in the world no longer focus on the synthesis or development of new pour point depressants, but have modified or compounded some original products. Chevron Corporation utilizes composite technology to develop a composite agent composed of alkenyl butyramide acid, polyethylene-vinyl acetate, polyethylene-acrylate, and produce a composite pour point depressant with good performance.

现在国内使用的商品化降凝剂,如聚醋酸乙烯酯-富马酸酯(polymericfumaric ester and vinyl acetate,简称PFVA,中国标号为T818),是由富马酸酯与醋酸乙烯酯共聚而成,该降凝剂虽然具有一定的降凝效果,但是随着原油中蜡含量的增高,润滑油领域亟需具有更加优异的降凝效果的降凝剂。Commercial pour point depressants currently used in China, such as polyvinyl acetate-fumarate (polymeric fumaric ester and vinyl acetate, referred to as PFVA, and the Chinese label is T818), are formed by the copolymerization of fumaric acid ester and vinyl acetate. Although the pour point depressant has a certain pour point depressant effect, as the wax content in crude oil increases, the field of lubricating oil urgently needs a pour point depressant with more excellent pour point depressant effect.

发明内容Contents of the invention

为了进一步提高降凝剂的降凝效果,拓宽其应用领域,本发明提供一种共聚物型润滑油降凝剂。In order to further improve the pour point depressant effect of the pour point depressant and broaden its application field, the invention provides a copolymer type lubricating oil pour point depressant.

本发明提供一种共聚物型润滑油降凝剂,该降凝剂为一种三嵌段共聚物或多种三嵌段共聚物的混合物,所述的三嵌段共聚物的结构式如下:The present invention provides a copolymer-type lubricating oil pour point depressant, which is a triblock copolymer or a mixture of multiple triblock copolymers. The structural formula of the triblock copolymer is as follows:

式中,n为7-17的整数,a、b、c分别为1-1000的整数,三嵌段共聚物的粘均分子量为10000-500000。In the formula, n is an integer of 7-17, a, b, and c are respectively an integer of 1-1000, and the viscosity-average molecular weight of the triblock copolymer is 10,000-500,000.

优选的是,所述的n为11-15的整数,更优选的n为11或者13,最优选的n为13。Preferably, said n is an integer of 11-15, more preferably n is 11 or 13, most preferably n is 13.

优选的是,所述的粘均分子量为10000-100000,更优选的为20000-40000。Preferably, the viscosity average molecular weight is 10,000-100,000, more preferably 20,000-40,000.

优选的是,所述的降凝剂为多种三嵌段共聚物的混合物,更优选的是所述的降凝剂为n为11的三嵌段共聚物和n为13的三嵌段共聚物按质量比1:1-7:3混合的混合物。Preferably, the described pour point depressant is a mixture of various triblock copolymers, more preferably the described pour point depressant is a triblock copolymer with n being 11 and a triblock copolymer with n being 13 The mixture is mixed according to the mass ratio of 1:1-7:3.

本发明还提供上述三嵌段共聚物的制备方法,该方法包括以下步骤:The present invention also provides the preparation method of above-mentioned triblock copolymer, and this method comprises the following steps:

(1)向装置中加入富马酸高级酯、醋酸乙烯酯和苯乙烯,其中,富马酸高级酯、醋酸乙烯酯和苯乙烯的摩尔分数分别为10-80%;(1) add fumaric acid higher ester, vinyl acetate and styrene in the device, wherein, the molar fraction of fumaric acid higher ester, vinyl acetate and styrene is respectively 10-80%;

(2)加入用量为富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.1-1%的自由基聚合引发剂;(2) adding consumption is the free radical polymerization initiator of 0.1-1% of the total mass of fumaric acid higher ester, vinyl acetate and styrene;

(3)升温至70-80℃,反应3-8小时;(3) be heated up to 70-80 ℃, react for 3-8 hours;

(4)减压蒸馏,除去过量的醋酸乙烯酯,得到三嵌段共聚物;(4) underpressure distillation, remove excessive vinyl acetate, obtain triblock copolymer;

所述的富马酸高级酯的结构式为式中,n为7-17的整数。The structural formula of described fumaric acid senior ester is In the formula, n is an integer of 7-17.

优选的是,所述的富马酸高级酯、醋酸乙烯酯和苯乙烯的摩尔分数分别为20-60%。Preferably, the mole fractions of the higher fumaric acid ester, vinyl acetate and styrene are respectively 20-60%.

优选的是,所述的自由基聚合引发剂的用量为富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.5%。Preferably, the amount of the free radical polymerization initiator is 0.5% of the total mass of fumaric acid higher ester, vinyl acetate and styrene.

优选的是,所述的自由基聚合引发剂为过氧化二苯甲酰或者偶氮二异丁腈。Preferably, the free radical polymerization initiator is dibenzoyl peroxide or azobisisobutyronitrile.

优选的是,所述的反应时间为4-6小时。Preferably, the reaction time is 4-6 hours.

本发明的有益效果:Beneficial effects of the present invention:

本发明在聚醋酸乙烯酯-富马酸酯共聚物降凝剂(T818)的基础上添加了第三单体苯乙烯,得到了一种具有优异降凝效果的润滑油降凝剂,该降凝剂能够是单一组分也能够是复配组分,对于基础油150N,复配后的降凝剂最高可以降低19℃,对于基础油150SN,复配后的降凝剂最高可以降低32℃,降凝效果明显优于T818。The present invention adds the third monomer styrene on the basis of polyvinyl acetate-fumarate copolymer pour point depressant (T818), and obtains a lubricating oil pour point depressant with excellent pour point depressant effect. The pour point depressant can be a single component or a compound component. For base oil 150N, the maximum pour point depressant can reduce the temperature by 19°C. For base oil 150SN, the maximum pour point depressant can reduce the maximum temperature by 32°C. , the depressing effect is obviously better than T818.

附图说明Description of drawings

图1为本发明对比例1制备的聚醋酸乙烯酯-富马酸酯降凝剂的红外光谱图;Fig. 1 is the infrared spectrogram of the polyvinyl acetate-fumarate pour point depressant prepared by comparative example 1 of the present invention;

图2为本发明实施例1制备的共聚物型润滑油降凝剂的红外光谱图。Fig. 2 is an infrared spectrogram of the copolymer-type lubricating oil pour point depressant prepared in Example 1 of the present invention.

具体实施方式detailed description

一种三嵌段共聚物,该三嵌段共聚物为醋酸乙烯酯、富马酸酯和苯乙烯的三元共聚物,结构式如下:A three-block copolymer, the three-block copolymer is a terpolymer of vinyl acetate, fumarate and styrene, and its structural formula is as follows:

式中,n为7-17的整数,a、b、c分别为1-1000的整数,三嵌段共聚物的粘均分子量为10000-500000。In the formula, n is an integer of 7-17, a, b, and c are respectively an integer of 1-1000, and the viscosity-average molecular weight of the triblock copolymer is 10,000-500,000.

优选的是,所述的n为11-15的整数,更优选的n为11或者13,最优选的n为13。Preferably, said n is an integer of 11-15, more preferably n is 11 or 13, most preferably n is 13.

优选的是,所述的粘均分子量为10000-100000,更优选的为20000-40000。Preferably, the viscosity average molecular weight is 10,000-100,000, more preferably 20,000-40,000.

一种共聚物型润滑油降凝剂,该降凝剂为一种上述三嵌段共聚物或多种上述三嵌段共聚物的混合物。A copolymer-type lubricating oil pour point depressant, the pour point depressant is a kind of above-mentioned three-block copolymer or a mixture of multiple above-mentioned three-block copolymers.

优选的是,所述的降凝剂为多种三嵌段共聚物的混合物,更优选的是所述的降凝剂为n为11的三嵌段共聚物和n为13的三嵌段共聚物的混合物。Preferably, the described pour point depressant is a mixture of various triblock copolymers, more preferably the described pour point depressant is a triblock copolymer with n being 11 and a triblock copolymer with n being 13 mixture of substances.

本发明还提供上述三嵌段共聚物的制备方法,该方法包括以下步骤:The present invention also provides the preparation method of above-mentioned triblock copolymer, and this method comprises the following steps:

(1)向装置中加入富马酸高级酯、醋酸乙烯酯和苯乙烯,其中,富马酸高级酯、醋酸乙烯酯和苯乙烯的摩尔分数分别为10-80%,富马酸高级酯、醋酸乙烯酯和苯乙烯的摩尔分数之和为100%;(1) Add fumaric acid higher ester, vinyl acetate and styrene in the device, wherein, the molar fractions of fumaric acid higher ester, vinyl acetate and styrene are respectively 10-80%, fumaric acid higher ester, The sum of the mole fractions of vinyl acetate and styrene is 100%;

(2)加入用量为富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.1-1%的自由基聚合引发剂;(2) adding consumption is the free radical polymerization initiator of 0.1-1% of the total mass of fumaric acid higher ester, vinyl acetate and styrene;

(3)升温至70-80℃,反应3-8小时;(3) be heated up to 70-80 ℃, react for 3-8 hours;

(4)减压蒸馏,除去过量的醋酸乙烯酯,得到浅黄色、粘稠状液体,即三嵌段共聚物,也就是单一组分的共聚物型润滑油降凝剂;(4) underpressure distillation, remove excessive vinyl acetate, obtain light yellow, viscous liquid, i.e. triblock copolymer, that is, the copolymer type lubricating oil pour point depressant of single component;

所述的富马酸高级酯的结构式为式中,n为7-17的整数。The structural formula of described fumaric acid senior ester is In the formula, n is an integer of 7-17.

当共聚物型润滑油降凝剂为复配组分,即多种三嵌段共聚物的混合时,先将多种三嵌段共聚物按上述方法制备,得到的多种三嵌段共聚物,经混合,即为复配组分共聚物型润滑油降凝剂,对于混合种类和混合比例没有限制,都能够实现本发明的技术效果,本发明实施例提供,150N和150SN两种基础油中,当复配后嵌段共聚物的n的平均碳数为13时降凝效果更好,优选n为11的三嵌段共聚物和n为13的三嵌段共聚物按质量比1:1-7:3混合,但本发明不限于此。When the copolymer-type lubricating oil pour point depressant is a compound component, that is, when a variety of tri-block copolymers are mixed, the various tri-block copolymers are first prepared according to the above method, and the obtained various tri-block copolymers , after mixing, it is a composite component copolymer-type lubricating oil pour point depressant. There is no restriction on the type and proportion of the mixture, and the technical effect of the present invention can be achieved. The embodiment of the present invention provides two base oils, 150N and 150SN Among them, when the average carbon number of n of the block copolymer after compounding is 13, the pour point depressing effect is better, preferably n is the triblock copolymer of 11 and n is the triblock copolymer of 13 by mass ratio 1: 1-7:3 mixing, but the invention is not limited thereto.

所述的富马酸高级酯、醋酸乙烯酯和苯乙烯的摩尔分数优选分别为20-60%,本发明的三嵌段共聚物,富马酸高级酯、醋酸乙烯酯和苯乙烯的配比中,增加苯乙烯的添加量能够提高降凝剂的降凝效果。The mole fraction of described fumaric acid higher ester, vinyl acetate and styrene is preferably respectively 20-60%, triblock copolymer of the present invention, the proportioning of fumaric acid higher ester, vinyl acetate and styrene Among them, increasing the addition of styrene can improve the pour point depressant effect.

本发明所述的自由基聚合引发剂没有特殊要求,优选为过氧化二苯甲酰、偶氮二异丁腈,用量优选为富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.5%。The radical polymerization initiator described in the present invention has no special requirements, preferably dibenzoyl peroxide and azobisisobutyronitrile, and the consumption is preferably 0.5% of the total mass of fumaric acid higher ester, vinyl acetate and styrene .

本发明的三嵌段共聚物聚合反应温度在70-80℃,为引发剂分解引发的温度,温度低于70℃,只能少量引发聚合反应,且需要较长时间,温度高于80℃,虽然也能够实现本发明,但是考虑到工业化生产成本,温度太高失去实际应用价值。The polymerization reaction temperature of the tri-block copolymer of the present invention is 70-80°C, which is the temperature for the decomposition of the initiator. The temperature is lower than 70°C, and the polymerization reaction can only be initiated in a small amount, and it takes a long time. The temperature is higher than 80°C. Although the present invention can also be realized, considering the cost of industrialized production, the temperature is too high to lose practical application value.

优选的是,所述的反应时间为4-6小时。Preferably, the reaction time is 4-6 hours.

本发明制备三嵌段共聚物的反应方程式如下:The present invention prepares the reaction equation of triblock copolymer as follows:

本发明的富马酸高级酯可以通过商购也可以通过实验室制备获得,其制备方法为现有技术,本发明提供一种富马酸高级酯的制备方法,但本发明不限于此,该方法包括以下步骤:Higher fumaric acid esters of the present invention can be purchased commercially and can also be obtained through laboratory preparation. The preparation method is prior art. The present invention provides a method for preparing higher fumaric acid esters, but the present invention is not limited thereto. The method includes the following steps:

(1)将碳数为8-18高碳醇与富马酸按摩尔比1:0.1-10加入反应装置中;(1) Adding higher carbon alcohols with 8-18 carbon atoms and fumaric acid in a molar ratio of 1:0.1-10 to the reaction device;

(2)加用量为高碳醇与富马酸总质量的40%-300%的溶剂兼带水剂;(2) Adding a solvent with an amount of 40%-300% of the total mass of higher alcohol and fumaric acid;

(3)升高反应体系温度至110-150℃;(3) Raise the temperature of the reaction system to 110-150°C;

(4)加入用量为高碳醇与富马酸总质量的1-2%催化剂,搅拌进行酯化反应3-10小时,搅拌速度50-500转/分;(4) Adding consumption is the 1-2% catalyst of high carbon alcohol and fumaric acid gross mass, stirring carries out esterification reaction 3-10 hour, stirring speed 50-500 rev/min;

(5)减压蒸馏,除去溶剂,得到富马酸高级酯。(5) Distill under reduced pressure to remove the solvent to obtain higher fumaric acid esters.

优选的是,步骤(3)中升温至120-140℃。Preferably, the temperature is raised to 120-140° C. in step (3).

优选的是,步骤(4)中搅拌速度为100-200转/分,反应5-6小时。Preferably, in step (4), the stirring speed is 100-200 rpm, and the reaction is performed for 5-6 hours.

优选的是,所述的高碳醇与富马酸的摩尔比为1:0.5-2。Preferably, the molar ratio of the higher alcohol to fumaric acid is 1:0.5-2.

所述的溶剂兼带水剂没有特殊要求,优选苯、甲苯、二甲苯、环己烷或者石油醚,用量优选为高碳醇与富马酸总质量的60%。There is no special requirement for the solvent and water agent, preferably benzene, toluene, xylene, cyclohexane or petroleum ether, and the dosage is preferably 60% of the total mass of higher alcohol and fumaric acid.

所述的催化剂为酯化反应常用催化剂皆可,优选对甲苯磺酸,用量优选为高碳醇与富马酸总质量的1.4-1.5%。The catalyst can be any catalyst commonly used in esterification reaction, preferably p-toluenesulfonic acid, and the dosage is preferably 1.4-1.5% of the total mass of higher alcohol and fumaric acid.

本发明制备富马酸高级酯的反应方程式如下:The present invention prepares the reaction equation of fumaric acid higher ester as follows:

本发明的共聚物型润滑油降凝剂适用于各种类别的润滑油,该降凝剂作为润滑油添加剂,在润滑油中的添加量为现有技术,添加的量一般不高于2wt%,添加的越高经济价值也就越低,优选降凝剂的添加量为0.5wt%,本发明实施例提供共聚物型润滑油降凝剂在150N和150SN型润滑油,降凝剂添加量为0.1wt%-0.5wt%的降凝效果,但本发明不限于此。The copolymer-type lubricating oil pour point depressant of the present invention is suitable for various types of lubricating oils. The pour point depressant is used as a lubricating oil additive. The amount added to the lubricating oil is the prior art, and the added amount is generally not higher than 2wt%. , the higher the added value, the lower the economic value. The preferred amount of pour point depressant added is 0.5wt%. The embodiment of the present invention provides copolymer lubricating oil pour point depressant in 150N and 150SN lubricating oils. The added amount of pour point depressant The pour point depressing effect is 0.1wt%-0.5wt%, but the present invention is not limited thereto.

本发明共聚物型润滑油降凝剂的降凝效果的检测为本领域公知技术,采用国标GB/T 3535-2006。The detection of the pour point depressant effect of the copolymer lubricating oil pour point depressant of the present invention is a well-known technology in the art, and the national standard GB/T 3535-2006 is adopted.

为了使本领域技术人员进一步理解本发明,下面结合实施例及附图进一步说明本发明。In order to enable those skilled in the art to further understand the present invention, the present invention will be further described below in conjunction with the embodiments and accompanying drawings.

对比例1Comparative example 1

结合图1说明对比例1Illustrate Comparative Example 1 in conjunction with Fig. 1

聚醋酸乙烯酯-富马酸酯(T818)的制备:Preparation of polyvinyl acetate-fumarate (T818):

(1)将0.1mol的十四醇与0.1mol富马酸加入到带有搅拌装置的反应器中,加入十四醇和富马酸总质量的60%的甲苯,加入十四醇和富马酸总质量的1.5%的对甲苯磺酸,在130℃温度下进行聚合5小时,得到富马酸高级酯;(1) Add 0.1 mol of myristyl alcohol and 0.1 mol of fumaric acid into a reactor with a stirring device, add 60% of the total mass of myristyl alcohol and fumaric acid toluene, add the total amount of myristyl alcohol and fumaric acid 1.5% p-toluenesulfonic acid by mass was polymerized for 5 hours at a temperature of 130° C. to obtain higher fumaric acid esters;

(2)在配有搅拌装置、温度传感装置的反应器中加入0.1mol的富马酸高级酯、0.13mol的醋酸乙烯酯,加入富马酸高级酯和醋酸乙烯酯总质量的0.5%的过氧化二苯甲酰,在70-80℃下反应5小时,经减压蒸馏,除去过量的醋酸乙烯酯,得到聚醋酸乙烯酯-富马酸酯降凝剂,粘均分子量为43000万,标记为PFVS01。(2) Add 0.1mol of fumaric acid higher ester, 0.13mol of vinyl acetate in the reactor equipped with stirring device and temperature sensing device, add 0.5% of the total mass of fumaric acid higher ester and vinyl acetate Dibenzoyl peroxide was reacted at 70-80°C for 5 hours, and excess vinyl acetate was removed by vacuum distillation to obtain polyvinyl acetate-fumarate pour point depressant with a viscosity-average molecular weight of 430 million. Marked as PFVS01.

将PFVS01在两种基础油150N和150SN中进行降凝效果测试,降凝剂的加剂量为0.5wt%(降凝剂/基础油),测试结果见表1。PFVS01 was tested for the pour point depressant effect in two base oils, 150N and 150SN, and the dosage of pour point depressant was 0.5wt% (pour point depressant/base oil). The test results are shown in Table 1.

图1为本发明实施例1的聚醋酸乙烯酯-富马酸酯降凝剂的红外光谱图,从图1可以看出,1为-(CH2)n-变形振动峰,2为-C-O-C伸缩振动峰,3为酯的变形振动峰,4为酯羰基伸缩振动峰,5为-C-CH2-C-对称伸缩振动峰,6为-C-CH2-C-不对称伸缩振动峰。Fig. 1 is the infrared spectrogram of the polyvinyl acetate-fumarate pour point depressant of Example 1 of the present invention, as can be seen from Fig. 1, 1 is -(CH 2 ) n -deformation vibration peak, 2 is -COC Stretching vibration peak, 3 is deformation vibration peak of ester, 4 is ester carbonyl stretching vibration peak, 5 is -C-CH 2 -C-symmetric stretching vibration peak, 6 is -C-CH 2 -C-asymmetric stretching vibration peak .

实施例1Example 1

结合图2说明实施例1Embodiment 1 is illustrated in conjunction with Fig. 2

单一组分共聚物型润滑油降凝剂的制备方法:The preparation method of single-component copolymer type lubricating oil pour point depressant:

(1)将0.08mol的十四醇与0.08mol的富马酸加入到带有搅拌装置的反应器中,加入十四醇和富马酸的总质量60%的甲苯,加入十四醇和富马酸总质量的1.5%的对甲苯磺酸,在130℃温度下进行聚合6小时,得到富马酸高级酯;(1) Add 0.08mol of myristyl alcohol and 0.08mol of fumaric acid into a reactor with a stirring device, add 60% of the total mass of myristyl alcohol and fumaric acid toluene, add myristyl alcohol and fumaric acid 1.5% of the total mass of p-toluenesulfonic acid was polymerized at a temperature of 130° C. for 6 hours to obtain a higher ester of fumaric acid;

(2)在配有搅拌装置、温度传感装置的反应器中加入0.08mol的富马酸高级酯、0.08mol的醋酸乙烯酯、0.08mol苯乙烯,加入富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.5%的过氧化二苯甲酰,在70-80℃下反应6小时,经减压蒸馏,除去过量的醋酸乙烯酯,得到共聚物型润滑油降凝剂,粘均分子量为65000,标记为PFVS02。(2) Add 0.08mol fumaric acid higher ester, 0.08mol vinyl acetate, 0.08mol styrene in the reactor equipped with stirring device and temperature sensing device, add fumaric acid higher ester, vinyl acetate and 0.5% dibenzoyl peroxide of the total mass of styrene, react at 70-80°C for 6 hours, and distill under reduced pressure to remove excess vinyl acetate to obtain a copolymer-type lubricating oil pour point depressant, viscosity average molecular weight For 65000, marked as PFVS02.

将PFVS02在两种基础油150N和150SN中进行单一组分降凝效果测试,降凝剂的加剂量为0.5wt%(降凝剂/基础油),测试结果见表1。PFVS02 was tested for single-component pour point depressant effect in two base oils 150N and 150SN, and the dosage of pour point depressant was 0.5wt% (pour point depressant/base oil). The test results are shown in Table 1.

图2为本发明实施例1的共聚物型润滑油降凝剂的红外光谱图,1为-(CH2)n-变形振动峰,2为-C-O-C伸缩振动峰,3为酯的变形振动峰,4为酯羰基伸缩振动峰,5为-C-CH2-C-对称伸缩振动峰,6为-C-CH2-C-不对称伸缩振动峰,7为单取代苯环C-H面外弯曲振动峰,8为苯环的骨架伸缩振动峰。Figure 2 is the infrared spectrogram of the copolymer-type lubricating oil pour point depressant in Example 1 of the present invention, 1 is the deformation vibration peak of -(CH 2 ) n -, 2 is the stretching vibration peak of -COC, and 3 is the deformation vibration peak of ester , 4 is the ester carbonyl stretching vibration peak, 5 is the symmetrical stretching vibration peak of -C-CH 2 -C-, 6 is the asymmetric stretching vibration peak of -C-CH 2 -C-, 7 is the out-of-plane bending of monosubstituted benzene ring CH The vibration peak, 8 is the stretching vibration peak of the skeleton of the benzene ring.

从图1和图2红外光谱对比可知,添加了第三单体苯乙烯的实施例1制备的共聚物型润滑油降凝剂的红外光谱要多出两个峰,分别是峰7、8,峰7代表单取代苯环C-H面外弯曲振动峰,峰8代表苯环的骨架伸缩振动峰,由此证明苯乙烯单体参与了共聚。From the comparison of the infrared spectra of Figure 1 and Figure 2, it can be seen that the infrared spectrum of the copolymer lubricating oil pour point depressant prepared in Example 1 with the addition of the third monomer styrene has two more peaks, which are peaks 7 and 8, respectively. Peak 7 represents the C-H out-of-plane bending vibration peak of the monosubstituted benzene ring, and peak 8 represents the skeleton stretching vibration peak of the benzene ring, which proves that the styrene monomer participates in the copolymerization.

实施例2Example 2

单一组分共聚物型润滑油降凝剂的制备方法:The preparation method of single-component copolymer type lubricating oil pour point depressant:

(1)将0.08mol的十四醇与0.08mol的富马酸加入到带有搅拌装置的反应器中,加入十四醇与富马酸总质量60%的甲苯,加入十四醇与富马酸总质量的1.5%的对甲苯磺酸,在120℃温度下进行聚合5.5小时,得到富马酸高级酯;(1) Add 0.08mol of myristyl alcohol and 0.08mol of fumaric acid into a reactor with a stirring device, add toluene with 60% of the total mass of myristyl alcohol and fumaric acid, add myristyl alcohol and fumaric acid The p-toluenesulfonic acid of 1.5% of the total mass of the acid was polymerized for 5.5 hours at a temperature of 120° C. to obtain a higher ester of fumaric acid;

(2)在配有搅拌装置、温度传感装置的反应器中加入0.08mol的富马酸高级酯、0.08mol的醋酸乙烯酯、0.04mol的苯乙烯,加入富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.5%的过氧化二苯甲酰,在70-80℃下反应4小时,经减压蒸馏,除去过量的醋酸乙烯酯,得到共聚物型润滑油降凝剂,粘均分子量为55000,标记为PFVS03。(2) Add 0.08mol of fumaric acid higher ester, 0.08mol of vinyl acetate, 0.04mol of styrene in the reactor equipped with stirring device and temperature sensing device, add fumaric acid higher ester, vinyl acetate React with 0.5% dibenzoyl peroxide of the total mass of styrene at 70-80°C for 4 hours, and distill under reduced pressure to remove excess vinyl acetate to obtain a copolymer-type lubricating oil pour point depressant, viscosity average The molecular weight is 55000, and it is marked as PFVS03.

将PFVS03在两种基础油150N和150SN中进行单一组分降凝效果测试,降凝剂的加剂量为0.5wt%(降凝剂/基础油),测试结果见表1。PFVS03 was tested for single-component pour point depressant effect in two base oils 150N and 150SN, and the dosage of pour point depressant was 0.5wt% (pour point depressant/base oil). The test results are shown in Table 1.

实施例3Example 3

单一组分共聚物型润滑油降凝剂的制备方法:The preparation method of single-component copolymer type lubricating oil pour point depressant:

(1)将0.08mol的十二醇与0.08mol的富马酸加入到带有搅拌装置的反应器中,加入十二醇和富马酸总质量60%的甲苯,加入十二醇和富马酸总质量的1.5%的对甲苯磺酸,在140℃温度下进行聚合5小时,得到富马酸高级酯;(1) Add 0.08mol of dodecyl alcohol and 0.08mol of fumaric acid into a reactor with a stirring device, add toluene with 60% of the total mass of dodecyl alcohol and fumaric acid, add the total mass of dodecyl alcohol and fumaric acid 1.5% p-toluenesulfonic acid by mass was polymerized at 140°C for 5 hours to obtain higher fumaric acid esters;

(2)在配有搅拌装置、温度传感装置的反应器中加入0.08mol的富马酸高级酯、0.08mol的醋酸乙烯酯、0.04mol的苯乙烯,加入富马酸高级酯、醋酸乙烯酯和苯乙烯总质量的0.5%的引发剂过氧化二苯甲酰,在70-80℃下反应5小时,经减压蒸馏,除去过量的醋酸乙烯酯,得到共聚物型润滑油降凝剂,粘均分子量为58000,标记为PFVS04。(2) Add 0.08mol of fumaric acid higher ester, 0.08mol of vinyl acetate, 0.04mol of styrene in the reactor equipped with stirring device and temperature sensing device, add fumaric acid higher ester, vinyl acetate React with dibenzoyl peroxide, an initiator of 0.5% of the total mass of styrene, at 70-80°C for 5 hours, and distill under reduced pressure to remove excess vinyl acetate to obtain a copolymer-type lubricating oil pour point depressant. The viscosity-average molecular weight is 58000, marked as PFVS04.

将PFVS04在两种基础油150N和150SN中进行单一组分降凝效果测试,降凝剂的加剂量为0.5wt%(降凝剂/基础油),测试结果见表1。PFVS04 was tested for the single-component pour point depressant effect in two base oils 150N and 150SN, and the dosage of pour point depressant was 0.5wt% (pour point depressant/base oil). The test results are shown in Table 1.

表1 单一组分降凝效果测试Table 1 Test of pour point depressing effect of single component

表1中,LZ803B为工业品聚α-烯烃降凝剂;从上表可以看出,不加苯乙烯的降凝剂PFVS01(商品T818)降凝效果明显要低于添加苯乙烯的降凝剂(PFVS02、PFVS03和PFVS04);PFVS02的降凝效果高于PFVS03和PFVS04,说明随着苯乙烯添加量的增加降凝效果增加;本发明单一组分共聚物型润滑油降凝剂的降凝效果不及工业品LZ803B优异。In Table 1, LZ803B is an industrial polyα-olefin pour point depressant; it can be seen from the above table that the pour point depressant effect of PFVS01 (commodity T818) without styrene is obviously lower than that of the pour point depressant with styrene (PFVS02, PFVS03 and PFVS04); the pour point depressing effect of PFVS02 is higher than that of PFVS03 and PFVS04, indicating that the pour point depressing effect increases with the increase of styrene addition; the pour point depressing effect of the single component copolymer type lubricating oil pour point depressant of the present invention It is not as good as the industrial product LZ803B.

实施例4Example 4

复配组分共聚物型润滑油降凝剂的制备方法:The preparation method of compound component copolymer type lubricating oil pour point depressant:

将实施例1制备的PFVS02和实施例3制备的PFVS04按质量比3:7混合,得到共聚物型润滑油降凝剂。The PFVS02 prepared in Example 1 and the PFVS04 prepared in Example 3 were mixed in a mass ratio of 3:7 to obtain a copolymer-type lubricating oil pour point depressant.

将实施例4制备的共聚物型润滑油降凝剂分别在两种基础油150N和150SN中进行复配组分降凝效果测试,降凝剂的加剂量分别为0.5wt%、0.2wt%和0.1wt%(降凝剂/基础油),测试结果见表2,表4和表5。The copolymer-type lubricating oil pour point depressant prepared in Example 4 was tested for the pour point depressing effect of the compound components in two base oils 150N and 150SN respectively, and the dosage of the pour point depressant was 0.5wt%, 0.2wt% and 0.1wt% (pour point depressant/base oil), the test results are shown in Table 2, Table 4 and Table 5.

表2 复配组分降凝效果测试Table 2 Test of pour point depressing effect of compound components

实施例5Example 5

复配组分共聚物型润滑油降凝剂的制备方法:The preparation method of compound component copolymer type lubricating oil pour point depressant:

将实施例1制备的PFVS02和实施例3制备的PFVS04按质量比1:1混合,得到共聚物型润滑油降凝剂。The PFVS02 prepared in Example 1 and the PFVS04 prepared in Example 3 were mixed at a mass ratio of 1:1 to obtain a copolymer-type lubricating oil pour point depressant.

将实施例5制备的共聚物型润滑油降凝剂分别在两种基础油150N和150SN中进行复配组分降凝效果测试,降凝剂的加剂量为0.5wt%(降凝剂/基础油),测试结果见表4和表5。The copolymer-type lubricating oil pour point depressant prepared in Example 5 was respectively tested for the pour point depressing effect of compound components in two kinds of base oils 150N and 150SN, and the dosage of the pour point depressant was 0.5wt% (pour point depressant/base Oil), the test results are shown in Table 4 and Table 5.

实施例6Example 6

复配组分共聚物型润滑油降凝剂的制备方法:The preparation method of compound component copolymer type lubricating oil pour point depressant:

将实施例2制备的PFVS03和实施例3制备的PFVS04按质量比3:7混合,得到共聚物型润滑油降凝剂。The PFVS03 prepared in Example 2 and the PFVS04 prepared in Example 3 were mixed in a mass ratio of 3:7 to obtain a copolymer-type lubricating oil pour point depressant.

将实施例6制备的共聚物型润滑油降凝剂分别在两种基础油150N和150SN中进行复配组分降凝效果测试,降凝剂的加剂量为0.5wt%(降凝剂/基础油),测试结果见表4和表5。The copolymer-type lubricating oil pour point depressant prepared in Example 6 was tested for the pour point depressing effect of the composite components in two base oils 150N and 150SN respectively, and the dosage of the pour point depressant was 0.5wt% (pour point depressant/base Oil), the test results are shown in Table 4 and Table 5.

实施例7Example 7

复配组分共聚物型润滑油降凝剂的制备方法:The preparation method of compound component copolymer type lubricating oil pour point depressant:

将实施例2制备的PFVS03和实施例3制备的PFVS04按质量比1:1混合,得到共聚物型润滑油降凝剂。The PFVS03 prepared in Example 2 and the PFVS04 prepared in Example 3 were mixed at a mass ratio of 1:1 to obtain a copolymer-type lubricating oil pour point depressant.

将实施例7制备的共聚物型润滑油降凝剂分别在两种基础油150N和150SN中进行复配组分降凝效果测试,降凝剂的加剂量分别为0.5wt%、0.2wt%和0.1wt%(降凝剂/基础油),测试结果见表3、表4和表5。The copolymer-type lubricating oil pour point depressant prepared in Example 7 was tested for the pour point depressing effect of the compound components in two base oils 150N and 150SN respectively, and the dosage of the pour point depressant was 0.5wt%, 0.2wt% and 0.1wt% (point depressant/base oil), the test results are shown in Table 3, Table 4 and Table 5.

表3 复配组分降凝效果测试Table 3 Test of pour point depressing effect of compound components

表4 复配组分降凝效果测试Table 4 Test of pour point depressing effect of compound components

表5 复配组分降凝效果测试Table 5 Test of pour point depressing effect of compound components

由上表2-5可知,对于基础油150N,复配后的降凝剂最高可以降低19℃,达到了工业品聚α-烯烃降凝剂LZ803B的效果;对于基础油150SN,复配后的降凝剂最高可以降低32℃,超过了工业品聚α-烯烃降凝剂LZ803B的效果。It can be seen from the above table 2-5 that, for the base oil 150N, the pour point depressant after compounding can reduce the temperature by up to 19°C, reaching the effect of industrial polyα-olefin pour point depressant LZ803B; for the base oil 150SN, the pour point depressant after compounding The pour point depressant can reduce the maximum temperature by 32°C, surpassing the effect of industrial poly-α-olefin pour point depressant LZ803B.

Claims (9)

1. terpolymer is as the application of pour depressant for lubricating oil, it is characterized in that, the structural formula of described terpolymer is as follows:
In formula, n is the integer of 7-17, and a, b, c are respectively the integer of 1-1000, and the viscosity-average molecular weight of terpolymer is 10000-500000;
Described terpolymer is prepared by following methods:
(1) in device, add the senior ester of fumaric acid, vinyl acetate and vinylbenzene, wherein, the senior ester of fumaric acid, vinyl acetate and cinnamic molar fraction are respectively 10-80%;
(2) radical polymerization initiator that consumption is the 0.1-1% of the senior ester of fumaric acid, vinyl acetate and vinylbenzene total mass is added;
(3) 70-80 DEG C is warming up to, reaction 3-8 hour;
(4) underpressure distillation, removes excessive vinyl acetate, obtains terpolymer;
The structural formula of the senior ester of described fumaric acid is in formula, n is the integer of 7-17.
2. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, described n is the integer of 11-15.
3. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, described viscosity-average molecular weight is 20000-40000.
4. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, described pour point depressant is the mixture of multiple described terpolymer.
5. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, described pour point depressant to be n be 11 terpolymer and n be the mixture of the terpolymer 1:1-7:3 mixing in mass ratio of 13.
6. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, the senior ester of described fumaric acid, vinyl acetate and cinnamic molar fraction are respectively 20-60%.
7. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, the consumption of described radical polymerization initiator is 0.5% of the senior ester of fumaric acid, vinyl acetate and vinylbenzene total mass.
8. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, described radical polymerization initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate.
9. terpolymer according to claim 1 is as the application of pour depressant for lubricating oil, it is characterized in that, the described reaction times is 4-6 hour.
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