CN114057609A - Perfluoropolyether type dihydric alcohol and preparation method thereof - Google Patents
Perfluoropolyether type dihydric alcohol and preparation method thereof Download PDFInfo
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- CN114057609A CN114057609A CN202111527385.3A CN202111527385A CN114057609A CN 114057609 A CN114057609 A CN 114057609A CN 202111527385 A CN202111527385 A CN 202111527385A CN 114057609 A CN114057609 A CN 114057609A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses perfluoropolyether diol, which has the following structural formula:
the perfluoropolyether diol of the invention can not only improve the content of fluorine element and reduce the surface energy, but also reduce the cost, and the synthesis method of the compound has simple operation and mild reaction conditions.
Description
Technical Field
The present invention relates to the field of perfluoropolyether glycols. More particularly, the invention relates to perfluoropolyether diol and a preparation method thereof.
Background
It is well known that fluorine has a shielding effect, with the lowest polarizability and the strongest electronegativity of all known elements. These characteristics impart low surface free energy, water and oil repellency, thermal stability, and chemical stability to the fluorochemical. It makes the treated material possess excellent hydrophobicity, heat stability, chemical stability, wear resistance, weather resistance, etc. The application in the field of aqueous polyurethane, the process for synthesizing fluorine-containing aqueous polyurethane is quite mature, researches show that fluorine material modified aqueous polyurethane (WFPU) has a plurality of special properties, such as good water and oil repellency because fluorine atoms are gathered on the surface of a WFPU film, so far, the following methods are generally adopted for modifying polyurethane by utilizing organic fluorine fragments, (1) organic fluorine is used as a blocking agent to modify aqueous polyurethane; (2) synthesizing fluoroalcohol as chain extender by using organic fluorine to modify waterborne polyurethane; (3) reacting organic fluorine and polyisocyanate to prepare hard segment modified waterborne polyurethane; (4) organic fluorine monomer is introduced into acrylic ester to react with the polyurethane prepolymer to modify the waterborne polyurethane. Research shows that the fluorine-containing chain segment can effectively improve the hydrophobicity of the modified polyurethane on the main chain of the polyurethane than the fluorocarbon chain on the side chain, because the fluorine atoms on the side chain can more effectively migrate to the surface of the polyurethane in the film forming process, and the migration of the fluorine atoms on the main chain can be influenced by the rigidity and strong interaction of the main chain.
Fluoride is commonly found on the market as a mono-alcohol as an end-capping agent or as a chain extender glycol attached to the main chain. Fluorine atoms are relatively few in side chains and are expensive.
Therefore, it is important to develop a novel perfluoropolyether diol having fluorine atoms in the side chains.
Disclosure of Invention
To achieve these objects and other advantages in accordance with the present invention, a preferred embodiment of the present invention provides a perfluoropolyether diol characterized by the following structural formula:
wherein R is
Another preferred embodiment of the present invention provides a process for preparing a perfluoropolyether diol comprising the steps of:
the method comprises the steps of carrying out trimethyl reaction by using isophorone diisocyanate, perfluoroalcohols, 2-dimethyl-1, 3-dioxane alcohols and acidic ion exchange resin as raw materials, acetone and methanol as solvents and dibutyltin dilaurate as a catalyst to obtain a target product perfluoropolyether type diol.
In a preferred embodiment of the present invention, the process for producing perfluoropolyether diol comprises mixing isophorone diisocyanate, perfluoroalcohols, 2-dimethyl-1, 3-dioxan alcohols, and acidic ion exchange resin in a mass ratio of (1-2) to 1.
In a preferred embodiment according to the present invention, the process for preparing perfluoropolyether glycols comprises the steps of: dissolving isophorone diisocyanate and dibutyltin dilaurate in acetone to obtain a reactant 1 for later use;
dissolving perfluoroalcohol in acetone to obtain a reactant 2 for later use;
dissolving 2, 2-dimethyl-1, 3-dioxane alcohol in acetone to obtain reactant 3 for later use
Mixing the reactant 1 and the reactant 2, and reacting to obtain an intermediate product 1;
mixing the intermediate product 1 and the reactant 3, and reacting to obtain an intermediate product 2;
and mixing the intermediate product 2 with acidic ion exchange resin and methanol, reacting, and purifying to obtain the target product perfluoropolyether diol.
In a preferred embodiment according to the present invention, the process for preparing perfluoropolyether glycols comprises the steps of:
dissolving 1-2 parts of isophorone diisocyanate and 0.02-0.04 part of dibutyltin dilaurate in acetone to obtain a reactant 1 for later use;
dissolving 1-2 parts of perfluoroalcohol in acetone to obtain a reactant 2 for later use;
dissolving 1-2 parts of 2, 2-dimethyl-1, 3-dioxane alcohol in acetone to obtain a reactant 3 for later use
Mixing the reactant 1 and the reactant 2, and reacting to obtain an intermediate product 1;
mixing the intermediate product 1 and the reactant 3, and reacting to obtain an intermediate product 2;
and mixing the intermediate product 2 with 1-2 parts of acidic ion exchange resin and methanol, reacting, and purifying to obtain the target product perfluoropolyether diol.
In a preferred embodiment according to the present invention, the perfluoropolyether diol is prepared in a process wherein the concentration of dibutyltin dilaurate is 0.1 wt%.
In a preferred embodiment of the present invention, in the preparation method of perfluoropolyether diol, the intermediate product 2 is mixed with 1-2 parts of acidic ion exchange resin and methanol, and the following operations are carried out before:
intermediate 2 was rotary evaporated to remove the solvent acetone.
In a preferred embodiment of the process for preparing perfluoropolyether diols according to the invention, the 2, 2-dimethyl-1, 3-dioxan alcohols in the formula, which require two methyl groups on C2, form acetone after ring opening.
In a preferred embodiment of the process for the preparation of perfluoropolyether glycols according to the invention, the starting materials are dehydrated before use to ensure their absence of water.
In a preferred embodiment of the present invention, in the preparation method of perfluoropolyether diol, 1 to 2 parts of isophorone diisocyanate and 0.02 to 0.04 part of dibutyltin dilaurate are dissolved in acetone to obtain a reactant 1 for standby; dissolving 1-2 parts of perfluoroalcohol in acetone to obtain a reactant 2 for later use; mixing the reactant 1 and the reactant 2, and reacting to obtain an intermediate product 1; all at 45-55 deg.
The invention at least comprises the following beneficial effects: the perfluoropolyether diol of the invention can not only improve the content of fluorine element and reduce the surface energy, but also reduce the cost, and the synthesis method of the compound has simple operation and mild reaction conditions.
The synthesis method has good selectivity, can greatly reduce the variety of byproducts, and has high fluorine content. In addition, the synthesized dihydric fluoroalcohol is unique and novel, and has great prospect in application of hydrophobic materials.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic diagram of the synthesis scheme of perfluoropolyether glycols of the present invention.
FIG. 2 is a hydrogen spectrum of the objective 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl ((5- (((3-hydroxy-2- (hydroxymethyl) propoxy) carbonyl) amino) -1,3, 3-trimethylcyclohexyl) methyl) carbamate in example 1 of the present invention.
FIG. 3 is a hydrogen spectrum of 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ((5- (((3-hydroxy-2- (hydroxymethyl) propoxy) carbonyl) amino) -1,3, 3-trimethylcyclohexyl) methyl) carbamate in example 2 of the present invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
Example 1
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl ((5- (((3-hydroxy-2- (hydroxymethyl) propoxy) carbonyl) amino) -1,3, 3-trimethylcyclohexyl) methyl) carbamate
4.45g of isophorone diisocyanate (IPDI) were dissolved in acetone, dibutyltin dilaurate (0.1% by weight) was added, and the mixture was placed in a three-necked flask equipped with a stirring blade. A mixed solution of acetone and 9.28g of perfluorooctyl ethanol was added to a constant pressure dropping funnel, and slowly dropped into a three-necked flask, N2Reacting for 6h under protection. A mixed solution of 2.92g of (2, 2-dimethyl-1, 3-dioxan-5-yl) methanol and acetone was added through a constant pressure funnel, and the reaction was continued for 6 hours. After the reaction was completed, the solvent acetone was removed by rotary evaporation, and 50ml of methanol and 1.5g of an ion exchange resin (Dowex-50WX2) and the rotary evaporated product were put into a flask and reacted at room temperature for 8 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain a crude product, which was purified by flash chromatography to obtain 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl ((5- (((3-hydroxy-2- (hydroxymethyl) propoxy) carbonyl) amino) -1,3, 3-trimethylcyclohexyl) methyl) carbamate in a yield of 75%. The hydrogen spectrum is shown in FIG. 1.
Elemental analysis (C)26H33F17N2O6,MW＝792.25):calc.(found),C％,39.40(40.52)；H％,4.20(4.62)；N％,3.53(3.63)。
Example 2
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ((5- (((3-hydroxy-2- (hydroxymethyl) propoxy) carbonyl) amino) -1,3, 3-trimethylcyclohexyl) methyl) carbamate
4.45g of isophorone diisocyanate (IPDI) were dissolved in acetone, dibutyltin dilaurate (0.1% by weight) was added, and the mixture was placed in a three-necked flask equipped with a stirring blade. A mixed solution of acetone and 7.28g of perfluorooctyl ethanol was added to a constant pressure dropping funnel, and slowly dropped into a three-necked flask, N2Reacting for 6h under protection. A mixed solution of 2.92g of (2, 2-dimethyl-1, 3-dioxan-5-yl) methanol and acetone was added through a constant pressure funnel, and the reaction was continued for 6 hours. After the reaction was completed, the solvent acetone was removed by rotary evaporation, and 50ml of methanol and 1.5g of an ion exchange resin (Dowex-50WX2) and the rotary evaporated product were put into a flask and reacted at room temperature for 8 hours. After the reaction is finished, the solvent is removed by rotary evaporation to obtain a crude product, and the crude product is purified by a flash chromatographic column to obtain 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ((5- (((3, 3, 6,7,7,8,8, 8-tridecafluorooctyl)-hydroxy-2- (hydroxymethyl) propoxy) carbonyl) amino) -1,3, 3-trimethylcyclohexyl) methyl) carbamate in 75% yield. The hydrogen spectrum is shown in FIG. 2.
The water drop angle of the polyurethane prepared by using the product of example 1 as the main raw material (the addition amount is more than 0.5 percent of the solid content) can reach more than 120 degrees, and the water drop angle of the polyurethane prepared by using the product of example 2 as the main raw material (the addition amount is more than 0.5 percent of the solid content) can reach more than 110 degrees.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. A perfluoropolyether diol is characterized in that the structural formula is as follows:
wherein R is
2. A process for preparing the perfluoropolyether diol of claim 1 comprising the steps of:
isophorone diisocyanate, perfluoroalcohols, 2-dimethyl-1, 3-dioxane alcohols and acidic ion exchange resin are used as raw materials, acetone and methanol are used as solvents, dibutyltin dilaurate is used as a catalyst, and three-step reaction is carried out, so that the target product perfluoropolyether type dihydric alcohol is obtained.
3. The process for producing a perfluoropolyether diol according to claim 2, wherein the mass ratio of isophorone diisocyanate, perfluoroalcohols, 2-dimethyl-1, 3-dioxan alcohols and acidic ion exchange resin is (1-2): (1-2): 1.
4. The process for preparing perfluoropolyether diol of claim 2 comprising the steps of:
dissolving isophorone diisocyanate and dibutyltin dilaurate in acetone to obtain a reactant 1 for later use;
dissolving perfluoroalcohol in acetone to obtain a reactant 2 for later use;
dissolving 2, 2-dimethyl-1, 3-dioxane alcohol in acetone to obtain reactant 3 for later use
Mixing the reactant 1 and the reactant 2, and reacting to obtain an intermediate product 1;
mixing the intermediate product 1 and the reactant 3, and reacting to obtain an intermediate product 2;
and mixing the intermediate product 2 with acidic ion exchange resin and methanol, reacting, and purifying to obtain the target product perfluoropolyether diol.
5. The process for producing a perfluoropolyether diol according to claim 3 or 4, comprising the steps of:
dissolving 1-2 parts of isophorone diisocyanate and 0.02-0.04 part of dibutyltin dilaurate in acetone to obtain a reactant 1 for later use;
dissolving 1-2 parts of perfluoroalcohol in acetone to obtain a reactant 2 for later use;
dissolving 1-2 parts of 2, 2-dimethyl-1, 3-dioxane alcohol in acetone to obtain a reactant 3 for later use
Mixing the reactant 1 and the reactant 2, and reacting to obtain an intermediate product 1;
mixing the intermediate product 1 and the reactant 3, and reacting to obtain an intermediate product 2;
and mixing the intermediate product 2 with 1-2 parts of acidic ion exchange resin and methanol, reacting, and purifying to obtain the target product perfluoropolyether diol.
6. The process for preparing perfluoropolyether diol of claim 5 wherein the concentration of dibutyltin dilaurate is 0.1 wt%.
7. The process for preparing perfluoropolyether diols according to claim 5 wherein the mixing of intermediate 2 with 1 to 2 parts of acidic ion exchange resin and methanol is preceded by the following steps:
intermediate 2 was rotary evaporated to remove the solvent acetone.
8. The process for producing perfluoropolyether diol according to claim 2, wherein the 2, 2-dimethyl-1, 3-dioxan alcohols have two methyl groups at C No. 2 and form acetone after ring opening.
9. The process for preparing perfluoropolyether glycols of claim 2 wherein the starting materials are dehydrated before use to ensure that they are anhydrous.
10. The method of preparing perfluoropolyether diol according to claim 2, wherein 1-2 parts of isophorone diisocyanate and dibutyltin dilaurate are dissolved in acetone to obtain reactant 1 for use; dissolving 1-2 parts of perfluoroalcohol in acetone to obtain a reactant 2 for later use; mixing the reactant 1 and the reactant 2, and reacting to obtain an intermediate product 1; all at 45-55 deg.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116425940A (en) * | 2023-03-13 | 2023-07-14 | 南京大学 | Perfluoropolyether block high polymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116425940A (en) * | 2023-03-13 | 2023-07-14 | 南京大学 | Perfluoropolyether block high polymer and preparation method and application thereof |
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