Piperazinyl fluorosilicone oil and preparation method thereof

Abstract

The invention relates to piperazinyl fluorosilicone oil and a preparation method thereof, and belongs to the technical field of organic synthesis. Piperazinyl cyclotrisiloxane, 1, 3, 5-trimethyl-1, 3, 5-tri (3, 3, 3-trifluoropropyl) cyclotrisiloxane, hexamethylcyclotrisiloxane, a polar solvent accelerant and water are adopted as raw materials, a reaction is catalyzed by a five-coordination silicon compound catalyst, piperazine groups in the prepared piperazinyl fluorosilicone oil do not have primary amino groups, the piperazinyl fluorosilicone oil is not prone to oxidation and yellowing, and the service life of the piperazinyl fluorosilicone oil is prolonged. The penta-coordinated silicon compound catalyst is high in catalytic reaction activity, few in generated ring bodies and narrow in molecular weight distribution, so that the product has excellent and stable use performance.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and relates to piperazine-based fluorosilicone oil and a preparation method thereof. Background Art

[0002] Fabric finishing agent is a finishing agent applied to fabrics, which can change the surface properties of fabrics and thus give them special functions. Amino silicone oil can give fabrics softness, smoothness, elasticity, wrinkle resistance, antistatic and other properties, and is non-toxic, pollution-free, and environmentally friendly. It has been widely used in the textile industry. When fluorine groups are introduced, it not only has a good darkening effect and saves textile water, but also can make fabrics hydrophobic, oleophobic, antifouling, and antistatic. It is easier to wash than ordinary fabrics, and has good softness, feel, and combing properties.

[0003] However, there are still some limitations in the application of existing aminofluorosilicone oil as a fabric finishing agent. For example, aminofluorosilicone oil is a primary aminofluorosilicone oil, which is easy to oxidize and yellow, causing the fabric to turn yellow. In addition, the commonly used fluorosilicone oil is trifluoropropyl silicone oil, which is easy to form a methyltrifluoropropylsiloxane mixed ring body, affecting the overall performance of the fabric finishing agent. At present, there are three main ways to modify the primary amino group that is easy to oxidize and yellow, namely epoxidation, amidation, and quaternization. Epoxidation modification has a certain degree of randomness, and it is difficult to emulsify after modification, the product viscosity is large, and the improvement effect is not good; amidation can only modify 30-70% of the primary amino groups. If the modification is too large, it will seriously affect its use effect, and the remaining primary amino groups will continue to be oxidized to chromophores; quaternization modification also has the disadvantage of not being able to completely modify the primary amino groups. Therefore, it is necessary to develop an aminofluorosilicone oil that is not easy to yellow and contains less fluorine ring bodies to meet the needs of practical applications. Summary of the invention

[0004] The object of the present invention is to provide a piperazine-based fluorosilicone oil and a preparation method thereof. The piperazine group in the prepared piperazine-based fluorosilicone oil has no primary amino group and is not easily oxidized and yellowed. The five-coordinated silicon compound catalyst has high catalytic reaction activity, produces less ring bodies, and has a narrow molecular weight distribution, so that the product has excellent and stable performance.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing piperazine-based fluorosilicone oil, the preparation method comprising:

[0007] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 10-200 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after reaching the reaction temperature, and the reaction is carried out for 2-24 hours. Hexamethyldisilazane is added to terminate the reaction for 1-4 hours, and the salt is filtered to remove the salt. The pressure is reduced to -0.09--0.1 MPa, the temperature is raised to 150-170°C to remove low boiling points, and the piperazinyl fluorosilicone oil is obtained after cooling.

[0008] Furthermore, the general structural formula of the piperazine trifluoropropyl silicone oil is as follows:

[0009]

[0010] Furthermore, the mass proportion of the m-link is 1-5%, the mass proportion of the n-link is 10-80%, and the mass proportion of the p-link is 15-89%; the viscosity of the piperazine-based fluorosilicone oil at 25° C. is 500-3000 mPa·S.

[0011] Furthermore, the raw materials of the piperazine-based fluorosilicone oil include, by weight, 1 to 5 parts of piperazine-based cyclotrisiloxane, 10 to 80 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 15 to 89 parts of hexamethylcyclotrisiloxane, 30 to 70 parts of a polar solvent promoter, 0.05 to 0.3 parts of water and 0.45 to 5.5 parts of hexamethyldisilazane.

[0012] Furthermore, the preparation method of the piperazinyl cyclotrisiloxane is:

[0013] 100 parts by weight of 1-allylpiperazine, 40-45 parts by weight of trimethylcyclotrisiloxane and 3-5 ppm of Custer platinum catalyst are added into a reactor, and the reaction is carried out at 50-70° C. for 2-3 hours. After the reaction is completed, low molecular weight is removed at 100-120° C. and a pressure of -0.095 to -0.1 MPa, and the piperazinylcyclotrisiloxane is obtained after cooling.

[0014] Furthermore, the structural formula of the piperazinylcyclotrisiloxane is as follows:

[0015]

[0016] Furthermore, the polar solvent promoter is selected from one or more of dimethyl sulfoxide, acetonitrile, tetrahydrofuran, and N,N-dimethylformamide.

[0017] Furthermore, the structural formula of the five-coordinated silicon compound catalyst is as follows:

[0018]

[0019] Furthermore, M in the five-coordinated silicon compound catalyst is selected from C 6 H 5 CH 2 NH(CH 3 ) 2 , C 6 H 5 CH 2 N(CH 3 ) 3 , Na, K.

[0020] Furthermore, the reaction temperature is 50-80°C.

[0021] Beneficial effects of the present invention:

[0022] (1) The present invention adopts piperazine as the amino group. Compared with traditional amino silicone oil, its structure is more stable. The nitrogen atom in the piperazine forms a relatively stable ring structure with the adjacent carbon atom, which is not easily oxidized. This stability enables the silicone oil molecules to better adhere to the surface of the fabric during the fabric treatment process, and it is not easy to undergo oxidation reaction and cause yellowing when used for a long time and exposed to air, thereby improving the durability of the fabric.

[0023] (2) The present invention adopts a five-coordinated silicon compound catalyst, which can promote the reaction of raw materials such as piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane and hexamethylcyclotrisiloxane, so that the molecular weight distribution of the generated silicone oil is more concentrated, and the cyclic siloxane polymer produced is less, thereby improving the yield of the product; when treating fabrics, silicone oil with a narrow molecular weight distribution can be more evenly attached to the surface of the fabric to form a more uniform protective film, thereby improving the performance and use effect of the fabric. DETAILED DESCRIPTION

[0024] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0025] Example 1

[0026] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0027] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 10 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added to react for 24 hours after the reaction temperature reaches 50°C, hexamethyldisilazane is added to terminate the reaction for 4 hours, the salt is filtered to remove the salt, the pressure is reduced to -0.09 MPa, the temperature is raised to 170°C to remove low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 2370 mPa·S.

[0028] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 1 part of piperazine-based cyclotrisiloxane, 10 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 89 parts of hexamethylcyclotrisiloxane, 30 parts of polar solvent promoter, 0.05 parts of water and 0.45 parts of hexamethyldisilazane.

[0029] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0030] 100 parts by weight of 1-allylpiperazine, 40 parts by weight of trimethylcyclotrisiloxane and 3 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 70° C. for 3 hours. After the reaction was completed, low molecular weight was removed at 100° C. and a pressure of -0.1 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0031] The polar solvent promoter in this embodiment is dimethyl sulfoxide.

[0032] In the five-coordinated silicon compound catalyst of this embodiment, M is C 6 H 5 CH 2 NH(CH 3 ) 2 .

[0033] Example 2

[0034] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0035] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 50ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added to react for 12h after the reaction temperature reaches 60°C, hexamethyldisilazane is added to terminate the reaction for 3h, the salt is filtered to remove the salt, the pressure is reduced to -0.1MPa, the temperature is raised to 150°C to remove the low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 2160mPa·S.

[0036] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 5 parts of piperazine-based cyclotrisiloxane, 80 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 15 parts of hexamethylcyclotrisiloxane, 50 parts of polar solvent promoter, 0.1 parts of water and 1.25 parts of hexamethyldisilazane.

[0037] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0038] 100 parts by weight of 1-allylpiperazine, 45 parts by weight of trimethylcyclotrisiloxane and 5 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 50° C. for 2 hours. After the reaction was completed, low molecular weight was removed at 120° C. and a pressure of -0.095 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0039] The polar solvent promoter in this embodiment is acetonitrile.

[0040] In the five-coordinated silicon compound catalyst of this embodiment, M is C 6 H 5 CH 2 N(CH 3 ) 3 .

[0041] Example 3

[0042] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0043] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 100 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after the reaction temperature reaches 70°C, and the reaction is carried out for 6 hours. Hexamethyldisilazane is added to terminate the reaction for 2 hours, and the salt is filtered to remove the salt, the pressure is reduced to -0.095 MPa, the temperature is raised to 160°C to remove the low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 1120 mPa·S.

[0044] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 5 parts of piperazine-based cyclotrisiloxane, 10 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 85 parts of hexamethylcyclotrisiloxane, 70 parts of polar solvent promoter, 0.2 parts of water and 3 parts of hexamethyldisilazane.

[0045] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0046] 100 parts by weight of 1-allylpiperazine, 43 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 60° C. for 2.5 hours. After the reaction was completed, low molecular weight was removed at 110° C. and a pressure of -0.098 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0047] The polar solvent promoter of this embodiment is tetrahydrofuran.

[0048] In the pentacoordinated silicon compound catalyst of this embodiment, M is Na.

[0049] Example 4

[0050] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0051] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 200 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added to react for 2 hours after the reaction temperature reaches 80°C, hexamethyldisilazane is added to terminate the reaction for 1 hour, the salt is filtered to remove the salt, the pressure is reduced to -0.093 MPa, the temperature is raised to 165°C to remove low boiling points, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 730 mPa·S.

[0052] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 1 part of piperazine-based cyclotrisiloxane, 80 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 19 parts of hexamethylcyclotrisiloxane, 70 parts of polar solvent promoter, 0.3 parts of water and 5.5 parts of hexamethyldisilazane.

[0053] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0054] 100 parts by weight of 1-allylpiperazine, 43 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 70° C. for 2 hours. After the reaction was completed, low molecular weight was removed at 110° C. and a pressure of -0.098 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0055] The polar solvent promoter in this embodiment is N,N-dimethylformamide.

[0056] In the pentacoordinated silicon compound catalyst of this embodiment, M is K.

[0057] Example 5

[0058] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0059] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 200 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after the reaction temperature reaches 60°C, and the reaction is carried out for 8 hours. Hexamethyldisilazane is added to terminate the reaction for 2 hours, and the salt is filtered to remove the salt, the pressure is reduced to -0.098 MPa, the temperature is raised to 165°C to remove the low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 1240 mPa·S.

[0060] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 3 parts of piperazine-based cyclotrisiloxane, 50 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 47 parts of hexamethylcyclotrisiloxane, 40 parts of polar solvent promoter, 0.2 parts of water and 2.1 parts of hexamethyldisilazane.

[0061] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0062] 100 parts by weight of 1-allylpiperazine, 43 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 50° C. for 3 hours. After the reaction was completed, low molecular weight was removed at 110° C. and a pressure of -0.098 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0063] The polar solvent promoter in this embodiment is acetonitrile.

[0064] In the five-coordinated silicon compound catalyst of this embodiment, M is C 6 H 5 CH 2 NH(CH 3 ) 2 .

[0065] Example 6

[0066] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0067] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 200 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after the reaction temperature reaches 60°C, and the reaction is carried out for 12 hours. Hexamethyldisilazane is added to terminate the reaction for 4 hours, and the salt is filtered to remove the salt, the pressure is reduced to -0.09 MPa, the temperature is raised to 170°C to remove the low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 520 mPa·S.

[0068] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 1 part of piperazine-based cyclotrisiloxane, 10 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 89 parts of hexamethylcyclotrisiloxane, 50 parts of polar solvent promoter, 0.3 parts of water and 3 parts of hexamethyldisilazane.

[0069] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0070] 100 parts by weight of 1-allylpiperazine, 43 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 50° C. for 3 hours. After the reaction was completed, low molecular weight was removed at 110° C. and a pressure of -0.098 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0071] The polar solvent promoter in this embodiment is dimethyl sulfoxide.

[0072] In the five-coordinated silicon compound catalyst of this embodiment, M is C6 H 5 CH 2 NH(CH 3 ) 2 .

[0073] Example 7

[0074] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0075] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 100 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after the reaction temperature reaches 60°C, and the reaction is carried out for 12 hours. Hexamethyldisilazane is added to terminate the reaction for 3 hours, and the salt is filtered to remove the salt, the pressure is reduced to -0.1 MPa, the temperature is raised to 170°C to remove low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 2930 mPa·S.

[0076] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 5 parts of piperazine-based cyclotrisiloxane, 80 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 15 parts of hexamethylcyclotrisiloxane, 50 parts of polar solvent promoter, 0.05 parts of water and 0.67 parts of hexamethyldisilazane.

[0077] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0078] 100 parts by weight of 1-allylpiperazine, 43 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 50° C. for 3 hours. After the reaction was completed, low molecular weight was removed at 110° C. and a pressure of -0.098 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0079] The polar solvent promoter in this embodiment is acetonitrile.

[0080] In the five-coordinated silicon compound catalyst of this embodiment, M is C 6 H 5 CH 2 N(CH 3 ) 3 .

[0081] Example 8

[0082] A method for preparing piperazine-based fluorosilicone oil, the preparation method of this embodiment is:

[0083] After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 200 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after the reaction temperature reaches 65°C, and the reaction is carried out for 8 hours. Hexamethyldisilazane is added to terminate the reaction for 2 hours, and the salt is filtered to remove the salt, the pressure is reduced to -0.098 MPa, the temperature is raised to 165°C to remove the low-boiling substances, and the piperazinyl fluorosilicone oil is obtained after cooling. The viscosity of the piperazinyl fluorosilicone oil at 25°C is measured to be 1450 mPa·S.

[0084] In parts by weight, the raw materials of the piperazine-based fluorosilicone oil of this embodiment include 3 parts of piperazine-based cyclotrisiloxane, 70 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 27 parts of hexamethylcyclotrisiloxane, 50 parts of polar solvent promoter, 0.2 parts of water and 2 parts of hexamethyldisilazane.

[0085] The preparation method of piperazinylcyclotrisiloxane of the present embodiment is:

[0086] 100 parts by weight of 1-allylpiperazine, 43 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were added into the reactor, and the reaction was carried out at 50° C. for 3 hours. After the reaction was completed, low molecular weight was removed at 110° C. and a pressure of -0.098 MPa, and piperazinylcyclotrisiloxane was obtained after cooling.

[0087] The polar solvent promoter in this embodiment is dimethyl sulfoxide.

[0088] In the five-coordinated silicon compound catalyst of this embodiment, M is C 6 H 5 CH 2 NH(CH 3 ) 2 .

[0089] Comparative Example 1

[0090] On the basis of Example 8, aminoethylaminopropyl trifluoropropyl silicone oil was used to replace piperazine-based fluorosilicone oil, wherein the preparation method of aminoethylaminopropyl trifluoropropyl silicone oil was as follows:

[0091] 3 parts by weight of aminoethylaminopropylcyclotrisiloxane, 70 parts by weight of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 27 parts by weight of hexamethylcyclotrisiloxane, 50 parts by weight of dimethyl sulfoxide and 0.2 parts by weight of water were fully mixed in a reaction generator, and then the temperature was raised to 65°C and M was added. 6 H 5 CH 2 NH(CH3 ) 2 200ppm of silicon compound catalyst was reacted for 8h, 2 parts by weight of hexamethyldisilazane was added and reacted for 2h, after filtering to remove salt, the pressure was reduced to -0.098MPa and the temperature was raised to 165°C to remove low boiling points, and aminoethylaminopropyltrifluoropropyl silicone oil was obtained after cooling, and the viscosity was measured to be 1380mPa·S.

[0092] The preparation method of aminoethylaminopropylcyclotrisiloxane is:

[0093] 100 parts by weight of ethylenediaminopropylene (CAS No. 148054-39-1), 62 parts by weight of trimethylcyclotrisiloxane and 4 ppm of Custer platinum catalyst were reacted at 60°C for 3 hours. After the reaction was completed, low molecular weight was removed at 110°C and a pressure of -0.098 MPa, and aminoethylaminopropylcyclotrisiloxane was obtained after cooling.

[0094] Comparative Example 2

[0095] On the basis of comparative example 1, 3 parts by weight of aminoethylaminopropylcyclotrisiloxane, 70 parts by weight of 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, 27 parts by weight of hexamethylcyclotrisiloxane, 2 parts by weight of hexamethyldisiloxane, and 50 parts by weight of dimethyl sulfoxide were fully mixed in a reaction generator, heated to 110°C, 200 ppm of tetramethylammonium hydroxide catalyst was added, reacted for 4 hours, heated to 140°C to remove the catalyst, reduced pressure to -0.098 MPa, heated to 165°C to remove low boiling points. After cooling, aminoethylaminopropyltrifluoropropyl silicone oil was obtained. The viscosity was measured to be 1440 mPa·S, and the measured

[0096] Comparative Example 3

[0097] On the basis of Example 8, 3 parts by weight of piperazinyl cyclotrisiloxane, 70 parts by weight of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 27 parts by weight of hexamethylcyclotrisiloxane, 2 parts by weight of hexamethyldisiloxane, and 50 parts by weight of dimethyl sulfoxide were fully mixed in a reaction generator, heated to 110°C, 200 ppm of tetramethylammonium hydroxide catalyst was added, reacted for 4 hours, heated to 140°C to remove the catalyst, reduced pressure to -0.098 MPa, heated to 165°C to remove low boiling points. After cooling, piperazinyl trifluoropropyl silicone oil was obtained. The viscosity was measured to be 1480 mPa·S, and the measured

[0098]

[0099] Comparative Example 4

[0100] 100 parts by weight of the fluorosilicone oil product obtained in Comparative Example 2 was added with 1 part by weight of acetic anhydride and stirred at 50° C. for 6 hours to obtain amidated modified aminoethylaminopropyltrifluoropropyl silicone oil.

[0101] Comparative Example 5

[0102] 100 parts by weight of the fluorosilicone oil product obtained in Comparative Example 2 was added with 3 parts by weight of 3-chloro-2-hydroxypropyltrimethylammonium chloride and stirred at 50° C. for 6 hours to obtain quaternary ammonium-modified aminoethylaminopropyltrifluoropropyl silicone oil.

[0103] 1. Take the fluorosilicone oil products of Example 8, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Comparative Example 5 and dissolve them in ethyl acetate at 0.5wt%, soak the white cotton fabric in the solution for 30 seconds, take it out and dry it at 100℃ for 3min, then cure it at 170℃ for 1min, and then place it in a dryer to balance at room temperature for 24h, and then test the water repellency and whiteness of the fabric respectively, where the water repellency is expressed by the contact angle, and the whiteness is tested by the WSB-VI whiteness meter, and then the fabric is aged for 168h at 70℃ and 95% relative humidity to repeat the above indicators. The results are as follows:

[0104] Table 1

[0105]

[0106] As can be seen from Table 1, the fabric treated with the piperazine trifluoropropyl silicone oil prepared by the present invention still maintains good water repellency and whiteness before and after aging.

[0107] 2. Take the fluorosilicone oils in Example 8, Comparative Example 1, Comparative Example 2 and Comparative Example 3 before and after the low-boiling point is removed under reduced pressure, and use GC-MS to test the total mass ratio of the methyltrifluoropropylsiloxane mixed ring body with a relative molecular mass of 1500g / mol. The test results are shown in Table 2 below.

[0108] Table 2

[0109] Before removing low boiling substances / % After removing low boiling substances / % Example 8 6.19 0.09 Comparative Example 1 5.84 0.07 Comparative Example 2 17.86 5.42 Comparative Example 3 18.79 6.71

[0110] As can be seen from Table 2, the ring body contents of Example 8 and Comparative Example 1 before and after the removal of low boiling points are significantly less than those of Comparative Example 2 and Comparative Example 3, indicating that the five-coordinated silicon compound catalyst used in the present invention has high catalytic reaction activity and produces less ring bodies.

[0111] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a piperazine-based fluorosilicone oil, characterized in that: The preparation method is: After piperazinyl cyclotrisiloxane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)cyclotrisiloxane, hexamethylcyclotrisiloxane, polar solvent promoter and water are fully mixed in a reaction generator, 10-200 ppm of a five-coordinated silicon compound catalyst based on the total mass of the mixture is added after reaching the reaction temperature, and the reaction is carried out for 2-24 hours. Hexamethyldisilazane is added to terminate the reaction for 1-4 hours, and the salt is filtered to remove the salt, the pressure is reduced to -0.09--0.1 MPa, the temperature is raised to 150-170°C to remove low boiling points, and the piperazinyl fluorosilicone oil is obtained after cooling.

2. The method for preparing a piperazine-based fluorosilicone oil according to claim 1, characterized in that: The general structural formula of the piperazine-based fluorosilicone oil is shown below:

3. A method for preparing a piperazine-based fluorosilicone oil according to claim 2, characterized in that: The mass proportion of the m-link is 1-5%, the mass proportion of the n-link is 10-80%, and the mass proportion of the p-link is 15-89%; the viscosity of the piperazine-based fluorosilicone oil at 25° C. is 500-3000 mPa·S.

4. The method for preparing a piperazine-based fluorosilicone oil according to claim 1, characterized in that: The raw materials of the piperazine-based fluorosilicone oil include, by weight, 1 to 5 parts of piperazine-based cyclotrisiloxane, 10 to 80 parts of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 15 to 89 parts of hexamethylcyclotrisiloxane, 30 to 70 parts of a polar solvent promoter, 0.05 to 0.3 parts of water and 0.45 to 5.5 parts of hexamethyldisilazane.

5. The method for preparing a piperazine-based fluorosilicone oil according to claim 1, characterized in that: The preparation method of the piperazinyl cyclotrisiloxane is: 100 parts by weight of 1-allylpiperazine, 40-45 parts by weight of trimethylcyclotrisiloxane and 3-5 ppm of Custer platinum catalyst are added into a reactor, and the reaction is carried out at 50-70° C. for 2-3 hours. After the reaction is completed, low molecular weight is removed at 100-120° C. and a pressure of -0.095 to -0.1 MPa, and the piperazinylcyclotrisiloxane is obtained after cooling.

6. The method for preparing a piperazine-based fluorosilicone oil according to claim 5, characterized in that: The structural formula of the piperazinylcyclotrisiloxane is shown below:

7. The method for preparing a piperazine-based fluorosilicone oil according to claim 1, characterized in that: The polar solvent promoter is selected from one or more of dimethyl sulfoxide, acetonitrile, tetrahydrofuran and N,N-dimethylformamide.

8. The method for preparing a piperazine-based fluorosilicone oil according to claim 1, characterized in that: The structural formula of the five-coordinated silicon compound catalyst is as follows:

9. The method for preparing a piperazine-based fluorosilicone oil according to claim 8, characterized in that: The M in the five-coordinated silicon compound catalyst is selected from one of C6H5CH2NH(CH3)2, C6H5CH2N(CH3)3, Na, and K.

10. The method for preparing a piperazine-based fluorosilicone oil according to claim 1, characterized in that: The reaction temperature is 50-80°C.

Images