Fluorine-containing amino silicone oil and preparation method and application thereof
阅读说明：本技术 一种含氟氨基硅油及其制备方法和应用 (Fluorine-containing amino silicone oil and preparation method and application thereof ) 是由 张恒 张永明 于 2019-09-25 设计创作，主要内容包括：本发明属于高分子材料技术领域,具体涉及一种含氟氨基硅油及其制备方法。所述的含氟氨基硅油,其结构式为：本发明通过六氟环氧丙烷齐聚体甲酯化后得到的甲酯衍生物与氨基硅油的氨基反应得到相应的氟醚化氨基硅油,并保留相应的氨值。氟醚化氨基硅油以0.2％的配比对棉织物进行浸轧烘焙后具有比氨基硅油更好的拨水拨油性能。氟醚化氨基硅油涂布于玻璃表面固化后也具有优良的涂层拨水拨油性能。(The invention belongs to the technical field of high polymer materials, and particularly relates to fluorine-containing amino silicone oil and a preparation method thereof. The fluorine-containing amino silicone oil has the structural formula:)
1. The fluorine-containing amino silicone oil is characterized in that: the structural formula is as follows:
wherein: r1Is CH3Or CH2CH3；
R2Containing amino or fluoroamide groups, particularly- (CH)2)a-NH-(CH2)b-NHCORf、-(CH2)a-N(CORf)-(CH2)b-NH2Or- (CH)2)a-N(CORf)-(CH2)b-NHCORfOne or a combination thereof in any proportion;
Rfis CF3CF2CF2O(CFCF3CF2O)n'CFCF3-，n'＝0-40；
R3Is CF3CH2CH2-；
A is CH3OH or-CH ═ CH2；
m is an integer of 0-20, n is an integer of 1-20, and p is an integer of 0-5;
a is an integer of 1 to 10, and b is an integer of 1 to 10.
2. A method for producing the fluorine-containing amino silicone oil according to claim 1, characterized in that: the method comprises the following steps:
1) adding amino silicone oil into a container, adding a solvent, stirring, and heating under the protection of nitrogen;
2) dropwise adding CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2Me or methyl pentafluoropropionate;
3) and after the reaction is finished, removing the solvent and the low-boiling-point substances to obtain the fluorine-containing amino silicone oil.
3. The method for producing a fluoroamino silicone oil according to claim 2, characterized in that: in the step 1), the ammonia value of the amino silicone oil is 0.3-2.0 mmol/g.
4. The method for producing a fluoroamino silicone oil according to claim 2, characterized in that: in the step 1), the solvent is: hydrofluoroether with a boiling point of 40-120 ℃, long-chain alkane with a boiling point of 40-120 ℃, toluene, xylene, tetrahydrofuran or butanone.
5. The method for producing a fluoroamino silicone oil according to claim 2, characterized in that: in the step 1), the temperature rise refers to the temperature rise to 25-120 ℃.
6. The method for producing a fluoroamino silicone oil according to claim 2, characterized in that: in step 2), the CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2The molar amount of Me or methyl pentafluoropropionate is from 10 to 100% of the theoretically calculated molar amount corresponding to the ammonia value.
7. Use of the fluorochemical silicone oil according to claim 1, wherein: used as parting agent, parting agent or fabric water and oil repellent finishing agent.
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to fluorine-containing amino silicone oil and a preparation method thereof.
Background
The amino silicone oil is a basic component specially used for a textile softening finishing agent, and because the polarity of amino is extremely strong, the amino silicone oil can interact with hydroxyl, carboxyl and other groups in fibers to generate extremely strong orientation and adsorption, so that siloxane is directionally arranged on the fibers, namely the film-forming property of the siloxane on the surfaces of the fibers is extremely good. In the later finishing and baking process, the polar groups of the fabric are easy to react with the polar groups in the fibers to generate covalent bonds, so that the treated fabric has better washing fastness. The amino silicone oil is subjected to acylation modification, so that the content of active hydrogen can be reduced, yellowing is inhibited, and the water absorption is reduced. The amino silicone oil has good surface property and lower surface energy, and the release force between the crosslinked reticular resin and the pressure-sensitive adhesive is lower, so that the amino silicone oil can be used as a release agent.
The amino silicone oil is used as a main raw material for release, demolding and fabric water and oil repellent finishing, the effect is good, but the problems of high release force, incomplete demolding or few demolding times, yellowing of the fabric, poor oil repellency and the like exist.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the modified fluorine-containing segment of the fluorine-containing amino silicone oil is a hexafluoroepoxy oligomer, the modified amino silicone oil has low surface energy of 6-7 dynes, and has very good water and oil repellent performance, the oil repellent performance of the modified amino silicone oil is improved compared with that of the amino silicone oil, and the modified amino silicone oil has ideal results in the aspects of release, demolding and fabric finishing.
The invention relates to fluorine-containing amino silicone oil, which has the structural formula:
wherein: r1Is CH3Or CH2CH3；
R2Containing amino or fluoroamide groups, particularly- (CH)2)a-NH-(CH2)b-NHCORf、-(CH2)a-N(CORf)-(CH2)b-NH2Or- (CH)2)a-N(CORf)-(CH2)b-NHCORfOne or a combination thereof in any proportion;
Rfis CF3CF2CF2O(CFCF3CF2O)n'CFCF3-，n'＝0-40；
R3Is CF3CH2CH2-；
A is CH3OH or-CH ═ CH2；
m is an integer of 0-20, n is an integer of 1-20, and p is an integer of 0-5;
a is an integer of 1 to 10, and b is an integer of 1 to 10.
The preparation method of the fluorine-containing amino silicone oil comprises the following steps:
1) adding amino silicone oil into a container, adding a solvent, stirring, and heating under the protection of nitrogen;
2) dropwise adding CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2Me or methyl pentafluoropropionate;
3) and after the reaction is finished, removing the solvent and the low-boiling-point substances to obtain the fluorine-containing amino silicone oil.
Wherein:
in the step 1), the ammonia value of the amino silicone oil is 0.3-2.0 mmol/g.
In the step 1), the solvent is: hydrofluoroether with a boiling point of 40-120 ℃, long-chain alkane with a boiling point of 40-120 ℃, toluene, xylene, tetrahydrofuran or butanone.
In the step 1), the temperature rise refers to the temperature rise to 25-120 ℃.
In step 2), the CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2The molar amount of Me or methyl pentafluoropropionate is from 10 to 100% of the theoretically calculated molar amount corresponding to the ammonia value.
The application of the fluorine-containing amino silicone oil is used for a release agent, a release agent or a fabric water and oil repellent finishing agent.
The release material used in the current industrial production develops towards the directions of environmental protection, high temperature resistance, rapid curing, low coating weight and uniformity. The fluorine-containing amino silicone oil is used as a raw material of a release material, can better solve the problem of rapid curing in the presence of a cross-linking agent, has the characteristic of high temperature resistance after cross-linking, can be used as the release agent, can also be used for surface coating treatment, has better low surface energy, has good water and oil repellent performance and scratch resistance, and effectively reduces the coating weight of a coating. The fluorine-containing amino silicone oil is diluted by an organic solvent or a cross-linking agent is added into the solution to be used as a mold release agent to be sprayed on a mold, so that the mold release agent has better mold release capacity and the mold release times are increased. The fluorine-containing amino silicone oil is used as a fabric finishing or fiber treatment material, and the water and oil repellent performance of the fluorine-containing amino silicone oil is obviously improved compared with that of amino silicone oil, and particularly the oil repellent performance of the fluorine-containing amino silicone oil is obviously improved compared with that of the amino silicone oil.
The invention has the following beneficial effects:
according to the invention, hexafluoro epoxy oligomer methyl ester derivative fluorinated modified raw materials are grafted to amino silicone oil to obtain the fluoroethylated amino silicone oil, the contact angle and surface energy tests show that the effect is excellent, the actual water and oil repellent performance tests are carried out on the fluoroethylated amino silicone oil, and the oil repellent performance of the fluoro amino silicone oil is very excellent and the stripping effect is far superior to that of the amino silicone oil.
Drawings
FIG. 1 is a graph showing a comparison of water-repellent and oil-repellent properties before and after modification with amino silicone oil;
the left graph corresponds to 0.2% amino silicone oil solution, and the right graph corresponds to 0.2% fluorine-containing amino silicone oil solution;
in the figure, from top to bottom: water, coffee, soy sauce, vinegar, peanut oil.
Detailed Description
The invention is further described with reference to specific examples.
The starting materials used in the examples are all commercially available except where otherwise indicated.
Example 1
The preparation method of the fluorine-containing amino silicone oil comprises the following specific steps:
1) adding 300g of amino silicone oil (monomer is KH-602) with ammonia value of 0.8 and 800mL of tetrahydrofuran into a 2L three-necked bottle equipped with a mechanical stirring and nitrogen protection device, starting stirring, and heating to reflux under the protection of nitrogen;
2) 30g of methyl pentafluoropropionate is added dropwise, and the reaction is carried out for 8 hours under the reflux condition;
3) after the reaction, the solvent and the reaction by-products were distilled off to obtain 308g of a pentafluoroacetyl-modified amino silicone oil product with a yield of 95% and a colorless viscous oily substance, and the ammonia value was determined to be 0.26.
Example 2
The preparation method of the fluorine-containing amino silicone oil comprises the following specific steps:
1) adding 300g of amino silicone oil (amino monomer is KH-602) with ammonia value of 0.8 and 800mL of tetrahydrofuran into a 3L three-necked flask equipped with a mechanical stirring and nitrogen protection device, starting stirring, and heating to reflux under the protection of nitrogen;
2) dropwise adding CF3CF2CF2OCFCF3CF2OCFCF3COOMe 87g, and reacting for 8 hours under the reflux condition;
3) after the reaction, the solvent and the reaction by-products were distilled off to obtain 321g of fluoroether-modified amino silicone oil product, the yield was 92%, the product was colorless viscous oil, and the ammonia value was determined to be 0.23.
Example 3
The preparation method of the fluorine-containing amino silicone oil comprises the following specific steps:
1) adding 300g of amino silicone oil (amino monomer is KH-602) with ammonia value of 0.5 and 1500mL of toluene into a 2L three-necked bottle equipped with a mechanical stirring and nitrogen protection device, starting stirring, and heating to reflux under the protection of nitrogen;
2) dropwise adding CF3CF2CF2O(CFCF3CF2O)n'CFCF3COOMe (average molecular weight 1600)170g, and reacting for 20 hours under the reflux condition;
3) after the reaction, the solvent and the reaction by-products were distilled off to obtain 455g of fluoroether-modified amino silicone oil product with a yield of 97% in the form of a pale yellow extremely viscous oil with an ammonia value of 0.17.
Example 4
Fiber treatment and water and oil repellent performance test
The fiber treatment method comprises the following steps: and (2) preparing the obtained fluorine-containing amino silicone oil into a solution with the concentration of 0.2% by using hydrofluoroether as a solvent, treating the cotton fabric by adopting a two-dipping and two-rolling process to obtain the cotton fabric subjected to the dip coating, then pre-drying at 80 ℃, and baking at 130 ℃ for 20min to obtain the cotton fabric finished by the fluorine-containing amino silicone oil.
The contact angle test results are shown in table 1.
Table 1 contact angle test results
The test results of the water and oil repellent performance are shown in figure 1.
Example 5
Film surface coating performance test
After the corresponding amino silicone oil is proportioned into 3 percent of hydrofluoroether solution, an anchoring agent and a bridging agent are added for coating, and after the coating is thermally cured with the cleaned glass surface, the contact angle is tested.
Fluorine-containing amino silicone oil
Water/°
CH2I2/°
Hexadecane/°
Amino silicone oil (N ═ 0.8)
117
79
35
Example 1
125
97
79
Example 2
131
115
106
Example 3
136
121
109
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