阅读说明：本技术 一种多效防锈剂及其制备方法和应用 (Multi-effect antirust agent and preparation method and application thereof ) 是由 何懿峰 李朝宇 白文娟 李华 陈靖 刘伟 刘欣阳 于 2019-10-28 设计创作，主要内容包括：公开一种多效防锈剂及其制备方法和应用。该多效防锈剂包含羊毛脂与下面式(I)所示的金属醇盐的反应产物,式(I)中,M为锆或钛或铪；R-1、R-2、R-3和R-4可以相同或不同,且各自独立地选自C-1-C-8烷基,C-3-C-8环烷基和C-6-C-(10)芳基；优选R-1、R-2、R-3和R-4为相同的基团。所述方法包括使羊毛脂与式(I)所示的金属醇盐在60-100℃的温度反应,得到初产物；及使所述初产物在140-230℃的温度下炼制。该多效防锈剂不仅具有优异的防锈性能,同时还具有优良的极压抗磨性、氧化安定性等。M(OR-1)(OR-2)(OR-3)(OR-4) 式(I)(Discloses a multi-effect antirust agent, a preparation method and application thereof. The multi-effect antirust agent comprises a reaction product of lanolin and metal alkoxide shown in the following formula (I), wherein in the formula (I), M is zirconium, titanium or hafnium; r 1 、R 2 、R 3 And R 4 May be the same or different and are each independently selected from C 1 ‑C 8 Alkyl radical, C 3 ‑C 8 Cycloalkyl and C 6 ‑C 10 An aryl group; preferably R 1 、R 2 、R 3 And R 4 Are the same group. The method comprises the steps of enabling lanolin to react with metal alkoxide shown in a formula (I) at the temperature of 60-100 ℃ to obtain a primary product; and refining the primary product at a temperature of 140 ℃ to 230 DEG C. The multi-effect antirust agent not only has excellent antirust performance, but also has excellent extreme pressure antiwear property, oxidation stability and the like. M (OR) 1 )(OR 2 )(OR 3 )(OR 4 ) Formula (I))

1. A multi-effect rust inhibitor comprising the reaction product of lanolin and a metal alkoxide having the following formula (I), M (OR)₁)(OR₂)(OR₃)(OR₄) Formula (I)

In the formula (I), M is zirconium, titanium or hafnium;

R₁、R₂、R₃and R₄May be the same or different and are each independently selected from C₁-C₈Alkyl radical, C₃-C₈Cycloalkyl and C₆-C₁₀An aryl group; preferably R₁、R₂、R₃And R₄Are the same group.

2. The multi-effect rust inhibitor of claim 1, wherein M is zirconium.

3. The multi-effect rust inhibitor of claim 1, wherein the metal alkoxide is selected from zirconium methoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, and combinations thereof.

4. The multi-effect rust inhibitor according to claim 1, wherein the lanolin has a softening point of 38-44 ℃, a saponification value of 92-106 mgKOH/g, and an iodine value of 18-36 mg I₂/g。

5. The multi-effect rust inhibitor of claim 1, wherein the weight ratio of lanolin to metal alkoxide is 100: 1-500.

6. A method for preparing a multi-effect rust inhibitor, comprising the steps of:

-reacting lanolin with a metal alkoxide having the following formula (I) at a temperature of 60-100 ℃ to obtain a primary product;

refining the primary product at the temperature of 140-230 ℃ to obtain the multi-effect antirust agent;

M(OR₁)(OR₂)(OR₃)(OR₄) Formula (I)

In the formula (I), M is zirconium or titanium,

R₁、R₂、R₃and R₄May be the same or different and are each independently selected from C₁-C₈Alkyl radical, C₃-C₈Cycloalkyl and C₆-C₁₀An aryl group; preferably R₁、R₂、R₃And R₄Are the same group.

7. The method of claim 6, further comprising the step of adding water to the primary product for further reaction.

8. The method of claim 6, wherein the metal alkoxide is selected from zirconium methoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, and combinations thereof.

9. The method of claim 6, wherein the weight ratio of lanolin to metal alkoxide is 100: 1-500.

10. Use of the multi-effect rust inhibitor of any one of claims 1 to 5 and the multi-effect rust inhibitor obtained by the method of any one of claims 6 to 9 as an additive for lubricating oils or greases.

Technical Field

The application relates to an antirust agent, in particular to a multi-effect antirust agent with antirust, extreme pressure antiwear, antioxidant and the like, a preparation method and application thereof.

Background

With the increasing development of the mechanical industry, the prevention of metal corrosion is an important issue for metal materials and mechanical products during storage, transportation, processing and use. Currently, preservation methods employed are broadly classified into permanent and temporary preservation methods. The permanent anticorrosion method is to change the internal or external structure and components of the metal material; the temporary corrosion prevention is performed by adopting antirust water, antirust emulsion, vapor phase inhibitor, antirust grease and the like, and the temporary corrosion prevention is characterized in that antirust materials can be smoothly removed according to needs without affecting workpieces.

The antirust agent is the main component of the temporary anticorrosive material and can be divided into water solubility and oil solubility, wherein the oil solubility can be used for antirust grease. Antirust grease has received wide attention because of its wide application range. The quality of the rust inhibitor directly determines the performance of the rust-proof grease. At present, the types of rust inhibitors in the market are many, and rust prevention is mainly performed, but the lubricity is poor, because the rust inhibitors generate competitive adsorption with extreme pressure antiwear agents which are polar at the same time, and the lubricity is weakened.

Disclosure of Invention

In order to solve the problems, the application provides an antirust agent based on lanolin, compared with traditional antirust agents such as lanolin, calcium lanolin, magnesium lanolin, barium lanolin, aluminum lanolin, sulfonated lanolin, calcium sulfonated lanolin, lanolin alcohol and the like, the antirust agent has excellent antirust performance, extreme pressure abrasion resistance and oxidation resistance, and can be used for various antirust lubricating greases and lubricating oils.

In one aspect, the present application provides a multi-effect rust inhibitor comprising a reaction product of lanolin and a metal alkoxide having the following formula (I),

M(OR₁)(OR₂)(OR₃)(OR₄) Formula (I)

In the formula (I), M is zirconium, titanium or hafnium;

R₁、R₂、R₃and R₄May be the same or different and are each independently selected from C₁-C₈Alkyl radical, C₃-C₈Cycloalkyl and C₆-C₁₀An aryl group; preferably R₁、R₂、R₃And R₄Are the same group.

In one embodiment, M is zirconium.

In one embodiment, the metal alkoxide is selected from the group consisting of zirconium methoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, and combinations thereof.

In one embodiment, the lanolin has a softening point of 38 to 44 ℃, a saponification value of 92 to 106mgKOH/g, and an iodine value of 18 to 36mgI₂/g。

In one embodiment, the weight ratio of lanolin to metal alkoxide is 100: 1-500.

In a second aspect, the present application provides a method of preparing a multi-effect rust inhibitor, comprising the steps of:

-reacting lanolin with a metal alkoxide having the following formula (I) at a temperature of 60-100 ℃ to obtain a primary product;

refining the primary product at the temperature of 140-230 ℃ to obtain the multi-effect antirust agent;

M(OR₁)(OR₂)(OR₃)(OR₄) Formula (I)

In the formula (I), M is zirconium or titanium or hafnium,

R₁、R₂、R₃and R₄May be the same or different and are each independently selected from C₁-C₈Alkyl radical, C₃-C₈Cycloalkyl and C₆-C₁₀An aryl group; preferably R₁、R₂、R₃And R₄Are the same group.

In one embodiment of the process, the process further comprises the step of adding water to the primary product for further reaction.

In one embodiment of the method, the metal alkoxide is selected from the group consisting of zirconium methoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, and combinations thereof.

In one embodiment of the method, the weight ratio of lanolin to metal alkoxide is 100: 1-500.

In yet another aspect, the present application also provides the use of the multi-effect rust inhibitor of the first aspect of the present application and the multi-effect rust inhibitor obtained by the method of the second aspect as an additive for lubricating oils or greases.

The lanolin-based antirust agent provided by the application has excellent antirust performance, excellent extreme pressure anti-wear property, oxidation stability and the like, and is equivalent to or even obviously superior to the existing antirust agents such as lanolin, calcium lanolin, magnesium lanolin, barium lanolin, aluminum lanolin, sulfonated lanolin, calcium sulfonated lanolin, lanolin alcohol and the like in the performances of antirust property, extreme pressure anti-wear property, oxidation stability and the like. In addition, the multi-effect anti-rusting agent based on the lanolin is simple in preparation process, simple and easily available in raw materials and excellent in product performance. In addition, the multi-effect anti-rusting agent based on the lanolin can also have good compatibility with other anti-rusting agents, extreme pressure anti-wear agents, antioxidants and the like, and can be combined and used for various lubricating greases and lubricating oil.

Detailed Description

The technical solution of the present application is further explained below according to specific embodiments. The scope of protection of the present application is not limited to the following examples, which are set forth for illustrative purposes only and do not limit the present application in any way.

One aspect of the present application provides a multi-effect rust inhibitor comprising a reaction product of lanolin and a metal alkoxide having the following formula (I),

M(OR₁)(OR₂)(OR₃)(OR₄) Formula (I)

In the formula (I), M is zirconium or titanium or hafnium,

R₁、R₂、R₃and R₄May be the same or different and are each independently selected from C₁-C₈Alkyl radical, C₃-C₈Cycloalkyl and C₆-C₁₀An aryl group; preferably R₁、R₂、R₃And R₄Are the same group.

In the present application, M is preferably zirconium, i.e. the metal alkoxide is a zirconium alkoxide. Preferably, R₁、R₂、R₃And R₄Each independently selected from C₁-C₈Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, and the like.

In one embodiment, the metal alkoxide is selected from the group consisting of zirconium methoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, and combinations thereof.

Lanolin is a secreted oil attached to wool and has CAS number 8006-54-0, contains mainly sterols, fatty alcohols and triterpene alcohols as esters with about equal amounts of fatty acids, about 95%, 4% free alcohol, and small amounts of free fatty acids and hydrocarbons. The softening point is 38-44 ℃, the saponification value is 92-106 mgKOH/g, and the iodine value is about 18-36 mg I₂/g。

In the present application, the weight ratio of said lanolin to said metal alkoxide is 100: 1-500, preferably 100: 10-80.

The multi-effect rust inhibitors of the present application comprise the reaction product of lanolin and a metal alkoxide. In one embodiment, the multi-effect rust inhibitor of the present application is obtained by:

(1) reacting lanolin with a metal alkoxide of formula (I) at a temperature of 60-100 ℃ to obtain a primary product;

(2) refining the primary product at the temperature of 140-230 ℃ to obtain the multi-effect antirust agent.

The reaction of lanolin and the metal alkoxide of formula (I) may be carried out at a temperature of 60-100 ℃. Also, since alcohols are formed during the reaction, in one embodiment, the reaction may be performed under vacuum to facilitate removal of the formed alcohols. The relative degree of vacuum of the reaction can be selected according to the alcohol species to be removed.

In one embodiment, after the above reaction period, a certain amount of water may be added to step (1) and the reaction may be continued for a further period of time. The addition of water may promote hydrolysis of the metal alkoxide, which in turn promotes the reaction of lanolin and metal alkoxide. The amount of water added may be 0 to 100% by weight, preferably 1 to 60% by weight, based on the weight of the metal alkoxide.

The product obtained in the step (1) can be further refined at the temperature of 140-230 ℃ to obtain the multi-effect antirust agent. One of the purposes of refining is to remove unreacted and volatile substances in the system to avoid introducing these substances into the final oil to affect the properties of the oil.

The multi-effect antirust agent has excellent antirust performance, extreme pressure abrasion resistance and oxidation resistance, and can be used for various antirust lubricating greases and lubricating oils.

Lanolin contains a plurality of esters which can be reacted with an alkoxide of formula (I) to introduce titanium, zirconium and/or hafnium into the lanolin system. The multi-effect antirust agent is a reaction product of lanolin and alkoxide shown in a formula (I), and has good antirust performance of the lanolin; meanwhile, because transition metal elements with special performance of titanium, zirconium and/or hafnium are introduced into the system, an oxide film of titanium, zirconium and/or hafnium with good abrasion resistance can be formed in the oil product added with the multi-effect antirust agent in the using process, so that the multi-effect antirust agent also has good extreme pressure abrasion resistance.

In another aspect, the present application provides a method of preparing a multi-effect rust inhibitor, the method comprising the steps of:

-reacting lanolin with a metal alkoxide having formula (I) at a temperature of 60-100 ℃ to obtain a primary product;

refining the primary product at the temperature of 140-230 ℃ to obtain the multi-effect antirust agent.

As noted above, in one embodiment, the reaction of lanolin with the metal alkoxide may be carried out under vacuum to facilitate removal of the resulting alcohol species. The relative degree of vacuum of the reaction can be selected according to the alcohol species to be removed. The reaction time of lanolin and metal alkoxide may be 20 minutes to 20 hours, for example 30 minutes to 6 hours.

After the lanolin is reacted with the metal alkoxide for a certain period of time, a step of adding water to the initial reaction product of the lanolin and the metal alkoxide for further reaction may be further carried out. The addition of water may promote hydrolysis of the metal alkoxide, which in turn promotes the reaction of lanolin and metal alkoxide. The amount of water added may be 0 to 100% by weight, preferably 1 to 60% by weight, based on the weight of the metal alkoxide.

In the present application, metal alkoxides which may be used are as described above, and the weight ratio of the lanolin to the metal alkoxide is 100: 1-500, preferably 100: 10-80.

As mentioned above, the multi-effect antirust agent has excellent antirust performance, extreme pressure antiwear property and oxidation resistance, and can be used in various antirust lubricating greases and lubricating oils. Thus, the third aspect of the present application also relates to the use of the multi-effect rust inhibitor of the first aspect of the present application and the multi-effect rust inhibitor obtained by the method of the second aspect as an additive for lubricating oils or greases.

The present application is further described below in terms of specific examples. In the following examples, all the starting materials are commercially available chemical reagents unless otherwise specified, and are not particularly limited.

Lanolin is available from carbofuran technologies;

base oil 500SN, kinematic viscosity at 100 ℃ of 11mm²And/s, from the petrochemical Yanshan, China.

Preparation example 1

The raw material components are as follows:

lanolin (softening point 38 ℃, saponification number 92mgKOH/g, iodine number 18mg I)₂/g)50kg

12kg of n-butyl zirconium (content 76 percent)

1.5kg of distilled water

Putting 50kg of lanolin into a 150L reaction kettle with heating, stirring, filtering and cooling functions, heating and stirring, heating to 60 ℃, adding 12kg of n-butyl alcohol zirconium, stirring for 30min, adding 1.5kg of distilled water, continuing to react for 2h, heating to 200 ℃, refining at a constant temperature for 5min, filtering while hot, and cooling the obtained filtrate to room temperature to obtain the antirust agent A.

Preparation example 2

The raw material components are as follows:

lanolin (softening point 42 ℃, saponification number 104mg KOH/g, iodine number 28 mgI)₂/g)50kg

24kg of n-butyl zirconium (content 76%)

4kg of distilled water

Putting 50kg of lanolin into a 150L reaction kettle which is provided with the functions of heating, stirring, filtering, cooling and vacuumizing, heating and stirring, raising the temperature to 90 ℃, adding 24kg of n-butyl alcohol zirconium, reacting for 15min, adding 4kg of distilled water, continuing to react for 4h, and vacuumizing and reducing the pressure of a container so as to remove the generated n-butyl alcohol. And then heating to 160 ℃, refining at constant temperature for 30min, filtering while hot, and cooling the obtained filtrate to room temperature to obtain the antirust agent B.

Preparation example 3

The raw material components are as follows:

lanolin (softening point 39 ℃, saponification value 98mgKOH/g, iodine value 32 mgI)₂/g)100kg

Zirconium tert-Butanol (99% content) 34kg

6kg of distilled water

Putting 100kg of lanolin into a 200L reaction kettle with heating, stirring, filtering and cooling functions, heating and stirring, heating to 80 ℃, adding 34kg of zirconium tert-butoxide, reacting for 20min, adding 6kg of distilled water, continuing to react for 1h, heating to 220 ℃, refining at constant temperature for 5min, filtering while hot, and cooling the obtained filtrate to room temperature to obtain the antirust agent C.

Preparation example 4

The procedure of production example 3 was repeated except that 24kg of zirconium ethoxide (99%) was used in place of 34kg of zirconium t-butoxide used in production example 3 while distilled water was added instead of 7kg, to finally obtain rust inhibitor D.

Preparation example 5

The procedure of production example 3 was repeated except that 62kg of zirconium n-propoxide (23%) was used in place of 34kg of zirconium t-butoxide used in production example 3 while distilled water was added in an amount of 17kg, to finally obtain rust inhibitor E.

Preparation example 6

The procedure of production example 3 was repeated except that 12.8kg of tetraisopropyl titanate was used in place of 34kg of zirconium t-butoxide used in production example 3 while distilled water was added instead of 4kg, to finally obtain rust inhibitor F.

Preparation example 7

The procedure of production example 3 was repeated except for using 6.4kg of tetraisopropyl titanate (98%) and 11.1kg of zirconium n-butoxide (76%) in place of 34kg of zirconium t-butoxide used in production example 3, to finally obtain rust inhibitor G.

Test example

To evaluate the performance thereof, the most commonly used lithium-based base grease at present was prepared as follows, and the obtained multi-effect rust inhibitor was added thereto in a certain ratio.

50kg of base oil 500SN oil (viscosity 11mm at 100 ℃) is added into a reaction kettle with the capacity of 200L and with heating, stirring, circulating and cooling functions²And/s) and 10kg of 12-hydroxystearic acid, stirring, heating to 80 ℃ to form a uniform system, slowly adding 1.43kg of lithium hydroxide monohydrate and 5kg of water, heating to 105 ℃ for draining and saponifying for 2 hours, heating to 210 ℃, adding 20kg of 500SN oil, stirring, cooling, homogenizing, filtering, degassing, discharging from a kettle to obtain lithium-based basic grease, wherein the lithium-based basic grease comprises the following components: 87.3 percent of base oil and 12.7 percent of thickening agent.

For comparison with the multi-effect rust inhibitor of the present application, commercially available calcium lanolin rust inhibitor (CRODA, Crobar RP5) and magnesium lanolin rust inhibitor (shandong lyon new material science and technology ltd) were purchased for comparison.

The preparation method of the lubricating grease comprises the following steps:

a certain amount of the above lithium base grease was heated to 80 ℃ and 1% of each rust inhibitor obtained in the above preparation examples was added thereto, and the mixture was stirred for 10min and ground with a three-roll mill for 2 times to obtain a grease.

The grease obtained was tested for parameters such as dropping point, working cone penetration, etc. according to the test methods listed in table 1 below. The test results are listed in table 1 below.

Table 1 grease testing parameters and results

Note: the pressure drop was too great and the test was not completed.

PB represents maximum seizure-free load, PD represents sintering load

Table 1 grease test parameters and results

As can be seen from Table 1, when the same amount of the rust inhibitor of the present invention was added to lithium grease along with commercially available calcium lanolin rust inhibitor and magnesium lanolin rust inhibitor, the rust inhibitor of the present invention did not damage the gel structure of the grease, and even slightly improved the structure.

The copper sheet corrosion results show that the lubricating grease using the rust inhibitor of the present application and commercially available calcium lanolin rust inhibitors and magnesium lanolin rust inhibitors all reach a 1b grade, but the results of dynamic salt water rust inhibition tests show that the effect of the lubricating grease using the rust inhibitor of the present application is significantly better than the lubricating grease using the calcium lanolin rust inhibitors and magnesium lanolin rust inhibitors of the prior art: grease using prior art calcium lanolin rust inhibitors and magnesium lanolin rust inhibitors can reach a level of 2-3, while grease using the present rust inhibitors can reach a level of 0.

Meanwhile, as the PB and PD results show, the lubricating grease using the antirust agent also has a remarkable extreme pressure antiwear effect and excellent lubricating performance: the PB value is improved by 2-3 times, and the PD value is improved by more than 50%, compared with the lubricating grease using the lanolin calcium antirust agent and the lanolin magnesium antirust agent in the prior art.

In addition, as shown by the oxidation stability test result, the antirust agent also shows remarkable antioxidation; however, the grease using the prior art calcium lanolin rust inhibitor and magnesium lanolin rust inhibitor and the grease without rust inhibitor could not complete the oxidation stability test.

It should be noted by those skilled in the art that the embodiments described herein are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present application. Thus, the present application is not limited to the above-described embodiments, but only by the claims.