CN108641593B - Preparation method of 'two-step' lubricating durable organic silicon anti-icing coating - Google Patents
Preparation method of 'two-step' lubricating durable organic silicon anti-icing coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a 'two-step' lubricating durable organic silicon anti-icing coating. Firstly, reacting hydrogen-containing polydimethylsiloxane and single-end vinyl polydimethylsiloxane to form a brush type graft polymer; and the second step is to prepare a uniform reaction solution by using a brush-type graft polymer as a main raw material, using double-end vinyl polydimethylsiloxane as a cross-linking agent and using polydimethylsiloxane which does not participate in cross-linking reaction as an additive, and prepare the durable organic silicon anti-icing coating with lubricity under the action of Karstedt't catalyst. The lubricating durable organic silicon anti-icing coating prepared by the two-step method has ultralow ice shear strength which is 2.4kPa at least and excellent abrasion resistance. The preparation method is simple and convenient, the materials are easy to obtain, and the prepared anti-icing coating has good transparency and is used in the field of hydrophobic and anti-icing coatings.
Description
Technical Field
The invention relates to a preparation method of a 'two-step' lubricating durable organic silicon anti-icing coating, belonging to the field of preparation of organic silicon coatings and application of hydrophobic and anti-icing coating materials.
Background
In the fields of aerospace, transportation, electric power communication and the like, ice coating on the surface of a substrate brings serious economic loss and serious harm to human beings and society. Although the traditional active deicing method, such as mechanical deicing, heating deicing, spraying antifreeze and the like, is widely applied, the defects of high consumption, low efficiency and environmental pollution also restrict the application of the traditional active deicing method in the field of ice coating prevention. The method for constructing the anti-icing and anti-icing functional coating on the surface of the substrate has low cost, simple and convenient application and implementation and greater development and application value. Ice-over resistant coatings can be classified into three categories according to their composition and performance characteristics: low surface energy coatings, surface lubrication coatings and super-hydrophobic anti-icing coatings.
Wetting of porous surfaces with lubricating fluids is the hotspot of current anti-icing coating research (Kreder MJ, Alvarenga J, Kim P, Aizenberg J. design of anti-icing surfaces: smooth, textured or slide.
The organosilicon material has lower surface energy and good hydrophobicity, and is widely applied to the preparation of the anti-icing coating. The organic silicon has lower glass transition temperature and good flexibility, so that the siloxane chain segment still has flexibility and outward migration capability at low temperature, and has good low-temperature resistance.
Kota et al mixed vinyl-, hydrosilylation and trimethyl-terminated polydimethylsiloxanes into a homogeneous solution and produced a lubricious durable polydimethylsiloxane gel with excellent mechanical durability and ultra-low ice adhesion strength by hydrosilylation, where trimethyl-terminated polydimethylsiloxanes served as plasticizers to control the crosslink density of the system while providing some lubrication to minimize the ice adhesion strength to 5.2kPa (beer DL, Wang W, KotaAK. Dual gels with ultra-low adhesion to journal of Materials chemistry A,2016,4: 18253-18258).
The polysiloxane has good low-temperature flexibility, is widely applied to the field of anti-icing materials, but has relatively poor mechanical property, and the ice shear strength is generally more than 50 kPa. In order to improve mechanical properties such as wear resistance of an organic silicon coating and prepare an anti-icing coating with ultralow ice shear strength, polydimethylsiloxane is used as a raw material, a main chain and a branch chain are firstly prepared into a brush-type graft polymer through hydrosilylation, then cross-linking agents and additives with different components and contents are added into the system, and a two-step method is adopted to prepare the lubricating durable organic silicon anti-icing coating. The coating still has ultralow ice shear strength after being worn for many times by combining the mechanical properties of regular molecular arrangement, better flexibility at low temperature and the like of the brush type graft polymer and the lubricating effect of the additive, ice can be removed from the coating by the action of wind and gravity, and the wear resistance of the coating is improved. This work is not currently reported.
Disclosure of Invention
The invention aims to provide a preparation method of a 'two-step' lubricating durable organic silicon anti-icing coating.
The invention takes polydimethylsiloxane-polymethylhydrosiloxane as a main chain, monovinyl polydimethylsiloxane as a branched chain, vinyl double-terminated polydimethylsiloxane as a cross-linking agent, and takes polydimethylsiloxane which does not participate in cross-linking reaction as an additive. The materials are used as raw materials, polysiloxane used as a main chain and a branched chain is subjected to hydrosilylation to synthesize PDMS brush type graft polymers with different grafting degrees, then cross-linking agents and additives with different components and contents are added into the system, and a two-step method is adopted to prepare the lubricating durable organic silicon anti-icing coating.
In order to achieve the aim, the invention provides a 'two-step method' for preparing a lubricating durable organic silicon anti-icing coating, which is characterized in that the prepared organic silicon anti-icing coating has ultra-low ice shear strength (the ice shear strength can be lower than 10kPa) and excellent abrasion resistance.
The invention discloses a preparation method of a 'two-step' lubricating durable organic silicon anti-icing coating, which comprises the following steps: the method comprises the following steps:
1) the PDMS brush type polymer is synthesized by the following components in percentage by weight:
hydrogen-containing polydimethylsiloxane: 4-30 wt%;
monovinyl polydimethylsiloxane: 6-20 wt%;
the balance being solvent;
mixing the main chain hydrogen-containing polydimethylsiloxane (PDMS-PMHS) and the branched single-ended vinyl polydimethylsiloxane (PDMS-V) with a solvent according to the mass ratio to prepare a reaction solution; adding a mixed solution (the mass fraction of the solution is 0.5-5 wt%) of Karstedt's catalyst (0.001% of the mass of the reaction substance) and a solvent into the system under the protection of nitrogen; heating to 60-90 ℃, and carrying out condensation reflux reaction for 10-58 h under stirring; and (3) taking out the crude product after the reaction is finished, carrying out rotary evaporation at the temperature of 30-70 ℃, removing the solvent as much as possible, and drying in a vacuum drying oven for 24-48 h to remove the residual solvent, thereby obtaining the PDMS brush type graft polymers with different grafting degrees.
2) The preparation method of the lubricating durable organic silicon anti-icing coating comprises the following material components in percentage by weight:
polydimethylsiloxane brush type graft polymer: 8-30 wt%;
vinyl-terminated polydimethylsiloxane: 3-15 wt%;
polydimethylsiloxane: 4-15 wt%;
karstedt's catalyst: 0.01-0.12 wt%;
the balance being solvent.
Weighing a PDMS brush type graft polymer, a cross-linking agent double-end vinyl polydimethylsiloxane (V-PDMS-V) and an additive Polydimethylsiloxane (PDMS) according to a determined mass ratio, preparing a reaction solution with a solvent, and ultrasonically stirring for 1-2 h to uniformly mix the solution to make the solution in a uniform and transparent state; coating a proper amount of solution on the surface of a base material, drying the surface for 1-4 hours at room temperature, then placing the base material into a blast drying oven at the temperature of 70-120 ℃ for crosslinking and curing for 3-6 hours to form a film, and preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The solvent is one of toluene, xylene, dichloromethane, ethyl acetate and tetrahydrofuran.
The coating method adopts methods such as drop coating, spin coating, spray coating or dip coating.
The molecular formula of the main chain PDMS-PMHS is as follows:
wherein m is 5 to 60, n/m is 0 to 324, and the molecular weight is 4000 to 120000.
The molecular formula of the branched chain PDMS-V is as follows:
wherein q is 4 to 93, and the molecular weight is 500 to 7000.
The molecular formula of the PDMS brush type graft polymer prepared from the branched chain PDMS-V is as follows:
wherein x is 0 to 60, y is 0 to 60, z is 4 to 93, p/x is 0 to 533, and the molecular weight is 8000 to 200000.
The molecular formula of the crosslinking agent V-PDMS-V is as follows:
wherein r is 4 to 268, and the molecular weight is 500 to 20000.
The formula of the additive PDMS which does not participate in the crosslinking reaction is as follows:
wherein t is 5 to 404 and the molecular weight is 532 to 30000.
The performance test method comprises the following steps:
1) water contact Angle test
The method is characterized in that deionized water is used as test liquid, a static water contact angle of the coating at room temperature is measured by a static liquid drop method, a five-point fitting method is utilized for calculating the contact angle, and each coating sample is tested five times and an average value is obtained. The contact angle tester is model number JC 2000D.
2) Ice shear Strength test
The ice shear strength of the coating was tested using a side-push method. The test procedure was as follows: three samples in each group are taken and placed on a cold table; vertically placing a hollow glass cylinder with the average diameter of 9.84mm and treated by perfluorooctyl trichlorosilane on the surface of the coating, and dripping 450 mu L of deionized water; cooling the cooling table to-15 ℃ at the speed of 2 ℃/min, and preserving heat for 2-3 hours to ensure that all deionized water in the hollow glass cylinder is frozen; the test ice shear force is pushed forward at a speed of 0.1-0.5 mm/s, and the maximum shear force and the test curve are recorded. The push-pull dynamometer is of the type Imada ZP-50N, japan, and the average value is obtained by three coating measurements for each component.
3) Abrasion resistance test
The silicone coated substrate was mounted on a Taber linear abrasion tester weighing about 1100g total. The grinder surface was reconditioned with sandpaper for 25cycles/min before each test. The wear test was carried out using 400-grim sandpaper at a pressure of 6.8kPa and at a speed of 25cycles/min, with a stroke length of 2.54 cm.
The invention has the advantages that the lubricating durable organic silicon anti-icing coating prepared by the two-step method has ultra-low ice shear strength and excellent wear resistance, the ice shear strength can be as low as 2.4kPa, and the wear resistance times can reach 100 cycles. The doped unreacted silicone oil serving as the oily lubricating liquid can be released and migrated to the surface of the coating at low temperature to form an oily lubricating layer, so that the ice adhesion strength is greatly reduced; the regular and ordered molecular arrangement of the PDMS brush type graft polymer further improves the flexibility of the anti-icing coating substrate, the wear resistance of the coating is greatly improved, and the better flexibility of the coating also makes a certain contribution to the ultralow ice shear strength of the coating.
The 'two-step' lubricating durable organic silicon anti-icing coating is used as a hydrophobic anti-icing material.
Drawings
FIG. 1: the contact angle of the coating in example 1 is shown schematically, with a static water contact angle of 98 °.
Detailed Description
The technical solution of the present invention is further described below with reference to the following embodiments, which are further illustrative of the present invention and do not limit the applicable scope of the present invention.
Example 1
1) Synthesis of PDMS brush type graft polymer
2.0g of main chain PDMS-PMHS (molecular weight 62000), 3.0g of branched chain PDMS-V (molecular weight 500) and 45.0g of tetrahydrofuran are mixed to prepare a uniform reaction solution with solute mass percentage of 10 wt%; adding 120 mu L of Karstedt's catalyst (0.001% of the mass of the reaction) tetrahydrofuran solution (the mass fraction of the solution is 2.75 wt%) into the system under the protection of nitrogen; heating to 60 ℃, and carrying out condensation reflux reaction for 18.8h under stirring; after the reaction, the crude product was taken out, rotary evaporated at 30 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 24 hours to remove the residual solvent.
A PDMS brush-type graft polymer (molecular weight 70000) having a degree of grafting of 20% was prepared.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with solute mass percentage of 25 wt% by using 2.0g of the PDMS brush type graft polymer (molecular weight is 70000), 3.0g of a cross-linking agent V-PDMS-V (molecular weight is 500), 2.0g of silicone oil PDMS (molecular weight is 11000) which does not participate in cross-linking reaction and 13.0g of tetrahydrofuran, adding 400 mu L of tetrahydrofuran solution of Karstedt's catalyst (the mass fraction of the solution is 1.9 wt%), and stirring for 1 hour by ultrasonic to mix uniformly to ensure that the solution is uniform and transparent; and (3) taking a proper amount of solution to be dripped on the surface of a base material, drying the solution at room temperature for 2 hours, then placing the dried solution into a blast drying oven at the temperature of 95 ℃ to be crosslinked and cured for 4 hours to form a film, and preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The static water contact angle of the coating is measured to be 98 degrees, the ice shear strength is measured to be 4.5kPa, and the abrasion resistance times can reach 85 times.
Example 2
1) Synthesis of PDMS brush type graft polymer
8.5g of main chain PDMS-PMHS (molecular weight is 8000) and 6.5g of branched chain PDMS-V (molecular weight is 3750) are mixed with 35.0g of toluene to prepare a uniform reaction solution with solute mass percentage of 30 wt%; 80 μ L of Karstedt's catalyst (0.001% of the mass of the reaction) in toluene (5.0 wt% of the mass of the solution) was added to the system under nitrogen; heating to 75 ℃, and carrying out condensation reflux reaction for 34h under stirring; after the reaction was completed, the crude product was taken out, rotary-evaporated at 55 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 48 hours to remove the residual solvent.
A PDMS brush type graft polymer (molecular weight 104000) having a grafting degree of 50% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
6.0g of the PDMS brush type graft polymer (molecular weight is 104000), 3.0g of a cross-linking agent V-PDMS-V (molecular weight is 8000), 3.0g of silicone oil PDMS (molecular weight is 15000) which does not participate in the cross-linking reaction and 8.0g of toluene are prepared into a solution with solute mass percentage of 60 wt%, 900 mu L of toluene solution of Karstedt's catalyst (the mass fraction of the solution is 3.0 wt%) is added, and the solution is stirred by ultrasound for 1h to be uniformly mixed, so that the solution is uniform and transparent; taking a proper amount of solution to spin on the surface of a base material, drying the solution at room temperature for 2.5 hours, then placing the dried solution into a blowing drying oven at the temperature of 90 ℃ to crosslink and solidify the solution for 3 hours to form a film, and preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The static water contact angle of the coating is measured to be 111 degrees, the ice shear strength is measured to be 9.9kPa, and the abrasion resistance times can reach 50 times.
Example 3
1) Synthesis of PDMS brush type graft polymer
3.0g of main chain PDMS-PMHS (molecular weight is 120000) and 2.0g of branched chain PDMS-V (molecular weight is 7000) are mixed with 5.0g of dichloromethane to prepare a uniform reaction solution with solute mass percentage of 50 wt%; adding 65 μ L of a dichloromethane solution (solution mass fraction is 5.0 wt%) of Karstedt's catalyst (0.001% of the mass of the reaction) into the system under the protection of nitrogen; heating to 90 ℃, and carrying out condensation reflux reaction for 10 hours under stirring; after the reaction, the crude product was taken out, rotary evaporated at 30 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 24 hours to remove the residual solvent.
A PDMS brush-type graft polymer (molecular weight 200000) having a degree of grafting of 33.3% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with solute mass percentage of 32 wt% by using 9.5g of the PDMS brush type graft polymer (molecular weight is 200000), 4.5g of a cross-linking agent V-PDMS-V (molecular weight is 20000), 2.0g of silicone oil PDMS (molecular weight is 15266) which does not participate in cross-linking reaction and 34.0g of dichloromethane, adding 250 mu L of dichloromethane solution of Karstedt's catalyst (the mass percentage of the solution is 4.0 wt%), and stirring by ultrasonic for 1.5h to mix uniformly to ensure that the solution is uniform and transparent; and (3) spraying a proper amount of solution on the surface of a base material, drying at room temperature for 4 hours, then placing the base material into a blast drying oven at the temperature of 70 ℃, and performing crosslinking curing for 4.5 hours to form a film, thus preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The static water contact angle of the coating is measured to be 98 degrees, the ice shear strength is measured to be 6.2kPa, and the abrasion resistance times can reach 70 times.
Example 4
1) Synthesis of PDMS brush type graft polymer
2.0g of main chain PDMS-PMHS (molecular weight is 4000), 3.0g of branched chain PDMS-V (molecular weight is 500) and 45.0g of toluene are mixed to prepare a uniform reaction solution with solute mass percentage of 10 wt%; adding 120 mu L of Karstedt's catalyst (0.001% of the mass of the reaction) in toluene (0.5 wt% of the mass of the solution) into the system under the protection of nitrogen; heating to 70 ℃, and carrying out condensation reflux reaction for 58h under stirring; after the reaction, the crude product was taken out, rotary evaporated at 50 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 48 hours to remove the residual solvent.
A PDMS brush-type graft polymer (molecular weight 8000) having a degree of grafting of 33.3% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with solute mass percentage of 15 wt% by using 4.0g of the PDMS brush type graft polymer (molecular weight is 8000), 1.5g of a cross-linking agent V-PDMS-V (molecular weight is 500), 2.0g of silicone oil PDMS (molecular weight is 532) which does not participate in cross-linking reaction and 42.5g of toluene, adding 60 mu L of a toluene solution of Karstedt's catalyst (the mass fraction of the solution is 5.0 wt%), and ultrasonically stirring for 1.5h to uniformly mix so as to ensure that the solution is uniform and transparent; the surface of a base material is dip-coated in a proper amount of solution, the solution is dried for 2.5 hours at room temperature, and then the base material is placed into a forced air drying oven at the temperature of 90 ℃ to be crosslinked and cured for 6 hours to form a film, and the lubricating durable organic silicon anti-icing coating is prepared by a two-step method.
The static water contact angle of the coating is measured to be 100 degrees, the ice shear strength is measured to be 4.8kPa, and the abrasion resistance times can reach 63 times.
Example 5
1) Synthesis of PDMS brush type graft polymer
3.0g of main chain PDMS-PMHS (molecular weight 62000), 2.0g of branched chain PDMS-V (molecular weight 7000) and 15.0g of dimethylbenzene are mixed to prepare a uniform reaction solution with the solute mass percentage of 25 wt%; 64 μ L of a xylene solution (solution mass fraction of 2.9 wt%) of Karstedt's catalyst (0.001% of the mass of the reaction) was added to the system under nitrogen; heating to 90 ℃, and carrying out condensation reflux reaction for 34h under stirring; after the reaction was completed, the crude product was taken out, rotary-evaporated at 70 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 48 hours to remove the residual solvent.
A PDMS brush type graft polymer (molecular weight 190000) having a degree of grafting of 50% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with solute mass percentage of 37.5 wt% by using 9.0g of the PDMS brush type graft polymer (molecular weight is 190000), 5.0g of a cross-linking agent V-PDMS-V (molecular weight is 10250), 4.75g of silicone oil PDMS (molecular weight is 30000) which does not participate in cross-linking reaction and 31.25g of xylene, adding 120 mu L of xylene solution of Karstedt's catalyst (the mass fraction of the solution is 1.9 wt%), and stirring with ultrasound for 1h to mix uniformly to ensure that the solution is uniform and transparent; and (3) taking a proper amount of solution to be dripped on the surface of a base material, drying the surface for 1h at room temperature, then placing the base material into a blast drying oven with the temperature of 120 ℃ for crosslinking and curing for 4h to form a film, and preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The static water contact angle of the coating is measured to be 119 degrees, the ice shear strength is measured to be 3.5kPa, and the abrasion resistance times can reach 45 times.
Example 6
1) Synthesis of PDMS brush type graft polymer
8.5g of main chain PDMS-PMHS (molecular weight is 4000), 3.5g of branched chain PDMS-V (molecular weight is 500) and 38.0g of toluene are mixed to prepare a uniform reaction solution with solute mass percentage of 24 wt%; under the protection of nitrogen, 110 μ L of Karstedt's catalyst (0.001% of the mass of the reaction) in toluene (3.0 wt% of the mass of the solution) was added to the system; heating to 80 ℃, and carrying out condensation reflux reaction for 32h under stirring; after the reaction was completed, the crude product was taken out, rotary-evaporated at 64 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 36 hours to remove the residual solvent.
A PDMS brush type graft polymer (molecular weight of 50000) having a degree of grafting of 33.3% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with the solute mass percentage content of 30 wt% by using 2.0g of the PDMS brush type graft polymer (the molecular weight is 50000), 1.0g of a cross-linking agent V-PDMS-V (the molecular weight is 500), 1.0g of silicone oil PDMS (the molecular weight is 7000) which does not participate in the cross-linking reaction and 6.0g of toluene, adding 150 mu L of toluene solution of Karstedt's catalyst (the solution mass percentage is 2.0 wt%), and ultrasonically stirring for 1.5h to uniformly mix so that the solution is uniform and transparent; taking a proper amount of solution to spin on the surface of a base material, drying the solution at room temperature for 2.5 hours, then placing the dried solution into a forced air drying oven at the temperature of 95 ℃ to crosslink and solidify for 4.5 hours to form a film, and preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The static water contact angle of the coating is measured to be 110 degrees, the ice shear strength is measured to be 6.9kPa, and the abrasion resistance times can reach 90 times.
Example 7
1) Synthesis of PDMS brush type graft polymer
Mixing 11.0g of main chain PDMS-PMHS (molecular weight is 62000) and 6.5g of branched chain PDMS-V (molecular weight is 7000) with 32.5g of ethyl acetate to prepare a uniform reaction solution with solute mass percentage of 35 wt%; 126 μ L of Karstedt's catalyst (0.001% of the mass of the reaction) in ethyl acetate (2.5 wt% of the solution) was added to the system under nitrogen; heating to 60 ℃, and carrying out condensation reflux reaction for 17h under stirring; after the reaction was completed, the crude product was taken out, rotary-evaporated at 35 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 36 hours to remove the residual solvent.
A PDMS brush type graft polymer (molecular weight: 80000) having a grafting degree of 50% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with the solute mass percentage content of 30 wt% by using 9.0g of the PDMS brush type graft polymer (the molecular weight is 80000), 4.0g of a cross-linking agent V-PDMS-V (the molecular weight is 10250), 2.0g of silicone oil PDMS (the molecular weight is 532) which does not participate in the cross-linking reaction and 35.0g of ethyl acetate, adding 100 mu L of an ethyl acetate solution of Karstedt's catalyst (the solution mass percentage is 2.0 wt%), and stirring with ultrasound for 2 hours to mix uniformly to ensure that the solution is uniform and transparent; and (3) spraying a proper amount of solution on the surface of a base material, drying at room temperature for 2 hours, then placing the base material into a blast drying oven at the temperature of 70 ℃, and performing crosslinking curing for 3 hours to form a film, thus preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
The static water contact angle of the coating is measured to be 99 degrees, the ice shear strength is measured to be 5.8kPa, and the abrasion resistance times can reach 38 times.
Example 8
1) Synthesis of PDMS brush type graft polymer
4.0g of main chain PDMS-PMHS (molecular weight is 10000) and 4.0g of branched chain PDMS-V (molecular weight is 7000) are mixed with 12.0g of ethyl acetate to prepare a uniform reaction solution with solute mass percentage of 45 wt%; under the protection of nitrogen, 115 μ L of Karstedt's catalyst (0.001% of the mass of the reaction) in ethyl acetate (3.2 wt% of the mass of the solution) was added to the system; heating to 55 ℃, and carrying out condensation reflux reaction for 20h under stirring; after the reaction was complete, the crude product was taken out, rotary evaporated at 35 ℃ to remove the solvent as much as possible, and dried in a vacuum oven for 28h to remove the residual solvent.
A PDMS brush-type graft polymer (molecular weight of 57500) having a degree of grafting of 33.3% was obtained.
2) Preparation of lubricating durable organic silicon anti-icing coating
Preparing a solution with solute mass percentage of 24 wt% by using 5.0g of the PDMS brush type graft polymer (molecular weight is 57500), 5.0g of a cross-linking agent V-PDMS-V (molecular weight is 12000), 2.0g of silicone oil PDMS (molecular weight is 30000) which does not participate in a cross-linking reaction and 38.0g of ethyl acetate, adding 150 mu L of an ethyl acetate solution of Karstedt's catalyst (the mass fraction of the solution is 2.0 wt%), and stirring by ultrasound for 1.5h to mix uniformly to ensure that the solution is uniform and transparent; the surface of a base material is dip-coated in a proper amount of solution, the solution is dried for 2.5 hours at room temperature, and then the base material is placed into a forced air drying oven at the temperature of 70 ℃ to be cross-linked and cured for 5 hours to form a film, and the lubricating durable organic silicon anti-icing coating is prepared by a two-step method.
The static water contact angle of the coating is measured to be 115 degrees, the ice shear strength is measured to be 2.4kPa, and the abrasion resistance times can reach 100 times.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (9)
1. A preparation method of a 'two-step' lubricating durable organic silicon anti-icing coating comprises the following steps: the method comprises the following steps:
1) the PDMS brush type polymer is synthesized by the following components in percentage by weight:
hydrogen-containing polydimethylsiloxane: 4-30 wt%;
monovinyl polydimethylsiloxane: 6-20 wt%;
the balance being solvent;
mixing the main chain hydrogen-containing polydimethylsiloxane and the branched single-ended vinyl polydimethylsiloxane with the solvent according to the mass ratio to prepare a reaction solution; preparing a Karstedt's catalyst accounting for 0.001% of the mass of a reactant into a solution with the mass fraction of 0.5-5 wt% under the protection of nitrogen, and adding the solution into the system; heating to 60-90 ℃, and carrying out condensation reflux reaction for 10-58 h under stirring; taking out the crude product after the reaction is finished, carrying out rotary evaporation at the temperature of 30-70 ℃, removing the solvent as much as possible, and drying in a vacuum drying oven for 24-48 h to remove the residual solvent, thereby obtaining PDMS brush type graft polymers with different grafting degrees;
2) the preparation method of the lubricating durable organic silicon anti-icing coating comprises the following material components in percentage by weight:
polydimethylsiloxane brush type graft polymer: 8-30 wt%;
vinyl-terminated polydimethylsiloxane: 3-15 wt%;
polydimethylsiloxane: 4-15 wt%;
karstedt's catalyst: 0.01-0.12 wt%;
the balance being solvent;
weighing PDMS brush type graft polymer, cross-linking agent double-end vinyl polydimethylsiloxane and additive polydimethylsiloxane according to a determined mass ratio, preparing a reaction solution with a solvent, and ultrasonically stirring for 1-2 h to uniformly mix the solution to make the solution uniform and transparent; coating a proper amount of solution on the surface of a base material, drying the surface for 1-4 hours at room temperature, then placing the base material into a blast drying oven at the temperature of 70-120 ℃ for crosslinking and curing for 3-6 hours to form a film, and preparing the lubricating durable organic silicon anti-icing coating by a two-step method.
2. The method of claim 1, wherein the hydrogenous polydimethylsiloxane has the formula:
wherein m is 5 to 60, n/m is 0 to 324, and the molecular weight is 4000 to 120000.
3. The method of claim 1, wherein the single-ended vinyl polydimethylsiloxane has the formula:
wherein q is 4 to 93, and the molecular weight is 500 to 7000.
4. The process as claimed in claim 1, wherein the polydimethylsiloxane-brush graft polymer has the formula:
wherein x is 0 to 60, y is 0 to 60, z is 4 to 93, p/x is 0 to 533, and the molecular weight is 8000 to 200000.
5. The method of claim 1, wherein the vinyl terminated polydimethylsiloxane has the formula:
wherein r is 4 to 268, and the molecular weight is 500 to 20000.
6. The method of claim 1, wherein the polydimethylsiloxane has the formula:
wherein t is 5 to 404 and the molecular weight is 532 to 30000.
7. The method according to claim 1, wherein the solvent is one of toluene, xylene, methylene chloride, ethyl acetate and tetrahydrofuran.
8. The method according to claim 1, wherein the coating method is a method of dropping, spin coating, spray coating or dip coating.
9. The lubricious durable silicone anti-icing coating prepared in claim 1 is used as a hydrophobic, anti-icing material.
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| CN110396197A (en) * | 2019-08-09 | 2019-11-01 | 雅思汀娜（北京）科技有限公司 | A kind of silicone oil graft polymers and a kind of hydrophobic film coating liuqid and preparation method thereof and a kind of hydrophobic membrane |
| CN110804379B (en) * | 2019-10-22 | 2022-03-04 | 西北工业大学 | Self-lubricating anti-icing material based on dynamic cross-linking system and preparation method thereof |
| CN111393987A (en) * | 2020-04-09 | 2020-07-10 | 天津大学 | Self-repairing lubricating anti-icing coating and preparation method thereof |
| CN114103281B (en) * | 2021-11-24 | 2024-01-19 | 四川中烟工业有限责任公司 | Moisturizing three-layer material and preparation method thereof |
| CN114103320B (en) * | 2021-11-24 | 2024-01-19 | 四川中烟工业有限责任公司 | Application of moisturizing three-layer material in aspect of regulating and controlling humidity of cigar microenvironment |
| CN115181494A (en) * | 2022-08-29 | 2022-10-14 | 清华大学 | Coating and preparation method and application thereof |
| CN116078646B (en) * | 2023-01-03 | 2024-02-09 | 中国科学院上海光学精密机械研究所 | Super-smooth surface modified by silicon-containing nonlinear polymer and preparation and application thereof |
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| CN1820034B (en) * | 2002-10-15 | 2010-10-27 | 埃克森美孚化学专利公司 | Polyolefin adhesive compositions and articles made therefrom |
| JP2005060501A (en) * | 2003-08-11 | 2005-03-10 | Wacker Asahikasei Silicone Co Ltd | Silicone composition for coating |
| US20070289495A1 (en) * | 2004-11-18 | 2007-12-20 | Dow Corning Corporation | Silicone Release Coating Compositions |
| FR2887895B1 (en) * | 2005-06-29 | 2007-10-12 | Rhodia Chimie Sa | SILOXANE-BASED COMPOSITION FOR TIRE MOLDING-DEMOLITION |
| US20070254170A1 (en) * | 2006-04-28 | 2007-11-01 | Hoover Kelly L | Erosion resistant anti-icing coatings |
| US7935465B2 (en) * | 2008-03-03 | 2011-05-03 | Xerox Corporation | Self lubricating photoreceptor |
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| EP2601245A1 (en) * | 2010-08-05 | 2013-06-12 | Biofilm IP, LLC | Cyclosiloxane-substituted polysiloxane compounds, compositions containing the compounds and methods of use thereof |
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| CN104277713B (en) * | 2014-09-11 | 2016-10-26 | 天津大学 | The preparation method of a kind of POSS cross-linking modified fluorine silicon coating and hydrophobic anti-icing application |
| CN104263238B (en) * | 2014-09-11 | 2016-09-07 | 天津大学 | One is fluorinated POSS composite organic coating and preparation method and ice-covering-proof application |
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