Highly branched polymethacrylate type pour-point and cloud-point depressant for lubricating oil, and preparation method therefor

Abstract

Provided in the present invention is an efficient and convenient method for preparing a highly branched polymethacrylate type pour-point and cloud-point depressant product for lubricating oil. The pour-point and cloud-point depressant product for lubricating oil is prepared by subjecting methacrylates that have different alkyl chain lengths and serve as main polymerization monomers and an optional diene branching agent to a free radical copolymerization reaction in a conventional base oil. The preparation method can not only effectively prevent the gelation of a polymerization system, but also does not require any post-treatment, thereby improving the stability of a polymer pour-point and cloud-point depressant for lubricating oil. The raw materials of the polymer pour-point and cloud-point depressant product for lubricating oil are widely available, and the preparation process therefor is simple; moreover, the polymerization system has good solubility and can be directly compounded with a target oil product, and the pour point and the cloud point of the target oil product can be effectively reduced when the product is added at a low dosage. By optimizing the preparation method for the polymer pour-point and cloud-point depressant product in the present invention, the cost can be effectively reduced, and the environmental pollution can be reduced; and the polymer pour-point and cloud-point depressant product has broad industrial application prospects.

Description

Highly branched polymethacrylate type pour point depressant and method for preparing the same TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating oil additive development, and in particular to the low-cost, high-efficiency and green preparation of a highly branched polymethacrylate (PMA) type pour point depressant and the evaluation of the application performance after compounding with commercial oil products. BACKGROUND

[0002] Finished lubricating oil usually contains a high proportion of n-alkanes, which are prone to precipitate wax crystals at low temperatures and quickly form a rigid network, thereby losing fluidity, which seriously affects the transportation, storage and use performance of the lubricating oil. Adding a pour point depressant is the most economical and effective way to improve the low-temperature performance of lubricating oil, and the dosage is only 0.1-1 wt.%, which can significantly reduce the pour point and cloud point of the lubricating oil.

[0003] There are three major categories of pour point depressants currently developed and put into production: alkyl naphthalenes, polyolefins and polyesters. Among them, the polymethacrylate (PMA) type pour point depressant is the mainstream pour point depressant used at home and abroad, and its global usage share is more than half in the blending of finished lubricating oil. The PMA type pour point depressant not only has the advantages of strong adjustability of composition and topological structure, high adaptability to various types of base oil, etc., but also has a simple production process, is usually prepared by free radical polymerization, has good compatibility with polar functional groups, low sensitivity to impurities and water vapor, and high product yield, so it is favored by lubricating oil producers and users.

[0004] Foreign large-scale lubricating oil producers, such as AkzoNobel, BASF, Clariant, Dow, Huntsman, Lubrizol, Nalco Water, Sanyo, and Wanhua, have developed a series of PMA type pour point depressant products to meet the growing market demand. The existing PMA type pour point depressant production in China still accounts for a low share in the world market, and the PMA type pour point depressant used in the market mainly depends on imports, accounting for about 90%, and the demand is increasing year by year, which puts higher requirements on domestic lubricating oil companies and related enterprises to quickly break through the technical bottleneck, realize product independent research and development, and upgrade. At present, some companies, such as Sinopec Lubricant Company, Mudanjiang Gaoxin Petroleum Additive Co., Ltd., Dalian Xinyi New Material Development Co., Ltd., and Jinzhou Kangtai Lubricant Additive Co., Ltd., have completed the independent formula, large-scale production and application of PMA type pour point depressant for mainstream lubricating oil products, which has improved the technological strength of the domestic petrochemical industry and laid a solid foundation for early independence from technology.

[0005] Under the environment of increasingly tight oil energy, market demand puts forward higher standards for the development of new technologies of lubricating oil additives. On the basis of reaching industrial performance, it is necessary to reduce the generation and emission of "three wastes", reduce environmental pollution, meet the requirements of green production, and save production cost.

[0006] In summary, the existing PMA-type pour point and turbidity depressant products in China cannot guarantee the self-sufficiency of the mainstream application market of lubricating oil additives, and cannot meet the market demand and production needs of increasingly stringent high-performance lubricating oil. Therefore, there is an urgent need in the art to optimize the production process of PMA-type pour point and turbidity depressant, and to develop a green preparation technology of high-performance and high-branched PMA-type pour point and turbidity depressant, so as to meet the application requirements of lubricating oil under complex working conditions under the "double carbon" target, while reducing cost, realizing the "win-win" of economy and environmental protection. SUMMARY

[0007] The purpose of the present application is to provide a convenient preparation method of green and environmentally friendly, low-cost high-branched PMA-type pour point and turbidity depressant product, which can meet the compounding needs of high-end lubricating oil, effectively reduce the pour point and turbidity point of industrial lubricating oil, and simplify the synthesis and post-processing process, greatly reduce the production cost.

[0008] In a first aspect of the present application, a high-branched PMA-type pour point and turbidity depressant is provided, which is prepared by the following method comprising the steps of:

[0009] free radical polymerization of components (a) and optionally component (b) in base oil to obtain a high-branched PMA-type pour point and turbidity depressant; wherein the mass of components (a) and component (b) is not more than 1 / 3 of the base oil;

[0010] wherein the component (a) is a combination of 3-8 different methyl methacrylate monomers 1a, and the structure of the methyl methacrylate monomers 1a is independently as follows:

[0011] wherein each R 1 is independently C4-C30 alkyl, C6 cycloalkyl, substituted C2-C6 alkyl, the substitution means that one or more hydrogens in C2-C6 alkyl are substituted by a substituent selected from the group consisting of hydroxyl, mercapto, C1-C6 alkyl hydroxyl, C1-C6 alkyl mercapto, -NR 1a R 1b , -L-R 1c , wherein R 1a , R 1b is independently C1-C15 alkyl, L is -(CH2CH2O) n1 , or -(CH2CH2S) n2 , R1c C1-C3 alkyl or hydroxy, wherein each of n1, n2 is independently an integer from 1 to 8;

[0012] The component (b) is a diene branching agent 1b, the structure of which is shown below:

[0013] Y 1 , Y 2 each independently is hydrogen, methyl;

[0014] R 2 is -L1-L2-L3, wherein L1 is C1-C10 alkylene, L2 is nothing or -CH2CH2O-, and L3 is C1-C10 alkylene.

[0015] In another preferred embodiment, each R 1 each independently is C4-C22 alkyl or C6 cycloalkyl.

[0016] In another preferred embodiment, each R 1 each independently is n-alkyl.

[0017] In another preferred embodiment, each R 1 each independently is n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, n-eicosyl, n-docosyl.

[0018] In another preferred embodiment, each of n1, n2 is independently an integer from 1 to 6, for example 1, 2, 3, 4, 5 or 6.

[0019] In another preferred embodiment, the methacrylate mono-olefins 1a are each independently selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, n-eicosyl methacrylate, n-docosyl methacrylate, 2-ethoxyethyl methacrylate, mercaptoethyl ethyl methacrylate, hydroxyethyl polyethylene glycol methacrylate, N,N-diethyl ethyl methacrylate, N-methyl-N-dodecyl ethyl methacrylate.

[0020] In another preferred embodiment, the component (a) is a combination of 3 to 6 different methacrylate mono-olefins 1a, for example 3, 4, 5, 6.

[0021] In another preferred embodiment, the component (a) is a combination of n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, n-eicosyl methacrylate, n-docosyl methacrylate, 2-ethoxyethyl methacrylate, hydroxyethyl polyethylene glycol methacrylate in a combination of 3 to 8 (e.g. 3, 4, 5, 6, 7, 8) species.

[0022] In another preferred embodiment, the component (a) is a combination of the species of methacrylate mono-olefin 1a in Examples 1-6.

[0023] In another preferred embodiment, the component (a) is a combination of n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate.

[0024] In another preferred embodiment, the component (a) is a combination of hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate.

[0025] In another preferred embodiment, the component (a) is a combination of butyl methacrylate, hexyl methacrylate, tetradecyl methacrylate, octadecyl methacrylate.

[0026] In another preferred embodiment, the component (a) is a combination of hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate.

[0027] In another preferred embodiment, the component (a) is a combination of n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate.

[0028] In another preferred embodiment, the component (a) is a combination of n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate.

[0029] In another preferred embodiment, the component (a) is a combination of n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate.

[0030] In another preferred embodiment, R2 is -(CH2)2-, -CH2C(CH3)2CH2- or -CH2[(CH2)2O] n CH2-(n = 3-8).

[0031] In another preferred embodiment, the diene branching agent 1b is dimethyl maleate.

[0032] In another preferred embodiment, the component (b) is present in a molar fraction of 0-10 mol%, preferably 1-5 mol%, for example 2 mol%, 4 mol%, relative to the component (a).

[0033] In another preferred embodiment, the sum of the mass of the component (a) and the component (b) is present in a mass fraction of 2-30%, preferably 8-20%, relative to the total mass of the feed.

[0034] In another preferred embodiment, the base oil is a conventional base oil, preferably a Group I base oil or a Group II base oil, more preferably one or both of the grades 60N, 100N, 150N, 250N, 350N, 500N, 75SN, 100SN, 150SN, 200SN, 250SN, 300SN, 350SN, 400SN, 500SN, 650SN.

[0035] In another preferred embodiment, the base oil is present in a mass fraction of 70-95%, for example 75-90%, relative to the total mass of the feed.

[0036] In another preferred embodiment, the high-branched PMA-type pour point and haze depressant has a mass fraction of the polymer of 5-70%, preferably 5-50%, more preferably 5-30%.

[0037] In another preferred embodiment, the high-branched PMA-type pour point and haze depressant has a mass fraction of the base oil of 30-95%, preferably 50-95%, more preferably 70-95%.

[0038] In another preferred embodiment, the high-branched PMA-type pour point and haze depressant has one or more of the following characteristics selected from the group consisting of:

[0039] (a) a decrease in the cloud point of a commercial oil product of more than 20°C, preferably more than 30°C, more preferably more than 40°C, at an addition level of 1 wt.%;

[0040] (b) a decrease in the pour point of a commercial oil product, preferably a decrease of more than 1°C, more preferably a decrease of more than 3°C, at an addition level of 1 wt.%;

[0041] (c) a decrease in the cloud point of a commercial oil product of more than 20°C, preferably more than 30°C, more preferably more than 40°C, at an addition level of 0.1 wt.%;

[0042] (d) the pour point of the commercial oil product is reduced, preferably by more than 1 °C, more preferably by more than 3 °C, at an additive amount of 0.1 wt.%.

[0043] In another preferred embodiment, the high-branched PMA-type pour point and haze depressant is prepared by the method as described in the second aspect of the present application.

[0044] In another preferred embodiment, the high-branched PMA-type pour point and haze depressant contains the polymer as described in the third aspect of the present application.

[0045] In the second aspect of the present application, a method for preparing the high-branched PMA-type pour point and haze depressant as described in the first aspect of the present application is provided, comprising the steps of:

[0046] radically copolymerizing the component (a) and optionally the component (b) in a base oil to obtain the high-branched PMA-type pour point and haze depressant; wherein the feeding mass of the component (a) and the component (b) is not more than 1 / 3 of the base oil;

[0047] The component (a) is a combination of 3-8 different methacrylate monomers 1a, each of which is independently of the others as shown below:

[0048] wherein each R 1 is independently of the others C4-C30 alkyl, C6 cycloalkyl, substituted C2-C6 alkyl, the substitution meaning that one or more hydrogens in the C2-C6 alkyl are replaced by a substituent selected from the group consisting of hydroxyl, mercapto, C1-C6 alkylhydroxyl, C1-C6 alkylmercapto, -NR 1a R 1b , -L-R 1c , wherein R 1a , R 1b are each independently C1-C15 alkyl, and L is -(CH2CH2O) n1 - or -(CH2CH2S) n2 , R 1c is C1-C3 alkyl or hydroxyl, wherein n1, n2 are each independently 1-8;

[0049] The component (b) is a diene branching agent 1b, which is as shown below:

[0050] Y 1 , Y 2 are each independently hydrogen, methyl;

[0051] R 2-L1-L2-L3, wherein L1 is C1-C10 alkylene, L2 is nothing or -CH2CH2O-, and L3 is C1-C10 alkylene.

[0052] In another preferred embodiment, the component (a), the component (b), each of the methacrylate mono-olefin 1a, and the base oil are each independently as described in the first aspect of the present application.

[0053] In another preferred embodiment, the method comprises the step of:

[0054] In an inert atmosphere, in a base oil, in the presence of a free radical initiator and a chain transfer agent, mixing the component (a) and optionally the component (b) to perform a free radical copolymerization reaction to obtain the PMA type pour point and turbidity depressant;

[0055] wherein the total feeding mass of the initiator, the chain transfer agent, the component (a) and the component (b) is not more than 1 / 3 of the base oil.

[0056] In another preferred embodiment, the inert atmosphere refers to a nitrogen or argon atmosphere.

[0057] In another preferred embodiment, the initiator is an azo initiator.

[0058] In another preferred embodiment, the initiator is selected from the group consisting of azobisisobutyronitrile (AIBN), azobiscyclohexylcarbonitrile (ACCN), azobisisoheptylcarbonitrile (ABVN), or a combination thereof, preferably azobisisobutyronitrile.

[0059] In another preferred embodiment, the molar ratio of the initiator to the component (a) is (0.01-0.8):100, preferably (0.02-0.5):100, for example 0.4:100.

[0060] In another preferred embodiment, the chain transfer agent is a thiol compound, preferably selected from the group consisting of n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, mercapto-polyethylene glycol monomethyl ether, or a combination thereof.

[0061] In another preferred embodiment, the chain transfer agent is n-dodecyl mercaptan.

[0062] In another preferred embodiment, the molar ratio of the chain transfer agent to the component (a) is (0.025-5):100, preferably (0.025-2.5):100, for example 2:100.

[0063] In another preferred embodiment, the molar ratio of the component (b) to the component (a) is (0-10):100, preferably (0-5):100.

[0064] In another preferred embodiment, the total amount of the initiator, chain transfer agent, component (a) and component (b) is 5-30%, preferably 10-25% of the total amount of the feed.

[0065] In another preferred embodiment, the initiator, chain transfer agent, component (a) and component (b) are fed in batches.

[0066] In another preferred embodiment, the reaction is carried out at 40-100°C, preferably at 50-80°C.

[0067] In another preferred embodiment, the reaction time is 20-72h, preferably 28-48h.

[0068] In another preferred embodiment, the reaction is carried out in a closed system, preferably in a sealed tube.

[0069] In another preferred embodiment, the reaction does not require a post-treatment step.

[0070] In another preferred embodiment, after the reaction is completed, the high-branched PMA type pour point and turbidity depressant product can be obtained by cooling and stirring.

[0071] In another preferred embodiment, in the method, the conversion rate of component (a) is more than 85%, preferably more than 90%, more preferably more than 95%.

[0072] In a third aspect of the present application, a polymer is provided, which is prepared by a method comprising the steps of:

[0073] (s1) subjecting component (a) and optionally component (b) to a free radical polymerization reaction in a base oil to obtain a base oil solution containing the polymer;

[0074] optionally (s2) separating the base oil to obtain the polymer;

[0075] wherein the amount of the component (a) and component (b) fed is not more than 1 / 3 of the base oil;

[0076] wherein the component (a) is a combination of 3-8 different methacrylate monomers 1a, each of which is independently as shown below:

[0077] wherein each R 1 is independently C4-C30 alkyl, C6 cycloalkyl, substituted C2-C6 alkyl, wherein the substitution means that one or more hydrogens in the C2-C6 alkyl are replaced by a substituent selected from the group consisting of hydroxyl, thiol, C1-C6 alkylhydroxyl, C1-C6 alkylthiol, -NR 1a R1b , -L-R 1c , wherein R 1a , R 1b each independently is C1-C15 alkyl, L is -(CH2CH20) n1 - or -(CH2CH2S) n2 -, R 1c is C1-C3 alkyl or hydroxy, wherein n1, n2 each independently is 1 to 8;

[0078] The component (b) is a diene branching agent 1b, the structure of which is shown below:

[0079] Y 1 , Y 2 each independently is hydrogen, methyl;

[0080] R 2 is -L1-L2-L3, wherein L1 is C1-C10 alkylene, L2 is none or -CH2CH20-, and L3 is C1-C10 alkylene.

[0081] In another preferred embodiment, the polymer-containing base oil solution is a highly branched PMA-type pour point and haze depressant as described in the first aspect of the present application.

[0082] In another preferred embodiment, the step (s1) corresponds to the method for preparing a highly branched PMA-type pour point and haze depressant as described in the second aspect of the present application.

[0083] In another preferred embodiment, the component (a), the component (b), the methacrylate mono-olefin 1a, and the base oil each independently are as described in the first aspect of the present application.

[0084] In another preferred embodiment, the polymer is a linear polymer or a randomly branched polymer.

[0085] In another preferred embodiment, the polymer has a relative number average molecular weight of 15 to 100 kg / mol, preferably 18 to 50 kg / mol, more preferably 20 to 50 kg / mol.

[0086] In another preferred embodiment, the polymer has a relative molecular weight distribution of 1.2 to 10.

[0087] In a fourth aspect of the present application, there is provided an article of manufacture comprising a highly branched PMA-type pour point and haze depressant as described in the first aspect of the present application.

[0088] In another preferred embodiment, the article of manufacture is a lubricating oil additive article.

[0089] In a fifth aspect of the present application, there is provided a lubricating oil comprising the highly branched PMA type pour point and cloud point depressant of the first aspect of the present application.

[0090] In another preferred embodiment, the highly branched PMA type pour point and cloud point depressant is present in the lubricating oil in an amount of 0.05 to 0.5 wt.%.

[0091] In another preferred embodiment, the lubricating oil further comprises a commercial oil.

[0092] In another preferred embodiment, the commercial oil is an industrial lubricating oil having a moderate pour point but a high cloud point (0°C to ambient temperature).

[0093] In another preferred embodiment, the commercial oil is one or more of 3#, 5#, 10#, 15#, 26#, 32#, 46# and 68#.

[0094] In a sixth aspect of the present application, there is provided the use of the highly branched PMA type pour point and cloud point depressant of the first aspect of the present application, the polymer of the third aspect of the present application, or the article of the fourth aspect of the present application, for the preparation of a pour point and cloud point depressant for a lubricating oil, for lowering the pour point and / or cloud point of a lubricating oil.

[0095] In another preferred embodiment, the cloud point of the lubricating oil is lowered by 20°C or more, preferably 30°C or more, more preferably 40°C or more, at a 1 wt.% addition level.

[0096] In another preferred embodiment, the pour point of the lubricating oil is lowered, preferably by 1°C or more, more preferably by 3°C or more, at a 1 wt.% addition level.

[0097] In another preferred embodiment, the cloud point of the lubricating oil is lowered by 20°C or more, preferably 30°C or more, more preferably 40°C or more, at a 0.1 wt.% addition level.

[0098] In another preferred embodiment, the pour point of the lubricating oil is lowered, preferably by 1°C or more, more preferably by 3°C or more, at a 0.1 wt.% addition level.

[0099] It should be understood that, within the scope of the present application, the above-mentioned technical features of the present application and the technical features specifically described hereinafter (e.g. in the examples) can be combined with each other to form new or preferred technical solutions. Due to the limited space, they will not be listed one by one here. BRIEF DESCRIPTION OF DRAWINGS

[0100] Figure 1 illustrates the topology of the polymers in the PMA type pour point and cloud point depressant product.

[0101] Figure 2 illustrates the appearance of three commercial oils at 0°C (from left to right: 10#, 32# and 68# commercial oils).

[0102] Figure 3 shows the appearance of three commercial oils after compounding with 0.1 wt.% PMA type pour point depressant and haze point depressant product at 0°C. (From left to right are 10#, 32#, 68# commercial oil samples after compounding) DETAILED DESCRIPTION

[0103] The present inventors have made extensive and in-depth research and for the first time discovered a green, environmentally friendly, low-cost, simple step method for preparing PMA type pour point depressant and haze point depressant. The method uses common methacrylate, branching agent, initiator and chain transfer agent to directly prepare a saleable product in one step without post-treatment.

[0104] The prior art pour point depressant preparation needs to be polymerized under high concentration of monomer conditions to improve polymerization efficiency and increase monomer conversion. The present application directly adds a large amount of base oil as a solvent, and at the same time can directly obtain a finished product after the reaction. Not only can the safety problem of high concentration polymerization reaction be avoided, but also the finished product can be obtained in one step without post-treatment. Surprisingly, it is found that in the system of the present application, even if the reaction is carried out at low concentration, excellent pour point depressant and haze point depressant finished products can be obtained without affecting the performance and monomer conversion.

[0105] And the PMA type pour point depressant and haze point depressant obtained can significantly reduce the pour point and haze point of commercial oil products at a low addition amount, meeting the use requirements under working conditions. In particular, the pour point depressant and haze point depressant finished product of the present application can surprisingly significantly reduce the haze point of lubricating oil, while the prior art cannot significantly reduce the haze point, at most only reducing the haze point by 1-5°C. On this basis, the present application is completed.

[0106] TERMS

[0107] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0108] As used herein, the terms "comprising", "including", "containing", are interchangeable and include both open- and closed-ended definitions. In other words, the terms include "consisting of" and "consisting essentially of".

[0109] As used herein, the term "C4-C30 alkyl" refers to a straight-chain or branched alkyl group having 4-30 carbon atoms, including C4-C20 alkyl, such as n-butyl, isobutyl, t-butyl, n-octyl, n-decyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, octadecyl, n-eicosyl, n-docosyl or the like.

[0110] Similarly, "C1-C15 alkyl", "C1-C3 alkyl", "C2-C6 alkyl" have similar meanings and can include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl and the like.

[0111] As used herein, the term "C1-C10 alkylene" refers to a divalent alkyl group having 1-10 carbon atoms, including C1-C6 alkylene, C1-C3 alkylene, such as methylene, ethylene, n-propylene, i-propylene, or the like.

[0112] As used herein, the term "C1-C6 alkylhydroxy" refers to a C1-C6 alkyl group substituted with a hydroxyl group, such as hydroxymethyl, hydroxyethyl, and the like.

[0113] Similarly, "C1-C6 alkylmercapto" has a similar meaning and refers to a C1-C6 alkyl group substituted with a mercapto-SH group.

[0114] PMA type pour point depressant and preparation method thereof

[0115] The present application provides a PMA type pour point depressant product, which can be realized by the following technical scheme:

[0116] The PMA type pour point depressant product is prepared by free radical copolymerization of a plurality of methacrylate mono-olefin 1a and a small amount (<10 mol.%) of di-olefin branching agent 1b in a conventional base oil.

[0117] In another preferred embodiment, the structural formula of the methacrylate mono-olefin 1a is independently as follows:

[0118] wherein each R 1 is independently C4-C22 alkyl, preferably C4H9~C 22 H 45 alkyl.

[0119] Alternatively, each R 1 is independently C4-C22 alkyl or C6 cycloalkyl; more preferably, each R 1 is independently n-butyl, i-butyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, n-eicosyl or n-docosyl.

[0120] Alternatively, each R 1 is independently n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, n-eicosyl, n-docosyl.

[0121] In another preferred embodiment, the plurality of methacrylate mono-olefins 1a is a combination of 3-5 (e.g. 3, 4) components.

[0122] In another preferred embodiment, the di-olefin branching agent 1b has the following structure:

[0123] wherein Y 1 , Y 2 are each independently hydrogen, methyl.

[0124] In another preferred embodiment, the di-olefin branching agent 1b has the following structure:

[0125] wherein R 2 is -(CH2)2-, -CH2C(CH3)2CH2-, -CH2[(CH2)2O] n CH2- (n = 3-8).

[0126] In another preferred embodiment, the PMA type pour point depressant and turbidity reducer product has a polymer content of 10-50% by mass and a conventional base oil content of 50-90% by mass.

[0127] In another preferred embodiment, the PMA type pour point depressant and turbidity reducer product has a polymer content of 10-50% by mass and a conventional base oil content of 50-90% by mass.

[0128] In another preferred embodiment, the PMA type pour point depressant and turbidity reducer product has a polymer content of 10-50% by mass and a conventional base oil content of 50-90% by mass.

[0129] In another preferred embodiment, the plurality of methacrylate mono-olefins 1a is a combination of 3-5 (e.g. 3, 4) components.

[0130] In another preferred embodiment, the PMA type pour point depressant and turbidity reducer product has a polymer content of 10-50% by mass and a conventional base oil content of 50-90% by mass. 2 is -CH2[(CH2)2O] n CH2- (n = 3-8).

[0131] The present application also provides a preparation scheme for the PMA type pour point depressant and turbidity reducer product, comprising the steps of:

[0132] The methyl acrylate monomer 1a, diene branching agent 1b, azo initiator, chain transfer agent are dissolved in the conventional base oil, under inert atmosphere, the temperature is raised, the reaction is carried out for a period of time, then cooled to room temperature, exposed to air, stirred overnight, to obtain the sale of pour point depressant product.

[0133] In another preferred example, the azo initiator is one or a mixture of two of azobisisobutyronitrile (AIBN), azobiscyclohexylcarbonitrile (ACCN), azobisisoheptyl nitrile (ABVN).

[0134] In another preferred example, the azo initiator and the methyl acrylate monomer 1a are in a molar ratio of (0.02-0.5):100.

[0135] In another preferred example, the chain transfer agent is a thiol compound selected from one of n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, mercapto-polyethylene glycol monomethyl ether.

[0136] In another preferred example, the chain transfer agent and the methyl acrylate monomer 1a are in a molar ratio of (0.025-2.5):100.

[0137] In another preferred example, the diene branching agent 1b and the methyl acrylate monomer 1a are in a molar ratio of (0-10):100.

[0138] In another preferred example, the methyl acrylate monomer 1a, diene branching agent 1b, azo initiator and chain transfer agent account for about 10-70% of the total mass of the feed, preferably 10-50%.

[0139] In another preferred example, the initiator, chain transfer agent, component (a) and component (b) can be fed in batches.

[0140] In another preferred example, the initiator, chain transfer agent, component (a) and component (b) are fed in an amount not more than 1 / 3 of the base oil.

[0141] In another preferred example, the conventional base oil is a type I base oil or a type II base oil, one or two of the grades 60N, 100N, 150N, 250N, 350N, 500N, 75SN, 100SN, 150SN, 200SN, 250SN, 300SN, 350SN, 400SN, 500SN, 650SN, accounting for 60-90% of the total mass of the feed, preferably 75-90%.

[0142] In another preferred example, the reaction temperature is 40-80°C, and the reaction time is 12-72h.

[0143] In another preferred embodiment, the preparation step is as follows: the methacrylate mono-olefin 1a, the di-olefin branching agent 1b, the azo initiator, and the chain transfer agent are dissolved in a conventional base oil in a certain proportion, and the mixture is heated in an inert atmosphere for a period of time, and after cooling, the product is obtained by stirring overnight in air.

[0144] In another preferred embodiment, the azo initiator is one or more of azobisisobutyronitrile (AIBN), azobiscyclohexylcarbonitrile (ACCN), and azobisisoheptylcarbonitrile (ABVN), and the addition amount is 0.02-0.5% of the number of moles of the methacrylate mono-olefin 1a.

[0145] In another preferred embodiment, the chain transfer agent is a mercaptan compound, preferably one of n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and mercapto-polyethylene glycol monomethyl ether, and the addition amount is 0.025-2.5% of the number of moles of the methacrylate mono-olefin 1a.

[0146] In another preferred embodiment, the conventional base oil in the PMA pour point and turbidity depressant product is one or both of a Group I base oil or a Group II base oil, and the grade is one of 60N, 100N, 150N, 250N, 350N, 500N, 75SN, 100SN, 150SN, 200SN, 250SN, 300SN, 350SN, 400SN, 500SN, and 650SN, and the amount is 60-90%, preferably 75-90%, of the total mass of the feed.

[0147] In another preferred embodiment, the addition amount of the di-olefin branching agent 1b is 0-10% of the number of moles of the methacrylate mono-olefin 1a.

[0148] In another preferred embodiment, the conversion rate of the methacrylate mono-olefin 1a is greater than 90%, and the conversion rate of 1b is greater than 95%.

[0149] In another preferred embodiment, the polymerization reaction temperature is 40-80°C, and the reaction time is 12-72h.

[0150] The PMA pour point and turbidity depressant of the present application can be directly compounded with various commercial oil products, and can effectively reduce the pour point and the cloud point of the commercial oil products at a low additive amount (<0.3%), meeting the use requirements under working conditions.

[0151] The method for preparing the PMA pour point and turbidity depressant of the present application can directly obtain a salable product by one-step method, without post-treatment, avoiding the use of organic solvents and the generation of excess industrial waste liquid, and meeting the green chemical industry and sustainable development strategy.

[0152] The application also provides the low-temperature performance of the PMA type pour point depressant and turbidity reducer product prepared by the above technical solution after being compounded with commercial oil products. The commercial oil products are industrial lubricating oils with moderate pour points but high turbidity points (0 DEG C to ambient temperature). The commercial oil products are provided by Ningbo Bohu Petroleum Chemical Co., Ltd., and the grades of the commercial oil products are one or more of 3#, 5#, 10#, 15#, 26#, 32#, 46# and 68#.

[0153] The preparation method of the poly-methacrylate type lubricating oil pour point depressant and turbidity reducer product of the application can effectively avoid gelation of the polymerization system and does not require post-treatment, thereby improving the stability of the polymer lubricating oil pour point depressant and turbidity reducer.

[0154] The raw material of the polymer lubricating oil pour point depressant and turbidity reducer product is widely available, and the preparation process is simple. Meanwhile, the polymerization system has good solubility and can be directly compounded with target oil products, and the pour point and turbidity point of the target oil products can be effectively reduced at a low additive dosage. Through optimization of the preparation method of the polymer pour point depressant and turbidity reducer product, the cost can be effectively reduced, and environmental pollution can be reduced, and the product has a wide industrial application prospect.

[0155] Polymer

[0156] The application provides a polymer which is dissolved in base oil to form the PMA type pour point depressant and turbidity reducer as described above.

[0157] In another preferred embodiment, the polymer has a linear or randomly branched structure.

[0158] In another preferred embodiment, the polymer has a topological structure as shown in FIG. 1.

[0159] In another preferred embodiment, the polymer has a relative number average molecular weight of 18-100 kg / mol (preferably 20-100 kg / mol) and a relative molecular weight distribution of 1.3-10.

[0160] The PMA type pour point depressant and turbidity reducer product prepared by the application has at least one of the following advantages compared with a conventional pour point depressant and turbidity reducer product:

[0161] (1) The PMA type pour point depressant and turbidity reducer product has good solubility, can be directly compounded with most commercial oil products, and can effectively reduce the pour point and turbidity point of the commercial oil products at a low additive dosage, and the effect of reducing the turbidity point is particularly remarkable; for example, when the PMA type pour point depressant and turbidity reducer product F provided by the application is added into BH-32# and 68# oil products at an additive dosage of 0.1 wt.%, the pour points of the oil products are reduced from -45 DEG C to -48 DEG C and from -36 DEG C to -39 DEG C (by 3 DEG C) respectively, the turbidity points are reduced to below the pour points, that is, <-48 DEG C and <-39 DEG C respectively, and no turbidity is observed in the entire test range before the oil products solidify.

[0162] (2) The PMA type pour point depressant and turbidity reducer product is directly obtained by a one-step polymerization of a production system, the process is simple, the use of a large amount of organic solvent and the generation of waste in the production and post-processing process are avoided, industrial pollution is reduced, and the production cost is greatly reduced.

[0163] (3) The structural unit composition and topological structure of the polymer in the PMA type pour point depressant and turbidity reducer product are easy to control, by changing the structures of the methacrylate, diene branching agent and chain transfer agent and the ratio among them, the molecular weight and its distribution, the average carbon number and the topological structure of the polymer can be adjusted to meet the performance requirements of lubricating oils for different industrial uses.

[0164] (4) The PMA type pour point depressant and turbidity reducer product has a wide source of raw materials, a simple preparation method, stable properties during use and storage, and can be produced on a large scale, and has a good industrial application prospect.

[0165] (5) The preparation method of the PMA type pour point depressant and turbidity reducer product can effectively avoid the gelation of the polymerization system, and the product can be obtained without post-processing.

[0166] Other technical features and advantages of the present application are described in detail in the specific embodiments.

[0167] The specific embodiments of the present application are further described below in conjunction with examples. It should be understood that these examples are only for understanding the present application and do not limit the scope of the present application, and the specific embodiments described in the following examples relate to the technical features described in the technical features and technical contents. It should be noted that the experimental operations involved in the following examples are routine operations unless otherwise specified; the raw materials and reagents involved in the following examples can be obtained from commercial channels unless otherwise specified.

[0168] Preparation of the PMA type pour point depressant and turbidity reducer product

[0169] Example 1

[0170] This example is used to illustrate an example of the PMA type pour point depressant and turbidity reducer product A and its preparation method provided by the present application.

[0171] Under inert atmosphere, 2.5 mmol of n-octyl methacrylate, 2.5 mmol of 2- ethylhexyl methacrylate, 2.5 mmol of dodecyl methacrylate, 2.5 mmol of hexadecyl methacrylate, 0.2 mmol of n-dodecanethiol, 0.1 mmol of ethylene glycol dimethacrylate and 0.04 mmol of azobisisobutyronitrile were dissolved in 24.0 mL of 150SN, with a total mass of 23.1 g. Then, the system was placed in a 65 °C oil bath, and reacted for 48 h at constant temperature. Finally, the system was naturally cooled to room temperature, exposed to air, stirred overnight, and the stirring device was removed, to obtain PMA type pour point and turbidity depressant product B, with a relative number average molecular weight of the polymer of 26.8 kg / mol, and a relative molecular weight distribution of 1.4. The mass fraction of the polymer was about 10%, and the mass fraction of the base oil 150SN was about 90%.

[0172] Example 2

[0173] This example is used to illustrate an example of PMA type pour point and turbidity depressant product B and a preparation method thereof provided by the present application.

[0174] Under inert atmosphere, 2.5 mmol of n-octyl methacrylate, 2.5 mmol of 2- ethylhexyl methacrylate, 2.5 mmol of dodecyl methacrylate, 2.5 mmol of hexadecyl methacrylate, 0.2 mmol of n-dodecanethiol, 0.1 mmol of ethylene glycol dimethacrylate and 0.04 mmol of azobisisobutyronitrile were dissolved in 24.0 mL of 150SN, with a total mass of 23.1 g. Then, the system was placed in a 65 °C oil bath, and reacted for 48 h at constant temperature. Finally, the system was naturally cooled to room temperature, exposed to air, stirred overnight, and the stirring device was removed, to obtain PMA type pour point and turbidity depressant product B, with a relative number average molecular weight of the polymer of 26.8 kg / mol, and a relative molecular weight distribution of 1.4. The mass fraction of the polymer was about 10%, and the mass fraction of the base oil 150SN was about 90%.

[0175] Example 3

[0176] This example is used to illustrate an example of PMA type pour point and turbidity depressant product C and a preparation method thereof provided by the present application.

[0177] Under inert atmosphere, 2.5 mmol of methyl methacrylate, 2.5 mmol of 2- ethylhexyl methacrylate, 2.5 mmol of dodecyl methacrylate, 2.5 mmol of tetradecyl methacrylate, 0.2 mmol of ethylene glycol dimethacrylate, 0.2 mmol of n-dodecanethiol and 0.04 mmol of azobisisobutyronitrile were dissolved in 11.0 mL of 150SN, with a total feed mass of 11.6 g. Then, the system was placed in a 70 °C oil bath, and the temperature was kept constant for 35 h. Finally, the system was naturally cooled to room temperature, exposed to air, stirred overnight, and the stirring device was removed, to obtain PMA-type pour point and turbidity depressant product C, in which the relative number average molecular weight of the polymer was 21.8 kg / mol, and the relative molecular weight distribution was 2.0. The mass fraction of the polymer was about 20%, and the mass fraction of the base oil 150SN was about 80%.

[0178] Example 4

[0179] This example is used to illustrate an example of PMA-type pour point and turbidity depressant product D and a preparation method thereof provided by the present application.

[0180] Under inert atmosphere, 2.5 mmol of methyl methacrylate, 2.5 mmol of 2- ethylhexyl methacrylate, 2.5 mmol of dodecyl methacrylate, 2.5 mmol of tetradecyl methacrylate, 0.2 mmol of ethylene glycol dimethacrylate, 0.2 mmol of n-dodecanethiol and 0.04 mmol of azobisisobutyronitrile were dissolved in 11.0 mL of 150SN, with a total feed mass of 11.6 g. Then, the system was placed in a 70 °C oil bath, and the temperature was kept constant for 35 h. Finally, the system was naturally cooled to room temperature, exposed to air, stirred overnight, and the stirring device was removed, to obtain PMA-type pour point and turbidity depressant product C, in which the relative number average molecular weight of the polymer was 21.8 kg / mol, and the relative molecular weight distribution was 2.0. The mass fraction of the polymer was about 20%, and the mass fraction of the base oil 150SN was about 80%.

[0181] Example 5

[0182] This example is used to illustrate an example of PMA-type pour point and turbidity depressant product E and a preparation method thereof provided by the present application.

[0183] Under an inert atmosphere, 2.5 mmol of hexyl methacrylate, 2.5 mmol of 2-ethylhexyl methacrylate, 2.5 mmol of dodecyl methacrylate, 2.5 mmol of tetradecyl methacrylate, 0.1 mmol of ethylene glycol dimethacrylate, 0.1 mmol of n-dodecyl mercaptan, and 0.04 mmol of azobisisobutyronitrile were dissolved in 11.0 mL of 150SN, with a total feed mass of 11.6 g. The solution was then placed in a 70°C oil bath and reacted at this temperature for 48 h. Finally, the system was allowed to cool naturally to room temperature while being exposed to air and stirred overnight. The stirring device was then removed, yielding PMA-type pour point depressant and turbidity reducer product E, in which the polymer has a relative number-average molecular weight of 34.7 kg / mol and a relative molecular weight distribution of 2.0. The polymer mass fraction is approximately 20%, and the 150SN base oil mass fraction is approximately 80%.

[0184] Example 6

[0185] This embodiment illustrates a PMA-type defoaming and turbidity-reducing agent product F provided by the present invention and its preparation method.

[0186] Under an inert atmosphere, 2.5 mmol of n-octyl methacrylate, 2.5 mmol of 2-ethylhexyl methacrylate, 2.5 mmol of dodecyl methacrylate, 2.5 mmol of hexadecyl methacrylate, 0.4 mmol of ethylene glycol dimethacrylate, 0.1 mmol of n-dodecyl mercaptan, and 0.04 mmol of azobisisobutyronitrile were dissolved in 11.1 mL of 150SN, with a total feed mass of 11.8 g. The solution was then placed in a 70°C oil bath and reacted at this temperature for 48 h. Finally, the system was allowed to cool naturally to room temperature while being exposed to air and stirred overnight. The stirring device was then removed, yielding PMA-type pour point depressant and turbidity depressant product F, in which the polymer had a relative number-average molecular weight of 46.5 kg / mol and a relative molecular weight distribution of 7.8. The polymer mass fraction was approximately 20%, and the 150SN base oil mass fraction was approximately 80%.

[0187] Low-temperature performance of PMA-type pour point depressant and turbidity depressant products blended with commercial oils

[0188] Test case

[0189] The test examples illustrate the pour point and cloud point testing of commercial oil products after the addition of the prepared PMA-type pour point and cloud point depressant product.

[0190] The commercial oil products are supplied by Ningbo Bohui Petrochemical Co., Ltd., and the grades of the commercial oil are 10#, 32#, and 68# as examples.

[0191] PMA type pour point depressant and turbidity reducer products A-F were added into 32# commercial oil product respectively, and the addition amount was 1wt.%, to obtain corresponding test oil samples a-f. The pour point and turbidity test results before and after adding the pour point depressant and turbidity reducer products are shown in Table 1.

[0192] Table 1 Pour point and turbidity test results of PMA type pour point depressant and turbidity reducer products A-F before and after being added into 32# commercial oil product

[0193] PMA type pour point depressant and turbidity reducer product F was added into 10#, 32# and 68# commercial oil product respectively, and the addition amount was 1wt.%, and then the initial blending oil was diluted according to the mass percentage given in Table 2 to obtain corresponding test oil samples I-III. The pour point and turbidity test results before and after adding the pour point depressant and turbidity reducer are shown in Table 2.

[0194] Table 2 Pour point and turbidity test results of PMA type pour point depressant and turbidity reducer product F before and after being added into 10#, 32# and 68# commercial oil product

[0195] In addition, the appearance of 10#, 32# and 68# commercial oil product at 0℃ without adding PMA type pour point depressant and turbidity reducer product is shown in Figure 2, and it can be seen that they all appear turbid. After adding 0.1wt.% PMA type pour point depressant and turbidity reducer product, the three commercial oil products all become clear and transparent, as shown in Figure 3.

[0196] From the above Tables 1-2 and Figures 2-3, it can be seen that the PMA type pour point depressant and turbidity reducer product prepared by the method of the present application has the effect of reducing the pour point and turbidity of commercial oil product within the scope of the present application, and the turbidity reduction effect is particularly prominent, meeting the use requirements of industrial lubricating oil.

[0197] In addition, it should be understood that, after reading the above teachings of the present application, those skilled in the art can make various modifications or changes to the present application, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims

1. A highly branched poly-methacrylate (PMA) type pour point depressant and cloud point depressant, prepared by a method comprising the steps of: the total mass of the components (a) and (b) is not more than 1 / 3 of the mass of the base oil; each of the methacrylate mono-olefins la is independently selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, n-eicosyl methacrylate, n-docosyl methacrylate, 2-ethoxyethyl methacrylate, mercaptoethyl ethyl methacrylate, hydroxyethyl polyethylene glycol methacrylate, N,N-diethyl ethyl methacrylate, N-methyl-N-dodecyl ethyl methacrylate; the molar ratio of each of the methacrylate mono-olefins la in the component (a) is (0.5-1.5):(0.5-1.5)... and so on to 3-8 methacrylate mono-olefins la, preferably (0.8-1.2):(0.8-1.2)... and so on to 3-8 methacrylate mono-olefins la, more preferably 1:1... and so on to 3-8 methacrylate mono-olefins la; the di-olefinic branching agent lb is ethylene glycol dimethacrylate; the molar fraction of the component (b) in the component (a) is 0-10 mol%, preferably 1-5 mol%; the mass of the base oil is 70% to 95% of the total mass of the feed; the base oil is a conventional base oil, preferably a Group I base oil or a Group II base oil, more preferably one or two of the grades 60N, 100N, 150N, 250N, 350N, 500N, 75SN, 100SN, 150SN, 200SN, 250SN, 300SN, 350SN, 400SN, 500SN, 650SN; comprising the steps of: mixing the components (a) and optionally (b) in the base oil to perform a free radical copolymerization reaction to obtain the highly branched PMA type pour point depressant and cloud point depressant; wherein the total mass of the components (a) and (b) is not more than 1 / 3 of the mass of the base oil; the method comprising the steps of: mixing the components (a) and optionally (b) in the base oil in an inert atmosphere in the presence of a free radical initiator and a chain transfer agent to perform a free radical copolymerization reaction to obtain the PMA type pour point depressant and cloud point depressant; wherein the total mass of the initiator, the chain transfer agent, the components (a) and (b) is not more than 1 / 3 of the mass of the base oil. The components (a) and optionally (b) are subjected to a free radical polymerization reaction in a base oil to obtain a highly branched PMA type pour point depressant / turbidity reducer; wherein, 1. A highly branched poly-methacrylate (PMA) type pour point depressant and cloud point depressant, prepared by a method comprising the steps of: the total mass of the components (a) and (b) is not more than 1 / 3 of the mass of the base oil; each of the methacrylate mono-olefins la is independently selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, n-eicosyl methacrylate, n-docosyl methacrylate, 2-ethoxyethyl methacrylate, mercaptoethyl ethyl methacrylate, hydroxyethyl polyethylene glycol methacrylate, N,N-diethyl ethyl methacrylate, N-methyl-N-dodecyl ethyl methacrylate; the molar ratio of each of the methacrylate mono-olefins la in the component (a) is (0.5-1.5):(0.5-1.5)... and so on to 3-8 methacrylate mono-olefins la, preferably (0.8-1.2):(0.8-1.2)... and so on to 3-8 methacrylate mono-olefins la, more preferably 1:1... and so on to 3-8 methacrylate mono-olefins la; the di-olefinic branching agent lb is ethylene glycol dimethacrylate; the molar fraction of the component (b) in the component (a) is 0-10 mol%, preferably 1-5 mol%; the mass of the base oil is 70% to 95% of the total mass of the feed; the base oil is a conventional base oil, preferably a Group I base oil or a Group II base oil, more preferably one or two of the grades 60N, 100N, 150N, 250N, 350N, 500N, 75SN, 100SN, 150SN, 200SN, 250SN, 300SN, 350SN, 400SN, 500SN, 650SN; comprising the steps of: mixing the components (a) and optionally (b) in the base oil to perform a free radical copolymerization reaction to obtain the highly branched PMA type pour point depressant and cloud point depressant; wherein the total mass of the components (a) and (b) is not more than 1 / 3 of the mass of the base oil; the method comprising the steps of: mixing the components (a) and optionally (b) in the base oil in an inert atmosphere in the presence of a free radical initiator and a chain transfer agent to perform a free radical copolymerization reaction to obtain the PMA type pour point depressant and cloud point depressant; wherein the total mass of the initiator, the chain transfer agent, the components (a) and (b) is not more than 1 / 3 of the mass of the base oil. wherein the component (a) is a combination of 3 to 8 different methacrylate mono-olefins 1a, the structure of each of the methacrylate mono-olefins 1a being independently as follows: wherein each R 1 each independently is C4-C30alkyl, C6cycloalkyl, substituted C2-C6alkyl, the substitution meaning that one or more hydrogens in the C2-C6alkyl are replaced by a substituent selected from the group consisting of hydroxyl, thiol, C1-C6alkylhydroxyl, C1-C6alkylthiol, -NR 1a R 1b , -L-R 1c , wherein R 1a , R 1b each independently is C1-C15alkyl, L is -(CH2CH2O) n1 - or -(CH2CH2S) n2 -, R 1c is C1-C3alkyl or hydroxyl, wherein n1, n2 each independently is 1 to 8; The component (b) is a diene branching agent 1b, the structure of which is shown below: Y 1 , Y 2 each independently is hydrogen, methyl; R 2 is -L1-L2-L3, wherein L1is C1-C10alkylene, L2is none or -CH2CH2O-, and L3is C1-C10alkylene.

2. The highly branched PMA type pour point depressant and haze reducer of claim 1, wherein each R 1 each independently n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, n-eicosyl, n-docosyl.

3. The highly branched PMA type pour point and haze depressant of claim 1, wherein, ​ 4. The highly branched PMA type pour point depressant and haze reducer of claim 1, wherein ​ 5. The highly branched PMA type pour point and haze depressant of claim 1, wherein, R 2 is -(CH2)2-, -CH2C(CH3)2CH2- or -CH2[(CH2)20] n CH2-(n = 3-8).

6. The highly branched PMA type pour point and haze depressant of claim 1, wherein, ​ 7. The highly branched PMA type pour point and haze depressant of claim 1, wherein, ​ 8. The highly branched PMA type pour point and haze depressant of claim 1, wherein, ​ 9. The highly branched PMA type pour point and haze depressant of claim 1, wherein, ​ 10. The process for the preparation of a highly branched PMA type pour point and haze depressant as claimed in claim 1, wherein, the process is carried out at a temperature in the range of 50 to 70 °C. ​ ​ The component (a) is a combination of 3 to 8 different methacrylate mono-olefins 1a, the structure of which is independently of each other as follows: wherein each R 1 each independently is C4-C30alkyl, C6cycloalkyl, substituted C2-C6alkyl, the substitution meaning that one or more hydrogens in the C2-C6alkyl are replaced by a substituent selected from the group consisting of hydroxyl, thiol, C1-C6alkylhydroxyl, C1-C6alkylthiol, -NR 1a R 1b , -L-R 1c , wherein R 1a , R 1b each independently is C1-C15alkyl, L is -(CH2CH2O) n1 - or -(CH2CH2S) n2 -, R 1c is C1-C3alkyl or hydroxyl, wherein n1, n2 each independently is 1 to 8; The component (b) is a diene branching agent 1b, the structure of which is shown below: Y 1 , Y 2 each independently is hydrogen, methyl; R 2 is -L1-L2-L3, wherein L1is C1-C10alkylene, L2is none or -CH2CH2O-, and L3is C1-C10alkylene.

11. The production method according to claim 10, wherein ​ ​ ​ 12. The production method according to claim 10, wherein The methacrylate monoolefins 1a are each independently selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, n-eicosyl methacrylate, n-docosyl methacrylate, 2-ethoxyethyl methacrylate, mercaptoethyl ethyl methacrylate, hydroxyethyl polyethylene glycol methacrylate, N,N-diethyl ethyl methacrylate, N-methyl-N-dodecyl ethyl methacrylate.

13. A polymer, characterized in that, Prepared by a process comprising the steps of: (s1) free-radically copolymerizing a plurality of methacrylate monoolefins 1a of component (a), and optionally a diene branching agent 1b of component (b) in a base oil to obtain a base oil solution containing a polymer; Optionally (s2) isolating the base oil to obtain the polymer; wherein the mass of the components (a) and (b) fed is not more than 1 / 3 of the base oil; wherein the component (a) is a combination of 3 to 8 different methacrylate mono-olefins 1a, the structure of each of the methacrylate mono-olefins 1a being independently as follows: wherein each R 1 each independently is C4-C30alkyl, C6cycloalkyl, substituted C2-C6alkyl, the substitution meaning that one or more hydrogens of the C2-C6alkyl are replaced by a substituent selected from the group consisting of hydroxyl, thiol, C1-C6alkylhydroxy, C1-C6alkylthio, -NR 1a R 1b , -L-R 1c , wherein R 1a , R 1b each independently is C1-C15alkyl, L is -(CH2CH20) n1 - or -(CH2CH2S) n2 -, R 1c is C1-C3alkyl or hydroxyl, wherein n1, n2 each independently is 1 to 8; The component (b) is a diene branching agent 1b, the structure of which is shown below: Y 1 , Y 2 each independently is hydrogen, methyl; R 2 is -L1-L2-L3, wherein L1is C1-C10alkylene, L2is none or -CH2CH2O-, and L3is C1-C10alkylene.

14. A lubricating oil characterised in that, The lubricating oil contains the highly branched PMA type pour point and cloud point depressant of claim 1.

15. Use of the highly branched PMA type pour point and cloud point depressant of claim 1 or the polymer of claim 13 for the preparation of a pour point and cloud point depressant for a lubricating oil for lowering the pour point and / or the cloud point of the lubricating oil.

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