CN109762632B - High-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate and preparation method thereof - Google Patents
High-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate and a preparation method thereof, belonging to the technical field of lubricant preparation. The high-performance calcium carbonate-containing composite calcium sulfonate-based lubricating grease comprises the following raw materials in parts by weight: 100 parts of high-base-number calcium sulfonate, 120-170 parts of base oil, 1-1.5 parts of alkyl benzene sulfonic acid, 0.5-2 parts of fatty acid, 1-10 parts of acetic acid, 5-15 parts of water and 15-25 parts of modified nano calcium carbonate. The modified nano calcium carbonate has the advantages of good cleaning effect, low-temperature corrosion resistance, wear resistance, friction reduction and the like when being used as an additive of lubricating grease. The composite calcium sulfonate grease prepared by the method not only has good extreme pressure, wear resistance, high and low temperature properties and colloid stability, but also has excellent hardening resistance and high temperature resistance and is not easy to throw oil.
Description
Technical Field
The invention relates to the technical field of lubricant preparation, in particular to a high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate and a preparation method thereof.
Background
The lubricating grease is used as an independent industrial part in the lubricant, and is widely applied to the fields of industrial machinery, agricultural machinery, transportation industry, electronic information industry and the like due to the characteristics of excellent water resistance, colloid stability, abrasion resistance, wide working temperature range and the like. The grease is mainly prepared by thickening a base oil with a thickener and adding an additive, and can be classified into metal soap-based grease, organic grease, hydrocarbon-based grease and inorganic grease according to the type of the thickener used, and the complex calcium sulfonate-based grease is most widely used in the metal soap-based grease.
The composite calcium sulfonate-based lubricating grease integrates the performance advantages of composite lithium-based lubricating grease, composite aluminum-based lubricating grease and composite calcium-based lubricating grease, shows excellent extreme pressure, wear resistance, high and low temperature properties and stability, and is called as new-generation lubricating grease. But it also exists: the defects of hardening and aging phenomena, obvious consistency change at high temperature, oil throwing phenomena at certain high-temperature lubrication parts and the like can occur along with the prolonging of the standing time. These drawbacks limit the development of complex calcium sulfonate-based greases.
Nano calcium carbonate is widely used as a novel functional inorganic material with stable performance and easy processing. In the field of lubricants, the modified nano calcium carbonate has the advantages of good cleaning effect, low-temperature corrosion resistance, wear resistance, friction reduction and the like when being used as an additive of lubricating grease.
The patent CN101993767A discloses a calcium carbonate-containing complex calcium sulfonate grease and a production method thereof, the method takes high-base-number synthesized calcium sulfonate, base oil, boric acid and C12-C22 saturated stearic acid as basic components, and then nano calcium carbonate with the particle size of 5-300 nm is added into the calcium sulfonate grease, so as to obtain the novel complex calcium sulfonate-based grease. The extreme pressure wear resistance and the colloid stability of the lubricating grease produced by the method are improved, but the problems of high temperature resistance and hardening prevention of the lubricating grease are not improved.
Patent CN103146465A discloses a high-performance composite calcium sulfonate-based lubricating grease and a preparation method thereof, wherein the lubricating grease is prepared by using high-base-number synthetic calcium sulfonate, base oil, lauric acid, boric acid, calcium oxide and HL-functional agent as basic components. The lubricating grease prepared by the method can ensure that the crystal grains of the converted calcium carbonate are more uniformly distributed, thereby effectively solving the problem of surface hardening of the composite calcium sulfonate-based lubricating grease. Patent CN105368542A discloses a modified complex calcium sulfonate-based lubricating grease and a preparation method thereof, the method uses diatomite modified by sucrose stearate to prepare novel high-base-number synthetic calcium sulfonate and then uses the modified novel high-base-number calcium sulfonate to prepare the lubricating grease, the prepared lubricating grease has good hydrophobic property and uniform system distribution, thereby effectively improving the problem of surface hardening of the complex calcium sulfonate-based lubricating grease. However, neither of the above patents can improve the high temperature resistance of the grease.
Patent CN102703185A discloses a composite calcium sulfonate-based grease and a preparation method thereof, the method is characterized in that an arylamine antioxidant is added in the thickening process, so that the operation can not only reduce the cost, but also improve the water resistance, heat resistance and lubricity of the product and reduce the loss of the product at high temperature. Patent CN106497641A discloses a modified complex calcium sulfonate grease composition and a preparation method thereof, which improves the mechanical stability of the grease and reduces the consistency change of the grease during storage by improving the types and contents of transforming agent and complexing agent required in the preparation process, thereby achieving the purpose of reducing the loss at high temperature, but the problem of surface hardening is still not improved.
In summary, at present, there are few reports on calcium sulfonate complex grease with aging hardening resistance and high temperature resistance, and the performance is a problem to be solved for the continuous development of the calcium sulfonate complex grease, so that it is necessary to find a calcium sulfonate complex grease with the above two performances and a preparation method thereof.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to provide a high-performance calcium sulfonate complex grease containing calcium carbonate and a preparation method thereof, and aims to solve the technical problem that the calcium sulfonate complex grease in the prior art cannot simultaneously have the performances of ageing hardening resistance, high temperature resistance and the like.
For this purpose, the invention proposes the following solutions:
a high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate comprises the following raw materials in parts by weight: 100 parts of high-base-number calcium sulfonate, 100 parts of base oil, 1-1.5 parts of alkyl benzene sulfonic acid, 0.5-2 parts of fatty acid, 1-10 parts of acetic acid, 5-15 parts of water and 15-25 parts of modified nano calcium carbonate.
Preferably, the overbased calcium sulfonate is a synthetic calcium sulfonate.
Preferably, the total base number of the synthetic calcium sulfonate is 300-500 mgKOH/g.
Preferably, the base oil is one or more of 150BS, 120BS, HV1500, MVI 150.
Preferably, the alkylbenzene sulfonic acid is C10～C18One of linear alkyl benzene sulfonic acids.
Preferably, the fatty acid is a long chain fatty acid containing hydroxyl groups.
Preferably, the water is deionized water.
Preferably, the modified nano calcium carbonate comprises the following raw materials in parts by weight: 100 parts of calcium carbonate whisker, 0.5-1 part of macromolecular modifier ABM, 10-20 parts of solvent, wherein the solvent is acetone;
the synthesis of the modified nano calcium carbonate comprises the following steps:
s1: putting the calcium carbonate crystal whisker into a 105 ℃ vacuum oven to be dried for 2 hours for later use, and keeping the water content of the calcium carbonate crystal whisker to be 0.3-0.6%;
s2: diluting a macromolecular modifier ABM by using an acetone solvent, and uniformly mixing to obtain a mixed solvent;
s3: and (4) putting the dried calcium carbonate whiskers into a three-roll continuous modification machine, slowly adding the mixed solvent obtained in the step (S2) under medium-speed stirring, and stirring for 30min to obtain the modified nano calcium carbonate.
Preferably, the macromolecular modifier ABM comprises the following raw materials in parts by mole:
the preparation method and the synthesis reaction formula of the macromolecular modifier ABM are as follows:
firstly, a synthesis step: adding ethyl acetate into a four-neck flask, heating a water bath to 55 ℃ under the protection of nitrogen, and continuously stirring at 800 r/min; adding propenyl phenyl ether, n-butyl acrylate, maleic anhydride, azobisisobutyronitrile and dodecanethiol into ethyl acetate in sequence, stirring for 30min, heating to 65 ℃, and continuously stirring for 2.5h to obtain a viscous system; putting the sticky matter into a normal hexane solution for washing, repeatedly washing for 3-4 times, and drying to obtain a macromolecular modifier ABM;
② the reaction formula for synthesizing the macromolecular modifier ABM:
wherein x, y and z are integers, x is more than 0 and less than or equal to 4, y is more than 2 and less than or equal to 10, z is more than 0 and less than or equal to 6, and the name ABM-1 is given, wherein x is 2, y is 6, and z is 2; ABM-2, wherein x is 4, y is 6, and z is 2; ABM-3, where x is 2, y is 6, and z is 5.
Preferably, the preparation method of the calcium carbonate-containing high-performance composite calcium sulfonate-based lubricating grease comprises the following steps:
s1: at room temperature, putting the high-base-number calcium sulfonate and a part of base oil into a reaction kettle, stirring and mixing, heating to 75-100 ℃, and continuously stirring in the heating process to obtain a mixed material A;
s2: adding alkylbenzene sulfonic acid, fatty acid and water into the mixed material A in sequence according to a proportion, and quickly adding acetic acid after uniformly stirring; keeping the temperature at 95 ℃ and continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding the modified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding the rest base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate, which is prepared by taking nano calcium carbonate modified by a macromolecular modifier ABM as an additive, wherein the macromolecular modifier has a longer molecular chain and more different functional groups than a common micromolecular modifier, and can realize the control and optimization of the interface structure of the nano calcium carbonate; and an anhydride group contained in a maleic anhydride chain segment in a molecule can form effective chemical connection with an active group on the surface of calcium carbonate, so that a modifier is anchored on the calcium carbonate, an active epoxy group in an allyl phenyl ether chain segment can form good compatibility with other base materials in the lubricating grease, and an n-butyl acrylate chain segment can be used for adjusting the modulus of a system. Therefore, the macromolecular modifier can endow the modified nano calcium carbonate with excellent dispersing performance.
2. The macromolecular modified nano calcium carbonate is used, carbon-oxygen bonds with stable performance are introduced on the surface of the filler, and other chemical bonds in the lubricating grease can be protected by sacrificing the carbon-oxygen bonds in the molecules in the high-temperature thermal aging process, so that the aging speed of a system is slowed down, and the high-temperature resistance is improved.
3. The experimental data in table 1 show that the lubricating grease prepared by the preparation method of the high-performance composite calcium sulfonate-based lubricating grease containing nano calcium carbonate can endow the lubricating grease with more excellent hardening resistance and high temperature resistance. The grease obtained in example 3 is compared with the grease obtained in comparative examples 1 and 2, the comprehensive performance sum of the examples is improved, and the macromolecular modifier ABM modified nano calcium carbonate is greatly helpful for improving the performance of the grease. Comparing the grease obtained in the prior art in example 3 with the grease obtained in comparative examples 3 and 4, the high temperature life of the grease in the examples is respectively improved by 19.77% and 17.11% compared with the optimal value of the ratio, and the surface hardening value of the grease is respectively improved by 55.56% and 42.85% compared with the optimal value of the ratio, which shows that the performances of the grease in all aspects are improved to different degrees under the conditions of using the preparation method of the invention and adding the modified nano calcium carbonate, and the technical problems of hardening aging resistance and high temperature resistance are solved at the same time.
4. According to the experimental data in Table 2, when the addition amount of the modified nano calcium carbonate is 15-25 parts, the hardening resistance and the high temperature resistance of the lubricating grease are better; wherein modified nano CaCO3When the amount of the additive is 20 parts, the hardening resistance and the high temperature resistance of the grease are the best. This is because calcium carbonate in grease is decomposed to generate CaO under high temperature and high pressure conditions, and forms a smooth sliding layer under pressure to reduce friction and wear, thereby protecting grease. When the addition amount of the modified nano calcium carbonate is too small, a small amount of nano particles can not form a finished sliding layer, so that the compression resistance, the abrasion resistance and the high temperature resistance of the modified nano calcium carbonate are low; when the addition amount of the modified nano calcium carbonate is too large, the nano particles have strong aggregation tendency due to large specific surface area and surface energy, so that the dispersibility of the nano particles in a system is poor, the contact wear is increased, and the compression resistance, the friction resistance and the high temperature resistance are also not facilitated.
5. Compared with the common preparation method, the preparation method of the calcium carbonate-containing high-performance composite calcium sulfonate-based lubricating grease provided by the invention ensures good extreme pressure, wear resistance, high and low temperature properties and colloid stability of the lubricating grease, and also endows the lubricating grease with excellent hardening resistance and oil throwing resistance at high temperature; and the preparation method also has the advantages of less formula components, simple and easy operation, suitability for industrial production and the like.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1:
a preparation method of high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate comprises the following steps:
s1: weighing 1000g of 350mgKOH/g high-base-number calcium sulfonate and 1300g of 150BS base oil at room temperature, putting into a reaction kettle, stirring and mixing, continuously stirring, and heating to 95 ℃ to obtain a mixed material A;
s2: sequentially adding 10g of dodecahydroxystearic acid, 12g of dodecylbenzene sulfonic acid and 100g of water into the mixed material A, mixing uniformly, quickly adding 20g of acetic acid, and keeping the system at 95 ℃ for continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding 150g of modified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding 150g of 150BS base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
The modified nano calcium carbonate comprises the following raw materials in parts by weight: 100 parts of calcium carbonate whisker, 0.7 part of macromolecular modifier ABM and 16 parts of solvent; the calcium carbonate whisker is a GY series product of Jinan Zi Anhua chemical Co., Ltd, is needle-shaped in shape, and has the particle size of 33.2-48.7 nm; the solvent is analytically pure acetone; the synthesis of the modified nano calcium carbonate comprises the following steps:
s1: putting the calcium carbonate crystal whisker into a vacuum oven at 105 ℃ to be dried for 2 hours for later use, and keeping the water content of the calcium carbonate crystal whisker at 0.4%;
s2: diluting a macromolecular modifier ABM by using an acetone solvent, and uniformly mixing to obtain a mixed solvent;
s3: and (4) putting the dried calcium carbonate whiskers into a three-roll continuous modification machine, slowly adding the mixed solvent obtained in the step S2 while stirring, and stirring for 30min to obtain the modified nano calcium carbonate.
The modified nano calcium carbonate is a product obtained by modifying calcium carbonate whiskers by a macromolecular modifier ABM (namely a ternary random copolymer of propenyl phenyl ether, n-butyl acrylate and maleic anhydride), wherein the used macromolecular modifier ABM comprises the following components in parts by mole:
the preparation method and the synthesis reaction formula of the macromolecular modifier ABM are as follows:
firstly, a synthesis step: adding ethyl acetate into a four-neck flask, heating a water bath to 55 ℃ under the protection of nitrogen, and continuously stirring at 800 r/min; adding propenyl phenyl ether, n-butyl acrylate, maleic anhydride, azobisisobutyronitrile and dodecanethiol into ethyl acetate in sequence, stirring for 30min, heating to 65 ℃, and continuously stirring for 2.5h to obtain a viscous system; washing the sticky substance in n-hexane solution, repeatedly washing for 3 times, and drying to obtain macromolecular modifier ABM;
② the reaction formula for synthesizing the macromolecular modifier ABM:
wherein x, y and z are integers, x is more than 0 and less than or equal to 4, y is more than 2 and less than or equal to 10, z is more than 0 and less than or equal to 6, and the name ABM-1 is given (x is 2, y is 6, and z is 2).
Example 2:
a preparation method of high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate comprises the following steps:
s1: weighing 1000g of 350mgKOH/g high-base-number calcium sulfonate and 1400g of 150BS base oil at room temperature, putting the weighed materials into a reaction kettle, stirring and mixing, continuously stirring, and heating to 95 ℃ to obtain a mixed material A;
s2: adding 15g of dodecahydroxystearic acid, 15g of dodecylbenzene sulfonic acid and 120g of water into the mixed material A in sequence for mixing, quickly adding 28g of acetic acid after uniform mixing, and keeping the system at 95 ℃ for continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding 200g of modified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding 220g of 150BS base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
The modified nano calcium carbonate comprises the following raw materials in parts by weight: 100 parts of calcium carbonate whisker, 0.7 part of macromolecular modifier (ABM) and 20 parts of solvent; the calcium carbonate crystal whisker is a GY series product of Jinan Zi Anhua chemical Limited company, is needle-shaped in shape, and has the particle size of 28.9-51.6 nm; the solvent is analytically pure acetone;
the synthesis of the modified nano calcium carbonate comprises the following steps:
s1: putting the calcium carbonate crystal whisker into a vacuum oven at 105 ℃ to be dried for 2 hours for later use, and keeping the water content of the calcium carbonate crystal whisker at 0.6%;
s2: diluting a macromolecular modifier ABM by using an acetone solvent, and uniformly mixing to obtain a mixed solvent;
s3: and (4) putting the dried calcium carbonate whiskers into a three-roll continuous modification machine, slowly adding the mixed solvent obtained in the step (S2) under medium-speed stirring, and stirring for 30min to obtain the modified nano calcium carbonate.
The modified nano calcium carbonate is a product obtained by modifying calcium carbonate whiskers by a macromolecular modifier ABM (namely a ternary random copolymer of propenyl phenyl ether, n-butyl acrylate and maleic anhydride), wherein the used macromolecular modifier ABM comprises the following components in parts by mole:
the preparation method and the synthesis reaction formula of the macromolecular modifier ABM are as follows:
firstly, a synthesis step: adding ethyl acetate into a four-neck flask, heating a water bath to 55 ℃ under the protection of nitrogen, and continuously stirring at 800 r/min; adding propenyl phenyl ether, n-butyl acrylate, maleic anhydride, azobisisobutyronitrile and dodecanethiol into ethyl acetate in sequence, stirring for 30min, heating to 65 ℃, and continuously stirring for 2.5h to obtain a viscous system; washing the sticky substance in n-hexane solution for 4 times, and drying to obtain macromolecular modifier ABM;
② the reaction formula for synthesizing the macromolecular modifier ABM:
wherein x, y and z are integers, x is more than 0 and less than or equal to 4, y is more than 2 and less than or equal to 10, z is more than 0 and less than or equal to 6, and the name ABM-2 is given (x is 4, y is 6, and z is 2).
Example 3:
a preparation method of high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate comprises the following steps:
s1: weighing 1000g of 450mgKOH/g of high-base-number calcium sulfonate and 1100g of 150BS base oil at room temperature, putting the weighed materials into a reaction kettle, stirring and mixing, continuously stirring, and heating to 95 ℃ to obtain a mixed material A;
s2: sequentially adding 10g of dodecahydroxystearic acid, 11g of dodecylbenzene sulfonic acid and 100g of water into the mixed material A, mixing uniformly, quickly adding 26g of acetic acid, and keeping the system at 95 ℃ for continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding 180g of modified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding 180g of 150BS base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
The modified nano calcium carbonate comprises the following raw materials in parts by weight: 100 parts of calcium carbonate whisker, 0.7 part of macromolecular modifier (ABM) and 16 parts of solvent; the calcium carbonate whisker is a GY series product of Jinan Zi Anhua chemical Limited company, is needle-shaped in shape, and has the particle size of 43.4-58.2 nm; the solvent is analytically pure acetone;
the synthesis of the modified nano calcium carbonate comprises the following steps:
s1: putting the calcium carbonate crystal whisker into a vacuum oven at 105 ℃ to be dried for 2 hours for later use, and keeping the water content of the calcium carbonate crystal whisker at 0.5 percent;
s2: diluting a macromolecular modifier ABM by using an acetone solvent, and uniformly mixing to obtain a mixed solvent;
s3: and (4) putting the dried calcium carbonate whiskers into a three-roll continuous modification machine, slowly adding the mixed solvent obtained in the step (S2) under medium-speed stirring, and stirring for 30min to obtain the modified nano calcium carbonate.
The modified nano calcium carbonate is a product obtained by modifying calcium carbonate whiskers by a macromolecular modifier ABM (namely a ternary random copolymer of propenyl phenyl ether, n-butyl acrylate and maleic anhydride), wherein the used macromolecular modifier ABM comprises the following components in parts by mole:
the preparation method and the synthesis reaction formula of the macromolecular modifier ABM are as follows:
firstly, a synthesis step: adding ethyl acetate into a four-neck flask, heating a water bath to 55 ℃ under the protection of nitrogen, and continuously stirring at 800 r/min; adding propenyl phenyl ether, n-butyl acrylate, maleic anhydride, azobisisobutyronitrile and dodecanethiol into ethyl acetate in sequence, stirring for 30min, heating to 65 ℃, and continuously stirring for 2.5h to obtain a viscous system; washing the sticky substance in n-hexane solution, repeatedly washing for 3 times, and drying to obtain macromolecular modifier ABM;
② the reaction formula for synthesizing the macromolecular modifier ABM:
wherein x, y and z are integers, x is more than 0 and less than or equal to 4, y is more than 2 and less than or equal to 10, z is more than 0 and less than or equal to 6, and the name ABM-3 is given (x is 2, y is 6, and z is 5).
Comparative example 1:
the modified nano calcium carbonate comprises the following raw materials in parts by weight: 100 parts of calcium carbonate whisker, 0.7 part of HK-560 type coupling agent and 16 parts of solvent; the calcium carbonate whisker is a GY series product of Jinnan Zi Anhua chemical Co., Ltd, is needle-shaped, and has a particle size of 40.7-56.4 nm; the solvent is analytically pure acetone;
the synthesis of the modified nano calcium carbonate comprises the following steps:
s1: putting the calcium carbonate crystal whisker into a vacuum oven at 105 ℃ to be dried for 2 hours for later use, and keeping the water content of the calcium carbonate crystal whisker at 0.5 percent;
s2: diluting the HK-560 type coupling agent by using an acetone solvent, and uniformly mixing to obtain a mixed solvent;
s3: and (4) putting the dried calcium carbonate whiskers into a three-roll continuous modification machine, slowly adding the mixed solvent obtained in the step (S2) under medium-speed stirring, and stirring for 30min to obtain the modified nano calcium carbonate.
A preparation method of high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate comprises the following steps:
s1: weighing 1000g of 450mgKOH/g of high-base-number calcium sulfonate and 1100g of 150BS base oil at room temperature, putting the weighed materials into a reaction kettle, stirring and mixing, continuously stirring, and heating to 95 ℃ to obtain a mixed material A;
s2: sequentially adding 10g of dodecahydroxystearic acid, 11g of dodecylbenzene sulfonic acid and 100g of water into the mixed material A, mixing uniformly, quickly adding 26g of acetic acid, and keeping the system at 95 ℃ for continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding 180g of modified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding 180g of 150BS base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
Note: the modified nano calcium carbonate described in comparative example 1 is nano calcium carbonate modified by HK-560 type coupling agent, and HK-560 contains groups similar to ABM, so the modification thereof was used for comparison.
Comparative example 2:
a preparation method of high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate comprises the following steps:
s1: weighing 1000g of 450mgKOH/g of high-base-number calcium sulfonate and 1100g of 150BS base oil at room temperature, putting the weighed materials into a reaction kettle, stirring and mixing, continuously stirring, and heating to 95 ℃ to obtain a mixed material A;
s2: sequentially adding 10g of dodecahydroxystearic acid, 11g of dodecylbenzene sulfonic acid and 100g of water into the mixed material A, mixing uniformly, quickly adding 26g of acetic acid, and keeping the system at 95 ℃ for continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding 180g of unmodified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding 180g of 150BS base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
Note: the unmodified nano calcium carbonate described in comparative example 2 is GY series calcium carbonate whisker of jiannan zi chemical industry ltd.
Comparative example 3:
the grease was prepared by the methods of examples 1 to 5 of the specification "a complex calcium sulfonate grease containing nano calcium carbonate and a method for producing the same (grant No. CN 101993767B)" in chinese patent literature.
Comparative example 4:
the grease was prepared by the methods of examples 1 to 3 of the specification "a complex calcium sulfonate grease and a method for preparing the same (grant No. CN 102703185B)" in chinese patent literature.
The specific test method comprises the following steps:
the composite calcium sulfonate grease prepared in the embodiments 1 to 3 and the comparative examples 1 to 4 are subjected to performance tests, and the dropping point, the working cone penetration, the surface hardening performance, the wear performance, the steel mesh oil separation, the water leaching loss, the bearing leakage and the high-temperature service life of the composite calcium sulfonate grease are respectively tested according to the standards GB/T3498, GB/T269, GB/T512, SH/T0202, SH/T0324, SH/T0109, SH/T0326 and SH/T0428. The results of the performance tests of the examples and comparative examples are shown in Table 1.
TABLE 1 results of Performance test of each example and comparative example
The experimental data in table 1 show that the lubricating grease prepared by the preparation method of the high-performance composite calcium sulfonate-based lubricating grease containing nano calcium carbonate can endow the lubricating grease with more excellent hardening resistance and high temperature resistance. The grease obtained in example 3 is compared with the grease obtained in comparative examples 1 and 2, the comprehensive performance sum of the examples is improved, and the macromolecular modifier ABM modified nano calcium carbonate is greatly helpful for improving the performance of the grease. Comparing the grease obtained in the prior art in example 3 with the grease obtained in comparative examples 3 and 4, the high temperature life of the grease in the examples is respectively improved by 20.64% and 17.94% compared with the optimal value of the ratio, and the surface hardening value of the grease is respectively improved by 55.56% and 42.86% compared with the optimal value of the ratio, which shows that the performances of the grease in all aspects are improved to different degrees under the conditions of using the preparation method of the invention and adding the modified nano calcium carbonate, and the technical problems of hardening aging resistance and high temperature resistance are solved at the same time.
Except that the addition amount of the modified nano calcium carbonate is different, the other process steps and parameters are the same as those in the best example 3, the influence of the addition amount of the modified nano calcium carbonate on the hardening resistance and the high temperature resistance of the lubricating grease is studied, and the results are shown in table 2:
TABLE 2 Effect of modified Nano calcium carbonate addition on grease Performance
According to the experimental data in Table 2, the modified nano CaCO3When the addition amount is 15-25 parts, the hardening resistance and the high temperature resistance of the lubricating grease are good; wherein modified nano CaCO3When the amount of the additive is 20 parts, the hardening resistance and the high temperature resistance of the grease are the best. This is because CaCO in grease when the grease is under high temperature and high pressure conditions3CaO is generated through decomposition, and a smooth sliding layer is formed under the action of pressure to reduce friction and abrasion, so that the grease is protected. When modified nano CaCO3When the addition amount is too small, a small amount of nano particles can not form a finished sliding layer, so the compression resistance, abrasion resistance and high temperature resistance of the material are low; when modified nano CaCO3When the addition amount is too large, the nanoparticles have strong aggregation tendency due to large specific surface area and surface energy, so that the dispersibility of the nanoparticles in a system is poor, contact abrasion is increased, and the compression resistance, the friction resistance and the high temperature resistance are also not facilitated.
Those skilled in the art will recognize that numerous variations are possible in light of the above description, and thus the examples are intended to describe one or more specific embodiments.
While there has been described and illustrated what are considered to be example embodiments of the present invention, it will be understood by those skilled in the art that various changes and substitutions may be made therein without departing from the spirit of the invention. In addition, many modifications may be made to adapt a particular situation to the teachings of the present invention without departing from the central concept described herein. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments and equivalents falling within the scope of the invention.
Claims (8)
1. The high-performance composite calcium sulfonate-based lubricating grease containing calcium carbonate is characterized by comprising the following raw materials in parts by weight: 100 parts of high-base-number calcium sulfonate, 120-170 parts of base oil, 1-1.5 parts of alkyl benzene sulfonic acid, 0.5-2 parts of fatty acid, 1-10 parts of acetic acid, 5-15 parts of water and 15-25 parts of modified nano calcium carbonate;
the modified nano calcium carbonate comprises the following raw materials in parts by weight: 100 parts of calcium carbonate whisker, 0.5-1 part of macromolecular modifier ABM and 10-20 parts of solvent; the solvent is acetone;
the synthesis of the modified nano calcium carbonate comprises the following steps:
s1: putting the calcium carbonate crystal whisker into a 105 ℃ vacuum oven to be dried for 2 hours for later use, and keeping the water content of the calcium carbonate crystal whisker to be 0.3-0.6%;
s2: diluting a macromolecular modifier ABM by using an acetone solvent, and uniformly mixing to obtain a mixed solvent;
s3: putting the dried calcium carbonate crystal whiskers into a three-roll continuous modification machine, slowly adding the mixed solvent obtained in the step S2 while stirring, and stirring for 30min to obtain modified nano calcium carbonate;
the macromolecular modifier ABM takes molar parts as units and comprises the following raw materials:
the preparation method and the synthesis reaction formula of the macromolecular modifier ABM are as follows:
firstly, a synthesis step: adding ethyl acetate into a four-neck flask, heating a water bath to 55 ℃ under the protection of nitrogen, and continuously stirring at 800 r/min; adding propenyl phenyl ether, n-butyl acrylate, maleic anhydride, azobisisobutyronitrile and dodecanethiol into ethyl acetate in sequence, stirring for 30min, heating to 65 ℃, and continuously stirring for 2.5h to obtain a viscous system; putting the sticky matter into a normal hexane solution for washing, repeatedly washing for 3-4 times, and drying to obtain a macromolecular modifier ABM;
② the reaction formula for synthesizing the macromolecular modifier ABM:
wherein x, y and z are integers, x is more than 0 and less than or equal to 4, y is more than 2 and less than or equal to 10, and z is more than 0 and less than or equal to 6; ABM-1 is named, wherein x is 2, y is 6, and z is 2; ABM-2, wherein x is 4, y is 6, and z is 2; ABM-3, where x is 2, y is 6, and z is 5.
2. The calcium carbonate-containing high-performance complex calcium sulfonate-based grease as claimed in claim 1, wherein the high base number calcium sulfonate is a synthetic calcium sulfonate.
3. The calcium carbonate-containing high-performance complex calcium sulfonate-based grease as claimed in claim 2, wherein the total base number of the synthetic calcium sulfonate is 300 to 500 mgKOH/g.
4. The calcium carbonate-containing high performance calcium complex sulfonate-based grease of claim 1, wherein the base oil is one or more of 150BS, 120BS, HV1500, MVI 150.
5. The calcium carbonate-containing high-performance complex calcium sulfonate-based grease according to claim 1, wherein the alkylbenzene sulfonic acid is C10～C18One of linear alkyl benzene sulfonic acids.
6. The calcium carbonate-containing high-performance calcium polysulfonate-based grease as claimed in claim 1, wherein said fatty acid is a long chain fatty acid containing a hydroxyl group.
7. The calcium carbonate-containing high-performance calcium polysulfonate-based grease as claimed in claim 1 wherein said water is deionized water.
8. A method for preparing a high-performance calcium sulfonate complex grease containing calcium carbonate according to any one of claims 1 to 7, comprising the steps of:
s1: at room temperature, putting the high-base-number calcium sulfonate and a part of base oil into a reaction kettle, stirring and mixing, heating to 75-100 ℃, and continuously stirring in the heating process to obtain a mixed material A;
s2: adding alkylbenzene sulfonic acid, fatty acid and water into the mixed material A in sequence according to a proportion, and quickly adding acetic acid after uniformly stirring; keeping the temperature at 95 ℃ and continuously stirring for 1.5h to obtain a viscous mixed material B;
s3: adding the modified nano calcium carbonate into the viscous mixed material B, keeping the temperature at 95 ℃ and continuously stirring for 15min, then heating to 180 ℃ and continuously stirring for 20min, carrying out dehydration reaction, adding the rest base oil after dehydration, cooling to 100 ℃, and grinding and homogenizing to obtain the composite calcium sulfonate base lubricating grease product.
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