WO2015027366A1 - Dendritic macromolecule friction modifier with polar end groups - Google Patents

Abstract

The present invention relates to a dendritic macromolecule friction modifier with polar end groups. A friction modifier molecule is a dendritic macromolecule, in a structure shown in formula (I). An internal framework structure thereof represents a dendritic macromolecule system of polyphenyl, polyester, polyether, polyamine, polyamide, polyurethane, or polysiloxane. An external end group P is a polar group containing nitrogen, oxygen, sulfur, phosphorus, fluorine, boron or chlorine heteroatoms. Compared with a traditional friction modifier molecule with a polar group in one end and a non-polar hydrocarbon in the other end, the functionalized polar end groups of the prepared dendritic macromolecule friction modifier with polar end groups coordinate with metal of surfaces of a friction pair respectively, and meanwhile the dendritic macromolecule makes two metal surfaces of the friction pair completely separated, preventing direct contact of two friction surfaces, implementing non-wear friction, and providing excellent anti-wear performance for lubricating oil.

Description

 - Dendrimer friction modifier with polar end groups

Technical field

 The present invention relates to a lubricating oil additive, and more particularly to a dendrimer friction modifier having polar end groups.

Background technique

 Typically, an organic friction modifier is a surfactant having a polar group at one end and a non-polar hydrocarbon group at the other end. The friction modifier can form a directional adsorption film on the friction surface, thereby improving the lubrication condition of the friction pair, effectively reducing the friction and wear of the machine, and achieving the effects of reducing energy consumption and improving fuel economy. The polar group of the friction modifier determines the bonding strength of the friction modifier to the surface, and is generally a compound containing a hetero atom such as nitrogen, oxygen, sulfur, phosphorus, or boron.

 A friction modifier comprising one or more amide functional groups is disclosed in the Chinese patent CN 102725385 A and the US patent US Pat. No. 20120283158 A1.

RrC - N wherein X is an oxygen atom or a sulfur atom, and RPR ₂ is an independently hydrogen or a hydrocarbon group. The polar group of the friction modifier is an amide or thioamide and forms a composition with a functional fluid such as an engine oil for use while maintaining the stability, clarity and/or compatibility of the composition.

 A succinimide-based friction modifier is disclosed in the Chinese patent CN 101323810 A and the US patent US 20070293406 A1:

Wherein, and 14 may be hydrogen, but are not hydrogen at the same time, and wherein R/4 may independently be a linear or branched hydrocarbon group having 1 to 34 carbon atoms such that the carbon atoms of R ₃ and R ₄ The total is about 11~35. The polar group of the friction modifier is succinimide, and the base oil and additive composition constitutes a power transmission fluid having improved durability and improved friction properties.

US Patent No. 20100210487 A1 discloses a fatty acid sorbitan ester friction modifier: H

 Where n is an integer from 6 to 28. The polar group of the friction modifier is a fatty acid sorbitan ester end and has a long-term antifriction property.

 After searching, no related reports of dendrimer friction modifiers with polar end groups were found.

Summary of the invention

 SUMMARY OF THE INVENTION It is an object of the present invention to provide a dendritic high molecular friction modifier having polar end groups which provides wear free friction.

 The technical solution of the present invention is: a dendrimer friction modifier having a polar end group, characterized in that the friction modifier molecule is a dendrimer, and comprises the following structure:

 The internal skeleton structure represents a dendrimer system of polyphenylene, polyester, polyether, polyamine, polyamide, polyurethane or polysiloxane, and the external terminal group P contains nitrogen, oxygen, sulfur, phosphorus, fluorine, a polar group of a boron or chlorine hetero atom, but is not limited to the above internal skeleton and an external polar group;

 The functionalized polar end groups of the friction modifier respectively coordinate with the metal of the surface of the friction pair, while the dendrimer polymer completely separates the two metal surfaces of the friction pair.

 a polar group represented by P, and a polar group containing a hetero atom, and a derivative thereof, which represents an amino group, an ester group, a carboxyl group, a hydroxyl group, an amide group, a boronic acid group, a nitrile group, a thiol group or a phosphate group, Or five- and six-membered heterocycles and their derivatives. Wherein, the polar group as a five-membered heterocyclic ring means furan, thiophene, tetrazole, triazole, pyrazole, pyrazolium, imidazole, oxazolidine, thiazolidine, pyrrolidine, pyrroline or pyrrole ring and their derivatives The polar group as a six-membered heterocyclic ring means pyridine, pyrimidine, piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine or piperidine ring and derivatives thereof, but is not limited thereto Group.

detailed description The embodiment in which the dendritic group having the polar end group of the present invention is divided into the rubbing improver is given, and is not limited to the principle, the process method, the raw materials used, and the like in the following examples.

Example 1

 Preparation of a dendrimer friction modifier having a polar pyrimidine end group: a hydroxylated carbosilane dendron is dissolved in a mixed solvent of dimethyl sulfoxide DMSO and dimethylformamide DMF, both Prepared by mixing 3:1, adding 16 times equivalent of 5-pyrimidine carboxylic acid while stirring, then adding 8 times equivalent of 4-dimethylaminopyridine DMAP and 1.6 times equivalent of ethyl dimethylaminopropyl carbonized The imine EDC is stirred under nitrogen at room temperature for 72 h; after the reaction is completed, the unreacted 5-pyrimidinecarboxylic acid and the catalyst are removed, and the mixture is dried under vacuum to obtain a dendrimer with a polar pyrimidine end group. The structure of the agent is as follows:

实施例 2

Example 2

 Preparation of a dendrimer ruthenium modifier having a polar imidazolinone end group: Operation as in Example 1, except that a corresponding amount of 2-imidazolidinone-4-carboxylic acid was used in place of the 5-pyrimidine carboxylic acid, The structure of the resulting dendrimer-type ruthenium modifier having a polar imidazolinone end group is as follows:

实施例 3

Example 3

Preparation of a dendrimer friction modifier having polar pyridine end groups: Operation as in Example 1, except that a corresponding amount of isonicotinic acid was used in place of the 5-pyrimidine carboxylic acid to obtain a dendrimer having a polar pyridine end group The structure of the polymer friction modifier is as follows: 0 0

实施例 4

Example 4

Preparation of a dendrimer friction modifier having polar thiazole end groups: Operation as in Example 1, except that the corresponding amount of benzothiazole-6-carboxylic acid was used in place of the 5-pyrimidine carboxylic acid, resulting in a polar thiazole The structure of the terminal-based dendrimer friction modifier is as follows:

 The experiments of low-speed friction tester (LVFA) and atomic force microscopy (AFM) prove that the dendrimer friction modifier with polar end groups provided by the invention can be combined with base oil and other required lubricating oil additives. The composition exhibits excellent anti-wear and anti-wear lubrication effects and achieves wear-free friction.

Industrial applicability

 The invention is characterized in that: the dendrimer friction modifier with polar end groups prepared by the invention is compared with the conventional friction modifier molecule with a polar group at one end and a non-polar hydrocarbon at the other end. The functionalized polar end groups are respectively coordinated with the metal of the friction pair surface, and the dendrimer completely separates the two metal surfaces of the friction pair to prevent direct contact between the two friction surfaces, thereby achieving wear-free friction. Provides excellent wear resistance for lubricating oils.

Claims

Claim  What is claimed is: 1. A dendrimer friction modifier having a polar end group, wherein: the friction modifier molecule is a dendrimer, and the structure is as follows:

 The internal skeleton structure represents a dendrimer system of polyphenylene, polyester, polyether, polyamine, polyamide, polyurethane or polysiloxane, and the external terminal group P contains nitrogen, oxygen, sulfur, phosphorus, fluorine, A polar group of boron or a chlorine hetero atom.  2 . The dendritic polymer friction modifier having polar end groups according to claim 1 , wherein: the functionalized polar end groups of the friction modifier respectively coordinate with the metal of the friction pair surface, At the same time, the dendrimer completely separates the two metal surfaces of the friction pair.  The dendrimer friction modifier having a polar end group according to claim 1, wherein the polar group represented by P represents an amino group, an ester group, a carboxyl group, a hydroxyl group, an amide group, The boronic group, the nitrile group, the thiol group or the phosphate group contains a hetero atom-containing polar group and derivatives thereof, or a five-membered or six-membered heterocyclic ring and derivatives thereof.  The dendrimer friction modifier having a polar end group according to claim 3, wherein: as a polar group of a five-membered heterocyclic ring, it represents furan, thiophene, tetrazole, triazole, pyridyl An azole, a pyrazolidine, an imidazole, an oxazolidine, a thiazolium, a pyrrolidine, a pyrroline or a pyrrole ring and derivatives thereof.  The dendrimer friction modifier having a polar end group according to claim 3, wherein: as a polar group of a six-membered heterocyclic ring, it represents a pyridine, a pyrimidine, a piperazine, a pyrazine, or a sulfur. A morpholine, thiazine, morpholine, oxazine or piperidine ring and derivatives thereof.