Polymeric self-assembling spherical micellar particles, methods of making and using the same

Abstract

The application provides a kind of polymerization induced self-assembly spherical micelle particle and its preparation method and application, belong to lubricating additive technical field. Including the following steps: thio carbonic acid ester chain transfer agent, methacrylic ester monomer, first initiator and organic solvent are mixed to carry out RAFT polymerization reaction, the macromolecular chain transfer agent obtained, benzyl methacrylate, second initiator and base oil are mixed to carry out polymerization induced self-assembly reaction. RAFT polymerization reaction can effectively control radical active growth, obtain the macromolecular chain transfer agent with narrow molecular weight distribution and good dispersity, in the process of polymerization induced self-assembly reaction, polymethyl benzyl methacrylate is used as nucleation segment, and is distributed in micelle inside, polymethyl methacrylate is used as stable segment and is distributed in micelle outside, because methacrylic ester monomer has strong lipophilicity, so spherical micelle particle can be stably dispersed in base oil.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating additive, in particular to a kind of polymeric self-assembly spherical micelle particle and its preparation method and application. BACKGROUND

[0002] Traditional nanoparticle lubricating oil additives, such as Cu, Ni, Co, MoS2, SiO2, CuO and other inorganic nanoparticles, due to Brownian motion, particles are easy to adsorb and aggregate, and due to gravity, the particles are settled, so that the lubricating oil loses the effect of reducing and anti-wear, and the particle aggregation problem exists, usually surface active agents or organic compounds are used for surface modification, such as commonly used organic compounds such as oleic acid (OA), silane coupling agent and other compounds grafted on the surface of particles can improve the dispersibility of particles in solvent. However, due to the large density difference between inorganic nanoparticles and lubricating oil, the stability of the particles still exists during long-term storage. SUMMARY

[0003] Therefore, the present application provides a kind of polymeric self-assembly spherical micelle particle and its preparation method and application. The spherical micelle particle prepared by the present application can be stably dispersed in oil.

[0004] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0005] The present application provides a preparation method of a polymeric self-assembly spherical micelle particle, comprising the following steps:

[0006] The reversible addition-fragmentation transfer radical polymerization reaction is carried out by mixing the thiocarbonic ester chain transfer agent, the methacrylate monomer, the first initiator and the organic solvent to obtain a macromolecular chain transfer agent;

[0007] The polymeric self-assembly reaction is carried out by mixing the macromolecular chain transfer agent, the benzyl methacrylate, the second initiator and the base oil to obtain the polymeric self-assembly spherical micelle particle.

[0008] Preferably, the molar ratio of the thiocarbonic ester chain transfer agent, the methacrylate monomer and the first initiator is 1: (40-50): 0.1.

[0009] Preferably, the thiocarbonic ester chain transfer agent includes one or more of 2-phenyl-2-propyl benzene dithioate, 4-cyano-4-thiobenzoyl valeric acid and 4-cyano-4-(2-phenylethylsulfonylthiocarbonyl) sulfonated valeric acid.

[0010] Preferably, the methacrylate monomer includes one or more of lauryl methacrylate, myristyl methacrylate, cetyl methacrylate and stearyl methacrylate.

[0011] Preferably, the temperature of the reversible addition fragmentation transfer radical polymerization reaction is 70-90 DEG C, and the time is 4-6h.

[0012] Preferably, the molar ratio of the macromolecular chain transfer agent, benzyl methacrylate and the second initiator is 1:(250-300):0.1.

[0013] Preferably, the molar ratio of the macromolecular chain transfer agent and the crosslinking agent after the polymerization induced self-assembly reaction is 1:(10-40).

[0014] Preferably, the temperature of the polymerization induced self-assembly reaction is 70-90 DEG C, and the time is 5-12h.

[0015] The application further provides the polymerization induced self-assembly spherical micelle particle prepared by the preparation method.

[0016] The application further provides the application of the polymerization induced self-assembly spherical micelle particle as a lubricating oil additive in the field of lubrication.

[0017] The application provides a preparation method of a polymerization induced self-assembly spherical micelle particle, which comprises the following steps: mixing a thiocarbonic ester chain transfer agent, a methacrylate monomer, a first initiator and an organic solvent to perform a reversible addition fragmentation transfer radical polymerization (RAFT polymerization) reaction, so as to obtain a macromolecular chain transfer agent; mixing the macromolecular chain transfer agent, benzyl methacrylate, a second initiator and base oil to perform a polymerization induced self-assembly reaction, so as to obtain the polymerization induced self-assembly spherical micelle particle.

[0018] In the application, the RAFT polymerization is one of active radical polymerization, has a wide range of reaction conditions and monomer selection, can effectively control the active growth of radicals, and obtain the macromolecular chain transfer agent with a narrow molecular weight distribution and good dispersity; the polymerization induced self-assembly can in-situ synthesize the spherical micelle particle with uniform structure in a wide concentration range; in the process of the polymerization induced self-assembly reaction, the polymethyl benzyl methacrylate is distributed in the micelle interior as a nucleating chain segment, and the polymethyl methacrylate is distributed on the micelle outside as a stabilizing chain segment; because the methacrylate monomer has strong lipophilicity, the long chain of the methacrylate monomer can be well dissolved in lubricating oil, so that the spherical micelle particle can be stably dispersed in the base oil; because the stabilizing chain segment has strong lipophilicity, the micelle particle can be stably dispersed in the base oil, and in the friction process, the micelle particle can be used as a lubricating oil additive to reduce the friction and wear at a high temperature and load.

[0019] Furthermore, the in-situ synthesis of micelle particles in lubricating oil is achieved during the polymerization-induced self-assembly reaction, requiring no other steps and simplifying the operation. Data from the examples show that the polymerization-induced self-assembled spherical micelle particles prepared by this invention did not exhibit stratification after being left to stand for one year and can still be used normally. Attached Figure Description

[0020] Figure 1 The results of GPC analysis of macromolecular chain transfer agents and micelle particles in Examples 2 and 3 are as follows;

[0021] Figure 2 TEM images of the micelle particles in column 2 were obtained;

[0022] Figure 3 These are tribological test diagrams of base oil PAO4 and products of embodiments 2, 3, and 4 under different loads;

[0023] Figure 4 L in Example 3 43 -B 204 Comparison of the stability of SiO2 nanoparticles and TiN nanoparticles as lubricant additives in PAO4. Detailed Implementation

[0024] This invention provides a method for preparing polymerization-induced self-assembled spherical micelle particles, comprising the following steps:

[0025] A reversible addition-fracture transfer radical polymerization reaction was carried out by mixing a thiocarbonate chain transfer agent, a methacrylate monomer, a first initiator and an organic solvent to obtain a macromolecular chain transfer agent.

[0026] The macromolecular chain transfer agent, benzyl methacrylate, the second initiator, and the base oil are mixed and subjected to a polymerization-induced self-assembly reaction to obtain the polymerization-induced self-assembled spherical micelle particles.

[0027] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0028] This invention involves mixing a thiocarbonate chain transfer agent, a methacrylate monomer, a first initiator, and an organic solvent to carry out a reversible addition-fracture transfer radical polymerization reaction to obtain a macromolecular chain transfer agent.

[0029] In this invention, the molar ratio of the thiocarbonate chain transfer agent (CTA), the methacrylate monomer, and the first initiator is preferably 1:(40-50):0.1.

[0030] In the present application, the thio carbonic ester chain transfer agent preferably comprises one or more of 2-phenyl-2-propyl benzene dithioate (CDB), 4-cyano-4-thio benzoyl valeric acid (CPDB) and 4-cyano-4-(2-phenyl ethyl sulfone thio carbonyl) sulfone valeric acid (PETTC).

[0031] In the present application, the methacrylate monomer preferably comprises one or more of lauryl methacrylate, myristyl methacrylate, cetyl methacrylate and stearyl methacrylate.

[0032] In the present application, the first initiator is preferably azobis isobutyronitrile (AIBN) or azobis isohexyl nitrile, which is preferably subjected to a purification treatment before use, and the present application does not have special limitations on the specific mode of the purification treatment, which can be performed in a manner well known to those skilled in the art.

[0033] In the present application, the temperature of the reversible addition-fragmentation transfer radical polymerization reaction is preferably 70-90°C, more preferably 75-85°C, and the time is preferably 4-6h, more preferably 5h.

[0034] In the present application, the principle of the reversible addition-fragmentation transfer radical polymerization reaction is shown in formula I:

[0035]

[0036] In formula I, m=8-16 and x=40-50.

[0037] In the present application, the organic solvent is preferably toluene or tetrahydrofuran.

[0038] In the present application, the thio carbonic ester chain transfer agent, the methacrylate monomer, the first initiator and the organic solvent are added to a Schlenk bottle, deoxygenated with argon for 30min in an ice bath, and then the RAFT polymerization reaction is performed.

[0039] After the reversible addition-fragmentation transfer radical polymerization reaction is completed, the present application preferably quenches the reaction after cooling, pours the obtained mixture into a beaker and adds methanol to fully stir the product, and dries the product in a vacuum oven at 40°C to obtain the macromolecular chain transfer agent.

[0040] After obtaining the macromolecular chain transfer agent, the present application mixes the macromolecular chain transfer agent, benzyl methacrylate, a second initiator and a base oil to perform a polymerization-induced self-assembly reaction to obtain the polymerization-induced self-assembly spherical micelle particles.

[0041] In the present application, the second initiator is preferably azobisisobutyronitrile or azobisisoheptyl nitrile, and the second initiator is preferably purified before use. The present application does not have special limitations on the specific mode of the purification treatment, and a mode well known to those skilled in the art can be used.

[0042] In the present application, the base oil is preferably PAO oil or silicone oil.

[0043] In the present application, the molar ratio of the macromolecular chain transfer agent, benzyl methacrylate and the second initiator is preferably 1:(250-300):0.1.

[0044] In the present application, the temperature of the polymerization-induced self-assembly reaction is preferably 70-90°C, more preferably 75-85°C, and the time is preferably 5-12h, more preferably 6-10h.

[0045] In the present application, the principle of the polymerization-induced self-assembly reaction is preferably as shown in formula II:

[0046]

[0047] In formula II, x and y are both monomer polymerization degrees, x=40-50, y=80-210, and m=8-16.

[0048] In the present application, the macromolecular chain transfer agent, benzyl methacrylate, the second initiator and the base oil are added to a Schlenk bottle, deoxygenated with argon for 30min in an ice bath, and then the polymerization-induced self-assembly reaction is carried out, so that the polymerization-induced self-assembly spherical micellar particles are obtained.

[0049] In the present application, the polymerization-induced self-assembly reaction preferably further comprises adding a crosslinking agent after the reaction, and the molar ratio of the macromolecular chain transfer agent and the crosslinking agent is preferably 1:(10-40).

[0050] In the present application, the crosslinking agent preferably comprises polyethylene glycol diacrylate or polyethylene glycol dimethacrylate. After the crosslinking agent is added, the product of the polymerization-induced self-assembly reaction continues to carry out a crosslinking reaction with the crosslinking agent, and the time of the crosslinking reaction is preferably 1-2h, and the temperature is preferably 70-90°C.

[0051] In the present application, the crosslinking agent is used to stabilize the structure of the micellar particles.

[0052] In the present application, taking polyethylene glycol diacrylate as an example, the principle of the crosslinking reaction is preferably as shown in formula III:

[0053]

[0054] In formula III, x=40-50, y=80-210, z=10-40, and m=8-16.

[0055] The application further provides the polymeric self-assembly spherical micelle particles prepared by the preparation method.

[0056] In the application, the polymeric self-assembly spherical micelle particles have a number average molecular weight of preferably ≥20000, a friction coefficient of preferably ≤0.16, and a pressure bearing capacity of preferably ≤1000N.

[0057] The application further provides application of the polymeric self-assembly spherical micelle particles as a lubricating oil additive in the field of lubrication.

[0058] In order to further illustrate the application, the polymeric self-assembly spherical micelle particles, the preparation method and the application thereof provided by the application are described in detail below with reference to examples, but they should not be understood as limiting the protection scope of the application.

[0059] In the embodiment of the application, the methacrylate monomer, the thio carbonic ester chain transfer agent and the initiator are provided by Saen Chemical Technology Co., Ltd.

[0060] Example 1

[0061] Step 1: 279.37 mg of 4-cyano-4-thiobenzoyl valeric acid, 14.6 mL of lauryl methacrylate, 16.4 mg of AIBN and 15 mL of toluene were mixed in a schlenk bottle and stirred by a magnetic stirrer, and deoxygenated by argon for 30 min, and then subjected to RAFT polymerization at 70°C for 5 h, and after quenching and cooling, the mixed product was poured into a beaker, and anhydrous methanol was added to purify the product, and the purified product was dried in a vacuum oven at 40°C for 12 h to remove residual solvent, to obtain a macromolecular chain transfer agent PLMA 43 -CTA.

[0062] Step 2: 2270 mg of PLMA 43 -CTA, 6.8 mL of benzyl methacrylate, 3.28 mg of AIBN and 45 mL of PAO4 were added to a schlenk bottle and stirred by a magnetic stirrer, and deoxygenated by argon for 30 min in an ice bath, and then subjected to polymerization-induced self-assembly at 90°C for 12 h, to obtain spherical micelle particles PLMA 43 -PBZMA 86 43 and 86 refer to the polymerization degree of the monomer.

[0063] Example 2

[0064] First step: 558.7 mg 4-cyano-4-thiobenzoyl valeric acid, 29.2 mL lauryl methacrylate, 32.8 mg AIBN and 30 mL toluene were added into a schlenk flask and stirred well with a magnetic stirrer, while argon deoxidation was carried out for 30 min; RAFT polymerization was carried out at 70°C for 5 h, after quenching and cooling, the mixed product was poured into a beaker, and anhydrous methanol was added for product purification, and the purified product was dried in a vacuum oven at 40°C for 12 h to remove residual solvent, to obtain a macromolecular chain transfer agent PLMA 43 -CTA (PLMA 43 ).

[0065] Second step: 794 mg PLMA 43 -CTA, 2.97 mL benzyl methacrylate, 1.15 mg AIBN and 18.7 mL PAO4 were added into a schlenk flask and stirred well with a magnetic stirrer, while argon deoxidation was carried out for 30 min in an ice bath; polymerization-induced self-assembly was carried out at 90°C for 5 h, to obtain spherical micellar particles PLMA 43 -PBZMA 103 (L 43 -B 103 ).

[0066] Example 3

[0067] First step: 558.7 mg 4-cyano-4-thiobenzoyl valeric acid, 29.2 mL lauryl methacrylate, 32.8 mg AIBN and 30 mL toluene were added into a schlenk flask and stirred well with a magnetic stirrer, while argon deoxidation was carried out for 30 min; RAFT polymerization was carried out at 70°C for 5 h, after quenching and cooling, the mixed product was poured into a beaker, and anhydrous methanol was added for product purification, and the purified product was dried in a vacuum oven at 40°C for 12 h to remove residual solvent, to obtain a macromolecular chain transfer agent PLMA 43 -CTA.

[0068] Second step: 794 mg PLMA 43 -PBZMA 204 (L 43 -B 204 ).

[0069] The micellar particles were subjected to GPC and TEM studies, and were subjected to tribological studies using a SRV-IV friction and wear tester.

[0070] Example 4

[0071] First step: 558.7 mg 4-cyano-4-thiobenzoyl valeric acid, 29.2 mL lauryl methacrylate, 32.8 mg AIBN and 30 mL toluene were added into a schlenk flask and stirred well with a magnetic stirrer, while argon deoxidation for 30 min; RAFT polymerization was carried out at 70°C for 5 h, after quenching and cooling, the mixture was poured into a beaker, while adding anhydrous methanol for product purification, the purified product was dried in a vacuum oven at 40°C for 12 h to remove residual solvent, to obtain macromolecular chain transfer agent PLMA 43 -CTA.

[0072] Second step: 794 mg PLMA43-CTA, 2.97 mL benzyl methacrylate, 1.15 mg AIBN and 18.7 mL PAO4 were added into a schlenk flask and stirred well with a magnetic stirrer, while argon deoxidation for 30 min in an ice bath; after 4 h polymerization induced self-assembly at 90°C, 0.2 mL polyethylene glycol diacrylate was added for crosslinking reaction for 1 h, to obtain spherical crosslinked micellar particles PLMA with a solid content of 20%. 43 -PBZMA 103 -PEGDA 10 (L 43 -B 103 -E 10 ).

[0073] Figure 1 For the results of GPC analysis of the macromolecular chain transfer agent and micellar particles of Examples 2 and 3, it can be seen that the molecular weight distribution of the micellar particles is uniform.

[0074] Figure 2 For the TEM image of the micellar particles in Example 2, it can be seen that the micellar particles have a spherical morphology, proving that the micellar particles have been successfully synthesized.

[0075] Figure 3The results of tribological research of base oil PAO4 and products of examples 2, 3 and 4 under different loads are obtained by using SRV-IV micro-tribological tester. In the experiment, Gcr15 material, steel ball with a diameter of 10 mm and stainless steel 304 material, steel support with a diameter of 24 mm and a height of 7.9 mm are selected as the friction pair. The experimental conditions are: temperature 25℃, frequency 25Hz, amplitude 1mm, load 50N-1000N. It is known that the friction coefficient of PAO4 is 0.25 and the critical load is 200N, while the friction coefficient of PAO4 containing micellar particles of example 4 is 0.16, which can still maintain stable lubrication effect when the load increases to 1000N. It is proved that the micellar particles can be used as lubricating oil additives, which can reduce the friction coefficient and also greatly improve the load-carrying capacity of the oil.

[0076] Figure 4 L43-B204 of example 3 43 -B 204 SiO2 nanoparticles and TiN nanoparticles as lubricating oil additives are compared in PAO4. The solid content of SiO2 nanoparticles and TiN nanoparticles in PAO4 is 1% (1wt%), and the solid content of L43-B204 is 20wt%. The samples are respectively placed at room temperature (r.t. represents room temperature). After two days, it is observed that SiO2 and TiN nanoparticles are all settled down, while the nanoparticles prepared by the present application have not been observed to settle after 300 days.

[0077] The above only describes the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which should also be considered as the protection scope of the present application.

Claims

1. A method for preparing polymeric self-assembled spherical micellar particles, characterized by, The method comprises the following steps: mixing a thio carbonic ester chain transfer agent, a methacrylate monomer, a first initiator and an organic solvent to perform a reversible addition fragmentation chain transfer radical polymerization reaction, to obtain a macromolecular chain transfer agent; mixing the macromolecular chain transfer agent, a benzyl methacrylate, a second initiator and a base oil to perform a polymerization induced self-assembly reaction, to obtain the polymerization induced self-assembly spherical micelle particles; the polymerization induced self-assembly reaction further comprises adding a crosslinking agent after the polymerization induced self-assembly reaction, and the molar ratio of the macromolecular chain transfer agent to the crosslinking agent is 1:(10-40).

2. The production method according to claim 1, characterized by, The molar ratio of the thio carbonic ester chain transfer agent, the methacrylate monomer and the first initiator is 1:(40-50):0.

1.

3. The production method according to claim 1 or 2, characterized by, The thio carbonic ester chain transfer agent comprises one or more of 2-phenyl-2-propyl benzene dithioate, 4-cyano-4-thiobenzoyl valeric acid and 4-cyano-4-(2-phenylethyl sulfonylthiocarbonyl) sulfonyl valeric acid.

4. The production method according to claim 1 or 2, characterized by, The methacrylate monomer comprises one or more of lauryl methacrylate, myristyl methacrylate, cetyl methacrylate and stearyl methacrylate.

5. The preparation method according to claim 1, characterized in that, The temperature of the reversible addition fragmentation chain transfer radical polymerization reaction is 70-90℃, and the time is 4-6h.

6. The method of claim 1, wherein, The molar ratio of the macromolecular chain transfer agent, the benzyl methacrylate and the second initiator is 1:(250-300):0.

1.

7. The preparation method according to claim 1, characterized in that, The temperature of the polymerization induced self-assembly reaction is 70-90℃, and the time is 5-12h.

8. The polymerization induced self-assembly spherical micelle particles prepared by the preparation method in any one of claims 1-7.

9. The polymerization induced self-assembly spherical micelle particles in claim 8 as a lubricating oil additive in the field of lubrication.

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