CN109928891B - Polyamide-linked perfluoropolyether, and preparation method and application thereof - Google Patents
Polyamide-linked perfluoropolyether, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides polyamide-linked perfluoropolyether, which has a structure shown as a formula (I), wherein R 1 、R 2 The definitions of m and n are shown in the specification. The invention also provides a preparation method of the polyamide-linked perfluoropolyether and application of the polyamide-linked perfluoropolyether as a stone protective agent. The polyamide-linked perfluoropolyether prepared by the invention has excellent water-proof, oil-proof and antifouling properties, good solubility in conventional alcohol solvents, strong permeability to stone, good stability, environmental friendliness and no pollution.
Description
Technical Field
The invention relates to the technical field of modified perfluoropolyether compounds and surface treatment, in particular to polyamide-linked perfluoropolyether, a preparation method thereof and application thereof as a stone protective agent.
Background
The stone is a building decoration material widely applied to indoor and outdoor decoration design, curtain wall decoration and public facility construction. Due to the fact that the stone is subjected to wind, rain and sunshine for a long time and is invaded by external liquid (rainwater, mortar, oil stain and the like), the service life and the appearance of the stone are influenced because the stone is prone to generating color stain, white bloom, rusty spot and the like. Protection of the stone is therefore important.
At present, the stone protective agent with the best performance on the market is mainly organic silicon protective agent and fluorine polymer protective agent. The organic silicon protective agent can endow the stone with good weather resistance, air permeability and hydrophobicity; the fluoropolymer protective agent has outstanding heat resistance, weather resistance, water and oil repellency, solvent corrosion resistance and other capabilities, so that the stone can be used in harsh environments.
Chinese patent CN102585232B provides a fluorine-containing organopolysiloxane composition for stone antifouling, and the protective agent has good waterproof, oil-proof, antifouling and aging-resistant performances, but the fluorine-containing alkyl segment used by the protective agent is a perfluorooctyl chain. Perfluorooctyl derivatives are difficult to degrade in the environment, have serious bioaccumulation properties, and have been banned from use in many countries.
The perfluoroether chains have similar properties to perfluoroalkane chains in water and oil repellency, but are not bioaccumulating. U.S. Pat. No. 4,4745009,09,09,09,220 provides a perfluoropolyether having functional groups at the end, such as carboxyl, amino, ester, for protecting stone surfaces, and having good water-proof properties. However, the perfluoropolyether has poor solubility, and a fluorine-containing solvent such as R113 is used as a solvent, while a Freon solvent such as R113 is destructive to the ozone layer.
The existing stone protective agent has the problems of being not environment-friendly, poor in solubility in a conventional solvent, low in permeability and the like. Therefore, it is necessary to develop a stone protective agent with better performance to overcome many defects and shortcomings in the prior art.
Disclosure of Invention
The invention provides polyamide-linked perfluoropolyether, which has good solubility in conventional alcohol solvents, strong permeability to stone, good stability, environmental friendliness and no pollution, and is particularly suitable for being used as a stone protective agent.
In order to achieve the purpose, the technical scheme is as follows:
in one aspect, the present invention provides a polyamide-linked perfluoropolyether having the structure of formula (I):
wherein m is more than or equal to 0, n is more than 0 1 、R 2 Each independently selected from alkylene, arylene, or a combination thereof.
Preferably, the polyamide-linked perfluoropolyether has n of 1 to 60, more preferably n of 1 to 40.
Preferably, m is 0 to 10, more preferably m is 0 to 5, in the polyamide-linked perfluoropolyether.
Preferably, said polyamide-linked perfluoropolyether, R 1 、R 2 Each independently an alkylene group having 1 to 10 carbon atoms; more preferably, R 1 、R 2 Each independently an alkylene group having 1 to 6 carbon atoms, for example: - (CH) 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 4 -、-(CH 2 ) 5 -、-(CH 2 ) 6 -and so on.
It will be further understood by those skilled in the art that the fluorochemical oligomer and polyamide used in the present invention will result in a mixture of compounds and therefore the formula (I) should be understood to mean a mixture of compounds, the numbers n, m in formula (I) representing the number of moles of each corresponding unit in the mixture. Thus, it is apparent that n, m may be non-integer values.
In another aspect, the present invention provides a method for preparing the polyamide-linked perfluoropolyether, comprising the steps of:
1) Reacting the diester with a diamine to provide an amino terminated polyamide having the formula:
wherein R is 1 、R 2 Each independently selected from alkylene, arylene, or combinations thereof, and m is greater than or equal to 0;
2) Reacting the amino-terminated polyamide obtained in the step 1) with perfluoropolyether acyl fluoride in a solvent B to obtain the polyamide-linked perfluoropolyether, wherein the reaction formula is as follows:
wherein n is greater than 0.
Preferably, in the method for preparing the polyamide-linked perfluoropolyether, the feeding molar ratio of the diamine and the diester in the step 1) is 2.
Preferably, in the preparation method of the polyamide-linked perfluoropolyether, the reaction in the step 1) is carried out in the absence of a solvent or in a solvent A, and the solvent A is selected from tetrahydrofuran or acetonitrile.
Preferably, in the method for preparing the polyamide-linked perfluoropolyether, the reaction temperature in the step 1) is 60 to 120 ℃, and more preferably 80 to 100 ℃.
Preferably, the preparation method of the polyamide-linked perfluoropolyether, step 1), further comprises the step of distilling a mixture obtained by reacting a diester with a diamine under reduced pressure at 120-150 ℃ and-0.1 MPa.
Preferably, in the preparation method of the polyamide-linked perfluoropolyether, the feeding molar ratio of the amino-terminated polyamide in the step 2) to the perfluoropolyether acyl fluoride is 1.
Preferably, in the preparation method of the polyamide-linked perfluoropolyether, the reaction in the step 2) is carried out in the presence of an acid-binding agent, and the acid-binding agent is preferably triethylamine.
Preferably, in the method for preparing polyamide-linked perfluoropolyether, the reaction in step 2) is carried out in an anhydrous nitrogen atmosphere.
Preferably, in the preparation method of the polyamide-linked perfluoropolyether, the solvent B in the step 2) is a polar aprotic solvent or a combination of a polar aprotic solvent and a fluorine-containing solvent, wherein the polar aprotic solvent is selected from tetraglyme, diglyme, tetrahydrofuran or acetonitrile, and the fluorine-containing solvent is selected from hexafluoropropylene dimer, hexafluoropropylene trimer, m-ditrifluoromethylbenzene, hexafluorobenzene, dodecafluorocyclohexane, difluorobenzene, trifluorobenzene or trichlorotrifluoroethane.
Further preferably, in the preparation method of the polyamide-linked perfluoropolyether, the polar aprotic solvent in the step 2) is tetrahydrofuran or acetonitrile, and the fluorine-containing solvent is m-bistrifluoromethylbenzene or hexafluorobenzene.
Preferably, in the preparation method of the polyamide-linked perfluoropolyether, the solvent B in the step 2) is subjected to strict anhydrous treatment to ensure that the water content is less than or equal to 100ppm, and the strict anhydrous treatment operation comprises the following steps: calcium hydride was added to the solvent and refluxed at 100 ℃ for 24h.
Further, the invention also provides a stone protective agent containing the polyamide-linked perfluoropolyether.
Preferably, the stone protective agent is directly diluted by the polyamide-linked perfluoropolyether, and the diluent is selected from ethanol, isopropanol or water.
The invention has the beneficial effects that:
compared with the existing stone protective agent, the polyamide-linked perfluoropolyether prepared by the invention has excellent waterproof, oil-proof and antifouling performances, good solubility in conventional alcohol solvents, strong permeability to stone, good stability, environmental friendliness and no pollution; the polyamide-linked perfluoropolyether can be used as a stone protective agent after being diluted by a solvent, the preparation method is simple, the obtained protective agent is convenient to use, and the stone can be effectively protected by directly smearing on the clean stone surface.
Definition of terms
The term "alkylene" as used herein denotes a saturated divalent group derived from a saturated straight, branched or cyclic alkane by removal of two hydrogen atoms. In some embodiments, the alkylene group contains 1 to 10 carbon atoms; in some embodiments, the alkylene group contains 1 to 6 carbon atoms. Examples of this include- (CH) 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 4 -、-(CH 2 ) 6 -and so on.
The term "arylene" as used herein refers to a divalent group resulting from the removal of two hydrogen atoms from an aromatic ring. Wherein "aromatic ring" means monocyclic, bicyclic, and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system contains 3 to 7 atoms. Examples of arylene groups include, but are not limited to:
and so on.
The term "or" as used herein means that alternatives, if appropriate, can be combined, that is, the term "or" includes each listed individual alternative as well as combinations thereof. For example, "the aprotic solvent in step (1) is selected from the group consisting of tetraglyme, diglyme, tetrahydrofuran and acetonitrile" means "the aprotic solvent in step (1) is selected from any one of tetraglyme, diglyme, tetrahydrofuran and acetonitrile, and may be a mixed solvent of any two or more thereof.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of elements, and the 75 th version of the handbook of chemistry and Physics, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", thomas Sorrell, university Science Books, sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, john Wiley & Sons, new York:2007, the entire contents of which are incorporated herein by reference.
The room temperature in the invention refers to the temperature in the range of 25 +/-5 ℃.
The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
Detailed Description
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications based on the inventive concept herein will occur to those skilled in the art and are intended to be included within the scope of the present invention. The starting materials used in the examples are all commercially available.
Example 1
Adding 60.0g of ethylenediamine and 32.0g of diethyl malonate into a 1L reaction kettle with a condensation reflux device, replacing gas in the reaction kettle with nitrogen atmosphere, setting the rotating speed at 200rpm, stirring at room temperature for 10min, heating to 100 ℃, and continuously reacting for 20h at the temperature to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to distill off excess ethylenediamine to give 20.3g of an intermediate amino-terminated polyamide in 79.3% yield, which was found to have an average molecular weight of 320g/mol.
Under the anhydrous and nitrogen atmosphere, adding 20.3g of the obtained intermediate, 220g of perfluoropolyether acyl fluoride (Mn =1730 g/mol) with double equivalent relative to the intermediate, 200mL of tetrahydrofuran strictly dehydrated and dried and 3mL of triethylamine into a 1L reaction kettle with a condensation reflux device, stirring at the rotating speed of 200rpm, heating to 65 ℃, and reacting at the temperature for 6 hours to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove tetrahydrofuran as a solvent and triethylamine as an acid-binding agent, to obtain 228g of the objective product represented by the formula (I) with a yield of 96.1%.
In the formula (I), R 1 ＝-(CH 2 ) 2 -，R 2 ＝-(CH 2 ) 3 -，m＝1.03，n＝9.42。
Example 2
Adding 60.0g of ethylenediamine and 34.8g of diethyl succinate into a 1L reaction kettle with a condensation reflux device, replacing gas in the reaction kettle with nitrogen atmosphere, setting the rotation speed to 200rpm, stirring at room temperature for 10min, heating to 100 ℃, and continuously reacting at the temperature for 20h to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to distill off excess ethylenediamine to give 21.0g of an intermediate amino-terminated polyamide in 73.9% yield, which was determined to have an average molecular weight of 366g/mol.
Under an anhydrous and nitrogen atmosphere, adding 21.0g of the obtained intermediate, 198g of perfluoropolyether acyl fluoride (Mn =1730 g/mol) with twice equivalent relative to the intermediate, 200mL of tetrahydrofuran strictly dehydrated and dried and 3mL of triethylamine into a 1L reaction kettle with a condensation reflux device, stirring at a rotating speed of 200rpm, heating to 65 ℃, and reacting at the temperature for 6 hours to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove the solvent and the acid-binding agent, to obtain 205g of the objective product represented by the formula (I) in a yield of 94.5%.
In the formula (I), R 1 ＝-(CH 2 ) 2 -，R 2 ＝-(CH 2 ) 4 -，m＝1.14，n＝9.42。
Example 3
Adding 60.0g of ethylenediamine, 40.4g of diethyl adipate and 50mL of acetonitrile into a 1L reaction kettle with a condensation reflux device, replacing gas in the reaction kettle with nitrogen atmosphere, setting the rotating speed at 200rpm, stirring at room temperature for 10min, heating to 85 ℃, and continuously reacting at the temperature for 20h to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to distill off excess ethylenediamine and acetonitrile solvent to afford 22.6g of an intermediate amino-terminated polyamide in 66.4% yield, which was determined to have an average molecular weight of 414g/mol.
Under an anhydrous and nitrogen atmosphere, adding 22.6g of the obtained intermediate, 189g of perfluoropolyether acyl fluoride (Mn =1730 g/mol) with twice equivalent relative to the intermediate, 200mL of tetrahydrofuran strictly dehydrated and dried and 3mL of triethylamine into a 1L reaction kettle with a condensation reflux device, stirring at a rotating speed of 200rpm, heating to 65 ℃, and reacting at the temperature for 6 hours to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove the solvent and the acid-binding agent, to obtain 200.3g of the objective product represented by the formula (I) in a yield of 95.7%.
In the formula (I), R 1 ＝-(CH 2 ) 2 -，R 2 ＝-(CH 2 ) 6 -，m＝1.08，n＝9.42。
Example 4
Adding 88.0g of 1, 4-butanediamine, 32.0g of diethyl malonate and 50mL of acetonitrile into a 1L reaction kettle with a condensation reflux device, replacing gas in the reaction kettle with nitrogen atmosphere, setting the rotating speed at 200rpm, stirring at room temperature for 10min, heating to 85 ℃, and continuing to react at the temperature for 20h to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove excess ethylenediamine and acetonitrile solvent to give 23.1g of intermediate amino terminated polyamide in 74.0% yield, which was determined to have an average molecular weight of 289g/mol.
Under the anhydrous and nitrogen atmosphere, adding 23.1g of the obtained intermediate, 277g of perfluoropolyether acyl fluoride (Mn =1730 g/mol) with double equivalent relative to the intermediate, 200mL of acetonitrile strictly dehydrated and dried, and 3mL of triethylamine into a 1L reaction kettle with a condensation reflux device, stirring at the rotation speed of 200rpm, heating to 85 ℃, and reacting at the temperature for 6 hours to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove the solvent and the acid-binding agent, to obtain 292.3g of the objective product represented by the formula (I) in a yield of 94.5%.
In the formula (I), R 1 ＝-(CH 2 ) 4 -，R 2 ＝-(CH 2 ) 3 -，m＝0.3，n＝9.42。
Example 5
Adding 60g of ethylenediamine and 32g of diethyl malonate into a 1L reaction kettle with a condensation reflux device, replacing gas in the reaction kettle with nitrogen atmosphere, setting the rotating speed to 200rpm, stirring at room temperature for 10min, heating to 100 ℃, and continuing to react for 20h at the temperature to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to distill off excess ethylenediamine to give 20.3g of an intermediate amino-terminated polyamide in 79.3% yield, which was found to have an average molecular weight of 320g/mol.
Under anhydrous and nitrogen atmosphere, adding 20.3g of the obtained intermediate, 453g of perfluoropolyether acyl fluoride (Mn =3570 g/mol) with twice equivalent relative to the intermediate, 300mL of acetonitrile dried by strictly removing water, 100mL of m-ditrifluoromethylbenzene and 3mL of triethylamine into a 2L reaction kettle with a condensation reflux device, stirring at the rotation speed of 200rpm, heating to 85 ℃, and reacting at the temperature for 6 hours to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove the solvent and the acid-binding agent, to obtain 434g of the objective product represented by the formula (I) in 92.3% yield.
In the formula (I), R 1 ＝-(CH 2 ) 2 -，R 2 ＝-(CH 2 ) 3 -，m＝1.03，n＝20.5。
Example 6
Adding 60g of ethylenediamine and 32g of diethyl malonate into a 1L reaction kettle with a condensation reflux device, replacing gas in the reaction kettle with nitrogen atmosphere, setting the rotating speed to 200rpm, stirring at room temperature for 10min, heating to 100 ℃, and continuing to react for 20h at the temperature to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to distill off excess ethylenediamine to give 20.3g of an intermediate amino-terminated polyamide in 79.3% yield, which was found to have an average molecular weight of 320g/mol.
Under the anhydrous and nitrogen atmosphere, adding 20.3g of the obtained intermediate, 800g of perfluoropolyether acyl fluoride (Mn =6310 g/mol) with double equivalent relative to the intermediate, 500mL of acetonitrile dried by strictly removing water, 200mL of hexafluorobenzene and 3mL of triethylamine into a 2L reaction kettle with a condensation reflux device, stirring at the rotating speed of 200rpm, heating to 85 ℃, and reacting at the temperature for 6 hours to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove the solvent and the acid-binding agent, to give 717g of the objective product represented by the formula (I) in a yield of 87.6%.
In the formula (I), R 1 ＝-(CH 2 ) 2 -，R 2 ＝-(CH 2 ) 3 -，m＝1.03，n＝37.0。
Example 7 application and Performance testing
The perfluoropolyether connected with the target product polyamide obtained in the embodiments 1 to 6 is prepared into a stone protective agent with the mass percent of 1% by using isopropanol for standby.
Cutting commercially available marble into 100-20mm squares, grinding 6 surfaces by using abrasive cloth, washing by using clear water, degreasing by using butanone, drying in a 75-DEG C oven for 24 hours, dipping the prepared protective agent sample by using a brush, uniformly coating 6 surfaces of the stone, and standing for one week at normal temperature to obtain the treated stone.
The stone treated by the protective agent is subjected to the following performance tests:
(1) Water resistance: the contact angle of the surface of the test stone was measured by a contact angle tester, and the test results are shown in table 1.
(2) Oil and stain repellency: dropping edible oil and blue ink on the upper surface of the test stone, standing at room temperature for 1h, washing with flowing clear water, slightly wiping with soft cloth, drying the surface, observing the surface pollution condition, and taking the sample pollution condition with the most serious pollution as an experimental result. The test results are shown in table 1.
0: the surface of the sample is pollution-free, and the stone is completely free of oil stain traces after being washed;
1: the surface of the sample is slightly polluted, and shallow oil spots exist after the sample is washed;
2: the surface of the sample is seriously polluted, and a large area of dark oil spots are formed after the sample is washed.
(3) Permeability: and (4) flatly cutting the test stone along the direction vertical to the thickness, immersing the section in water, and measuring the thickness of the surface layer which is not wetted by the water to be accurate to mm. The test results are shown in table 1.
(4) Surface discoloration property: the change of the surface color of the stone is visually tested. The test results are shown in table 1.
TABLE 1 Performance test results for stone protectant
| Surface water contact angle | Prevention of oil contamination | Preventing ink contamination | Permeability (mm) | Surface discoloration property | |
| Comparative example | 88° | 2 | 2 | 0 | Without change |
| Example 1 | 136° | 0 | 0 | 3.2 | Without change |
| Example 2 | 131° | 0 | 0 | 3.1 | Without change |
| Example 3 | 128° | 1 | 0 | 2.6 | Is substantially unchanged |
| Example 4 | 132° | 0 | 0 | 2.8 | Without change |
| Example 5 | 144° | 0 | 0 | 2.4 | Is substantially unchanged |
| Example 6 | 142° | 0 | 0 | 2.2 | Is substantially unchanged |
Remarking: the comparative example is stone without coating protective agent.
As can be seen from the data in Table 1, compared with the stone without the protective agent, the stone treated by the protective agent of the invention has obvious water-proof, oil-proof and antifouling properties, and good permeability, and can maintain the original appearance of the stone.
Claims (8)
1. A polyamide-linked perfluoropolyether having the structure of formula (I):
wherein n is 1 to 60, m is 0 to 10 1 、R 2 Each independently an alkylene group having 1 to 10 carbon atoms.
2. A process for preparing the polyamide-linked perfluoropolyether of claim 1 comprising the steps of: 1) Reacting the diester with a diamine to provide an amino terminated polyamide having the formula:
wherein R is 1 、R 2 Each independently an alkylene group having 1 to 10 carbon atoms, and m is 0 to 10;
2) Reacting the amino-terminated polyamide obtained in the step 1) with perfluoropolyether acyl fluoride in a solvent B to obtain the polyamide-linked perfluoropolyether, wherein the reaction formula is as follows:
wherein n is 1 to 60.
3. The method of claim 2, wherein the reaction of step 1) is carried out in the absence of a solvent or in a solvent a selected from tetrahydrofuran or acetonitrile.
4. The method of claim 2, wherein the reaction temperature in step 1) is 60 to 120 ℃.
5. The method for preparing polyamide-linked perfluoropolyether as claimed in claim 2, wherein the diamine to diester feed mole ratio of step 1) is in the range of 2:1 to 10: 1.
6. The method of preparing a polyamide-linked perfluoropolyether of claim 2 wherein the molar ratio of the amino terminated polyamide to the perfluoropolyether acyl fluoride feed in step 2) is 1:2.
7. The method of claim 2, wherein the solvent B of step 2) is a polar aprotic solvent or a combination of a polar aprotic solvent and a fluorine-containing solvent, wherein the polar aprotic solvent is selected from tetraglyme, diglyme, tetrahydrofuran, or acetonitrile; the fluorine-containing solvent is selected from hexafluoropropylene dimer, hexafluoropropylene trimer, m-ditrifluoromethylbenzene, hexafluorobenzene, dodecafluorocyclohexane, difluorobenzene, trifluorobenzene or trichlorotrifluoroethane.
8. A stone protectant comprising the polyamide-linked perfluoropolyether of claim 1.
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| US3876617A (en) * | 1972-04-26 | 1975-04-08 | Montedison Spa | Fluorine-containing elastomeric polyamides and copolyamides and process for their preparation |
| DE2461131A1 (en) * | 1973-12-28 | 1975-07-10 | Montedison Spa | N, N'-BIS-AMINOALKYLAMIDES OF POLYOXA-PERFLUORALKANE-DICARBONIC ACIDS, DERIVATIVES AND METHODS FOR THEIR PRODUCTION |
| CN102307851A (en) * | 2008-12-11 | 2012-01-04 | 3M创新有限公司 | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
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| US8907120B2 (en) * | 2009-12-30 | 2014-12-09 | 3M Innovative Properties Company | Perfluoropolyether-containing compounds with oxalylamino groups |
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| US3876617A (en) * | 1972-04-26 | 1975-04-08 | Montedison Spa | Fluorine-containing elastomeric polyamides and copolyamides and process for their preparation |
| DE2461131A1 (en) * | 1973-12-28 | 1975-07-10 | Montedison Spa | N, N'-BIS-AMINOALKYLAMIDES OF POLYOXA-PERFLUORALKANE-DICARBONIC ACIDS, DERIVATIVES AND METHODS FOR THEIR PRODUCTION |
| CN102307851A (en) * | 2008-12-11 | 2012-01-04 | 3M创新有限公司 | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
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