Perfluoropolyether polyol and preparation method thereof

Abstract

The invention belongs to the field of fluorine-containing ether compounds, and particularly relates to perfluoropolyether polyol and a preparation method thereof, the perfluoropolyether polyol has a structure shown as R4-R3-R2-R1-R '2-R3-R4, R1 is a perfluoropolyether chain, R2 is a perfluoropolyether chain, R3 is a perfluoropolyether chain, and R4 is a perfluoropolyether chain. R2 is-O-CF2-CH2-(CH2CH2O) x-, R '2 is-CF2-CH2-(OCH2CH2) y-, and x or y represents the same or different average polymerization degrees and ranges from 0 to 50; r3 is a divalent linking group for connecting R4 and R2 or R4 and R '2 through an etherified alkyl group; and R4 is a trihydroxy alkane group containing a tertiary amine group. The resin prepared by taking the perfluoropolyether polyol provided by the invention as a cross-linking agent shows excellent base material adhesive force after being cured to form a film, and meanwhile, the durability and reliability of a coating are remarkably enhanced.

Description

Technical Field

[0001] The present invention belongs to the field of fluorinated ether compounds, and particularly relates to a perfluoropolyether polyol and a preparation method thereof. Background Art

[0002] Perfluoropolyethers are compounds widely used in lubricants or coating agents. It is well known that derivatives with terminal group -CH 2 OH have a wide range of uses. Among them, Ausimont Company (New fluorinated thermoplastic elastomers. J.Appl. Polym. Sci. 1996;59:311-327.) disclosed its structure: HO-CH 2 CF 2 O-(CF 2 CF 2 O) m -(CF 2 O) n -CF 2 -CH 2 -OH where m, n represent integers ≥ 1, and m / n = 0.9 - 1.1.

[0003] As an important member of the perfluoropolyether series, the functional derivatives of the reactive end groups of perfluoropolyether alcohols have been favored by many researchers for a long time. By utilizing the reaction activity of the end groups of perfluoropolyether alcohols, a wide variety of perfluoropolyether polyol structures have been creatively prepared.

[0004] For example, CN101878249A proposes to react a ternary alcohol with at least one protected two - hydroxyl functional group and one free - hydroxyl group with an activator. Then, the activated protected ternary alcohol is reacted with a perfluoropolyether polyol, and then a perfluoropolyether tetrol or even a perfluoropolyether octol is generated through a de - protection method. This patent prepares perfluoropolyether tetrol and octol by reacting a specific ternary alcohol with a perfluoropolyether polyol and de - protecting, and the structure and properties of its products are restricted by the starting materials and reaction steps.

[0005] Chinese Patent Documents CN118201983A and CN118382611A introduce the structures of various perfluoropolyether polyol derivatives and their applications in magnetic recording media. However, these synthetic routes are long, with a large number of side reactions, and the post-treatment process is complex, making the overall synthesis difficult. Moreover, they are only applicable to the preparation of perfluoropolyether polyols with relatively small molecular weights, and the synthesis of perfluoropolyether polyols with large molecular weights is even more difficult, limiting their applications. In addition, due to the relatively strong molecular chain rigidity and relatively lack of polar functional groups of perfluoropolyether alcohols, when participating in film formation as cross-linking agents, they often result in insufficient chemical bonding between the coating and the substrate, and there is a phenomenon of local stress concentration in the curing network. This structural characteristic limits the interfacial adhesion and long-term chemical stability of the coating to a certain extent. Summary of the Invention

[0006] The present invention provides a linear perfluoropolyether polyol and a preparation method thereof to solve the above problems in the prior art.

[0007] To achieve the above object, the present invention adopts the following technical solutions: A perfluoropolyether polyol is represented by the following formula (1), R 4 -R 3 -R 2 -R 1 -R′ 2 -R 3 -R 4 (1) In formula (1), R 1 is a perfluoropolyether chain; R 2 is -O-CF 2 -CH 2 -(CH 2 CH 2 O) x -, R′ 2 is -CF 2 -CH 2 -(OCH 2 CH 2 ) y -, where x or y represents the same or different average degree of polymerization, taking values from 0 to 50; R 3 is a divalent linking group connecting R 4 to R 2 or R 4 to R′ 2 through an ether alkyl group; R 4 is a trihydroxyalkane group containing a tertiary amino group. Preferably, x + y = 1 to 20, and more preferably, x + y = 2 to 9.

[0008] The definition of the average degree of polymerization is: the number of repeating units or structural units contained in each polymer molecule on average in the polymer molecular chain.

[0009] Preferably, R in the formula (1) 1 is any one of the following formulas (2-1) to (2-4): - (CF 2 CF 2 O) n - (CF 2 O) m -(2-1) In formula (2-1), n and m represent the average degree of polymerization, m represents 0 to 20, n represents 0.1 to 20, and m / n = 0.2 to 5.0; - (CF 2 CF 2 CF 2 O) k -CF 2 CF 2 -(2-2) In formula (2-2), k represents the average degree of polymerization, indicating 0.1 to 20; - (CF 2 CF 2 CF 2 CF 2 O) d -CF 2 CF 2 CF 2 -(2-3) In formula (2-3), d represents the average degree of polymerization, indicating 0.1 to 10; - (CF 2 CF(CF 3 )O) r -CF(CF 3 ) -(2-4) In formula (2-4), r represents the average degree of polymerization, indicating 0.1 to 20.

[0010] More preferably, the R 1 is - (CF 2 CF 2 O) n - (CF 2 O) m -, and m / n = 0.9 to 1.1.

[0011] Preferably, the formula R 3 is a group represented by any one of the following formulas (3-1) to (3-5): (3-1); (3-2) f represents an integer from 1 to 20; (3-3) z represents an integer from 1 to 10; (3-4); (3-5).

[0012] Further preferably, R 3 contains a hydroxyl group, and R 3 is preferably a group represented by formulae (3-2) to (3-5).

[0013] Preferably, the formula of R 4 is a terminal group represented by any one of the following formulae (4-1), (4-2), (4-3), and (4-4): (4-1) (4-2) (4-3) (4-4) In formula (4-1), p and q are any same or different integers from 1 to 5; in formula (4-4), b and c are any same or different integers from 1 to 5; in formulae (4-1) to (4-4), there are three hydroxyl groups of any same or different structures connected to a nitrogen atom.

[0014] Preferably, R in the formula (1) 4 contains 3 hydroxyl groups.

[0015] Preferably, the number-average molecular weight of the perfluoropolyether polyol is in the range of 500 to 50,000 g / mol, and further preferably, the number-average molecular weight of the perfluoropolyether polyol is 1,000 to 5,000 g / mol.

[0016] Preferably, the compound of formula (1) is represented by any one of the following formulae A to AD: (A) where m and n represent integers from 1 to 10, and x and y are any integers from 0 to 50; preferably, m / n = 1.1 and x + y = 3.5.

[0017] (B) where m and n represent integers from 1 to 10, and either x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 3.5; (C) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 3.5; (D) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 3.5; (E) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 3.5; (F) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 4; (G) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 4; (H) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 4; (I) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 4; (J) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 4; (K) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 5.25; (L) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 5.25; (M) where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 5.25; (N) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 5.25; (O) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 5.25; (P) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1, x + y = 9, and f = 9; (Q) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1, x + y = 9, and f = 9; (R) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1, x + y = 9, and f = 9; (S) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1, x + y = 9, and f = 9; (T) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1, x + y = 9, and f = 9; (U) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 2; (V) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 2; (W) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 2; (X) Among them, m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 2; (Y) Where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 1.1 and x + y = 2; (Z) Where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 0.92 and x + y = 5.5; (AA) Where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 0.92 and x + y = 5.5; (AB) Where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 0.92 and x + y = 5.5; (AC) Where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50; preferably, m / n = 0.92 and x + y = 5.5; (AD) Where m and n represent integers from 1 to 10, and x or y is any integer from 0 to 50. Preferably, m / n = 0.92 and x + y = 5.5.

[0018] The present invention also provides a method for preparing the above perfluoropolyether polyol, comprising the following steps: (a) Reacting an epoxide having at least one epoxy group and at most one halogenated hydrocarbon with a perfluoropolyether alcohol under basic conditions to form a perfluoropolyether with an epoxy group; The structural formula of the perfluoropolyether alcohol is: HO-R 2 -R 1 -R′ 2 -OH.

[0019] (b) Reacting a diol or triol with a primary or secondary amine under basic conditions with the perfluoropolyether having an epoxy group in step (a) to carry out a ring-opening reaction to form a perfluoropolyether polyol with an amino group, i.e., formula (1).

[0020] This method can manufacture end groups functionalized with polyols, and the reaction activity of each step is good, with fewer side reactions and by-products, and the post-treatment is simple and convenient.

[0021] Preferably, the epoxide in step (a) is selected from one of epichlorohydrin, diallyl ether oxide, and ethylene glycol diglycidyl ether. Further preferably, non-limiting examples of the compound having at least one epoxyethyl group and at most one halogenated hydrocarbon are: Epichlorohydrin having the following formula: (5-1); Diglycidyl ether having the following formula: (5-2); Ethylene glycol diglycidyl ether having the following formula: (5-3); Polyethylene glycol diglycidyl ether having the following formula: (5-4), The value range of f is 1 to 20, and preferably f is 9; 1,4-Butanediol diglycidyl ether having the following formula: (5-5); 1,6-Hexanediol diglycidyl ether having the following formula: (5-6); Neopentyl glycol diglycidyl ether having the following formula: (5-7); 1,4-Bis[(glycidyloxy)methyl]cyclohexane having the following formula (5-8).

[0022] Preferably, the basic condition in step (a) is: carried out in the presence of a base soluble in the reaction medium. The base is potassium tert-butoxide, sodium hydroxide or potassium hydroxide. Further preferably, an organic base and preferably potassium tert-butoxide are preferred when the hydroxyl group reacts with the epoxy group, and an inorganic base and preferably NaOH or KOH are preferred when the hydroxyl group reacts with the halogenated hydrocarbon.

[0023] Preferably, step (a) is carried out in a mixed solvent of a fluorinated solvent and a non-fluorinated solvent.

[0024] The non-fluorinated solvent is one of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and preferably diethylene glycol dimethyl ether. The fluorinated solvent in this step is used to dissolve perfluoropolyether alcohol and reduce the viscosity of the reaction system, and is selected from one or more of 3M-7100, meta-trifluorotoluene, perfluorohexane, HT-110, and preferably 3M-7100.

[0025] Preferably, in step (a), the molar ratio of the epoxide to the perfluoropolyether alcohol is 2 to 20:1, the reaction temperature is 50 to 150 °C, and the reaction time is 5 to 80 h. More preferably, the molar ratio of the epoxide to the perfluoropolyether alcohol is 10 to 15:1, the reaction temperature is 70 to 100 °C, and the reaction time is 18 to 25 h. The addition amount of the base is 0.5 to 10 wt% of the perfluoropolyether alcohol. More preferably, the addition amount of the base is 2 to 7 wt%.

[0026] Preferably, after the reaction in step (a) is completed, the reaction product is cooled to room temperature, neutralized with an acid, extracted and purified with a fluorinated solvent, concentrated, and then separated and refined using a chromatographic column to obtain a perfluoropolyether with an epoxy group. The fluorinated solvent in this step is selected from one or more of 3M-7200, perfluorobenzene, 1,1,2-trifluorotrichloroethane, and perfluoro(4-methyl-2-pentene), preferably 1,1,2-trifluorotrichloroethane.

[0027] Preferably, non-limiting examples of the compound of a diol or triol with a primary amine or secondary amine used in step (b) are: Diethanolamine having the following formula (6-1); 2-[(Hydroxymethyl)amino]ethanol having the following formula (6-2); 1-(2-Hydroxy-ethylamino)-propan-2-ol having the following formula (6-3); 1,1'-Azanediylbis(2-methylpropan-2-ol) having the following formula (6-4); Diisopropanolamine having the following formula (6-5); Tris(hydroxymethyl)aminomethane having the following formula (6-6).

[0028] More preferably, a diol with a secondary amine is used.

[0029] Preferably, the basic condition in step (b) is: carried out in the presence of a base soluble in the reaction medium. More preferably, when the primary amine or secondary amine reacts with the epoxy group, the organic base triethylamine is preferred. The molar ratio of triethylamine to the perfluoropolyether obtained in step (a) can be between 2 and 10:1.

[0030] Preferably, after the reaction in step (b) is completed, the reaction solution is extracted and purified using a fluorinated solvent, and then purified by silica gel column chromatography to obtain perfluoropolyether polyol. Here, the fluorinated solvent is selected from one or more of 3M-7300, 1,1,2-trifluorotrichloroethane, and 3M-7200, preferably 3M-7300.

[0031] Preferably, in step (b), the molar ratio of the diol or triol with a primary or secondary amine to the perfluoropolyether with an epoxy group is 10-40:1, and the reaction temperature is 55-125 °C.

[0032] More preferably, in step (b), the molar ratio of the diol containing a secondary amine to the perfluoropolyether with an epoxy group is 10-40:1, the reaction temperature is 85-125 °C, and thin-layer chromatography (TLC) is used as an indicator for the end point of the reaction (developer 3M-7300:F113 = 1:10-10:1). More preferably, the mass ratio of the diol containing a secondary amine to the perfluoropolyether with an epoxy group is 0.8:1-1.8:1. The reaction temperature is 85-95 °C.

[0033] Step (b) is generally a two-phase reaction including an organic phase and an organofluorine phase (perfluoropolyether with an epoxy group in the intermediate product). The reactant, the diol or triol with a primary or secondary amine, is the organic phase, and the perfluoropolyether with an epoxy group has poor solubility with the organic phase. Therefore, a phase transfer catalyst can promote the forward progress of the reaction. For example: tetrabutylammonium bromide, tetraalkylammonium hydroxide, tetrabutylammonium hydrogensulfate, tetrabutylammonium fluoride. Preferably tetrabutylammonium bromide. The addition amount of tetrabutylammonium bromide accounts for about 5-20% of the mass of the organofluorine phase.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects or advantages: (1) The present invention focuses on the modification of perfluoropolyether polyol, especially changes the structure of perfluoropolyether polyol, and improves its performance by introducing nitrogen element and increasing the number of hydroxyl groups. The resin prepared as a crosslinking agent shows excellent adhesion to the substrate after curing into a film, and at the same time significantly enhances the durability and reliability of the coating, such as resisting vibration, temperature difference changes, and reducing the risk of corrosion penetration.

[0035] (2) The method of the present invention is more flexible in product structure design, can accurately synthesize perfluoropolyether polyol with specific properties according to specific requirements, and the synthesis method is simple and convenient for post-treatment. Description of the Drawings

[0036] Figure 1 1H-NMR spectrum of compound A'. 1 H-NMR spectrum.

[0037] Figure 21H-NMR spectrum of compound A 1 1H-NMR spectrum.

[0038] Figure 3 1H-NMR spectrum of compound B 1 1H-NMR spectrum.

[0039] Figure 4 1H-NMR spectrum of compound C 1 1H-NMR spectrum.

[0040] Figure 5 1H-NMR spectrum of compound D 1 1H-NMR spectrum.

[0041] Figure 6 1H-NMR spectrum of compound E 1 1H-NMR spectrum.

[0042] Figure 7 1H-NMR spectrum of compound F′ 1 1H-NMR spectrum.

[0043] Figure 8 1H-NMR spectrum of compound K′ 1 1H-NMR spectrum.

[0044] Figure 9 1H-NMR spectrum of compound P′ 1 1H-NMR spectrum.

[0045] Figure 10 1H-NMR spectrum of compound U′ 1 1H-NMR spectrum.

[0046] Figure 11 1H-NMR spectrum of compound Z′ 1 1H-NMR spectrum. Detailed implementation mode

[0047] The present invention will be further specifically described below through examples. In addition, the present invention is not limited to the following examples. The perfluoropolyether alcohol used in the examples of the present invention is prepared by purchasing or referring to CN1031064C and CN100487020C, and other raw materials are all commercially available products.

[0048] Example 1 Step 1: Add HO(CH 2 CH 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O)n (CF 2 O) m CF 2 CH 2 (CH 2 CH 2 O) y 26.0 g of the compound shown (Mn = 2600 g / mol, m / n = 1.1, x + y = 3.5), 18 g of ethylene glycol diglycidyl ether, and 10 mL of t-BuOH were added to 50 mL of a mixed solvent of 3M-7100 and diethylene glycol dimethyl ether. The mixture was stirred at room temperature until homogeneous. Further, 0.9 g of t-BuOK was added, and the reaction was carried out by stirring at 70 °C for 18 h. The resulting reaction product was cooled to 25 °C, neutralized with 0.5 mol / L hydrochloric acid, extracted and purified using the fluorinated solvent 1,1,2-trifluorotrichloroethane, the solution was concentrated, and purified by silica gel column chromatography to obtain 17.1 g of the compound shown as (A′).

[0049] (A′) The structure of the compound (A′) was determined by 1 H-NMR test results, and the NMR spectrum is as Figure 1 shown.

[0050] 1 1H-NMR: δ [ppm] = 5.24~5.11 (2H), 4.72~4.6 (4H), 4.49~4.43 (2H), 3.97~3.85 (2H), 3.37~3.52 (32H), 3.46 - 3.35 (3H), 3.26 - 3.15 (3H).

[0051] Step 2: 5.0 g of the compound synthesized in the first step, 0.5 g of tetrabutylammonium bromide, 4.0 g of diethanolamine, and 1 mL of triethylamine were placed in a 100 mL three-necked round-bottom flask equipped with a condenser and a thermometer. The mixture was stirred and gradually heated to 90 °C and maintained at this temperature until the reaction was carried out for 5 h. The end point of the reaction was indicated by thin-layer chromatography (TLC) (developer 3M-7300:F113 = 10:1). The mixture was extracted with the fluorinated solvent 3M-7300 (3 × 30 mL). The crude product was collected by solvent evaporation and purified by silica gel column chromatography to obtain 3.88 g of product A.

[0052] (A) The structure of the compound (A) was determined by 1 H-NMR test results, and the NMR spectrum is as Figure 2 shown.

[0053] 1H-NMR: δ [ppm] = 5.23~5.13 (2H), 4.50~4.42 (2H), 4.09~3.77 (8H), 3.75~3.51 (42H), 3.49~3.14 (4H), 2.78~2.60 (12H).

[0054] Example 2 5.5 g of diisopropanolamine was used to replace 4.0 g of diethanolamine in Step 2 of Example 1. Otherwise, the same operations as in Example 1 were carried out, and 2.81 g of Product B was obtained.

[0055] (B) where m / n = 1.1 and x + y = 3.5.

[0056] Compound (B) was 1 tested by H-NMR to determine the structure, and the NMR spectrum was as Figure 3 shown.

[0057] 1 H-NMR: δ [ppm] = 5.23~5.13 (2H), 4.50~4.42 (2H), 4.09~3.77 (12H), 3.75~3.29 (34H), 3.26~3.08 (4H), 2.81~2.55 (12H), 1.30~1.07 (12H).

[0058] Example 3 5.0 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used to replace 4.0 g of diethanolamine in Step 2 of Example 1. Otherwise, the same operations as in Example 1 were carried out, and 2.85 g of Product C was obtained.

[0059] (C) where m / n = 1.1 and x + y = 3.5.

[0060] Compound (C) was 1 tested by H-NMR to determine the structure, and the NMR spectrum was as Figure 4 shown.

[0061] 1 H-NMR: δ [ppm] = 5.23~5.13 (2H), 4.50~4.42 (2H), 4.09~3.77 (12H), 3.75~3.35 (40H), 3.25~3.14 (4H), 2.78~2.60 (12H).

[0062] Example 4 Using 8.0 g of 1,1'-azobis(2-methylpropan-2-ol) to replace 4.0 g of diethanolamine in Step 2 of Example 1, and performing the same operations as in Example 1 otherwise, 1.88 g of Product D was obtained.

[0063] (D) where m / n = 1.1 and x + y = 3.5.

[0064] Performing 1 1H-NMR test on compound (D) to determine the structure, and the NMR spectrum is as Figure 5 shown.

[0065] 1 1H-NMR: δ [ppm] = 5.23~5.13 (2H), 4.53~4.42 (2H), 4.11~3.77 (8H), 3.75~3.11 (34H), 2.94~2.8 (4H), 2.78~2.60 (12H), 1.35~1.18 (24H).

[0066] Example 5 Using 7.0 g of 2-[(hydroxymethyl)amino]ethanol to replace 4.0 g of diethanolamine in Step 2 of Example 1, and performing the same operations as in Example 1 otherwise, 2.85 g of Product E was obtained.

[0067] (E) where m / n = 1.1 and x + y = 3.5.

[0068] Performing 1 1H-NMR test on compound (E) to determine the structure, and the NMR spectrum is as Figure 6 shown.

[0069] 1 1H-NMR: δ [ppm] = 5.23~5.13 (2H), 4.50~4.42 (2H), 4.32~4.22 (4H), 4.1~3.79 (4H), 3.98~3.14 (46H), 2.9~2.68 (8H).

[0070] Example 6 Step 1: Add 5 mL of 3 mol / L NaOH solution, 13.4 g of epichlorohydrin, and 50 mL of a mixed solvent of 3M-7100 and diethylene glycol dimethyl ether to a 250 mL reaction flask under an anhydrous and anaerobic N 2 atmosphere, equipped with a condenser reflux tube, a thermometer and a vacuum pump, and stir evenly. Add HO(CH 2 CH 2 O) x CH2 CF 2 O(CF 2 CF 2 O) n (CF 2 O) m CF 2 CH 2 (CH 2 CH 2 O) y OH (Mn = 2400 g / mol, where m / n = 1.1, x + y = 4) 24.0 g was added dropwise slowly and uniformly, and the addition was completed in 3 h. After the addition, it was stirred at low temperature until it became homogeneous. After stirring for two hours, it was heated to 80 °C at a rate of 10 °C / 30 min and reacted for 18 h. The resulting reaction product was cooled to 25 °C, neutralized with 0.5 mol / L hydrochloric acid, extracted and purified using the fluorinated solvent 1,1,2-trifluorotrichloroethane, the solution was concentrated, and purified by silica gel column chromatography to obtain 18.9 g of the compound shown as (F′).

[0071] (F′) The structure of the compound (F′) was determined by 1 1H-NMR test results, and the NMR spectrum is as Figure 7 shown.

[0072] 1 1H-NMR: δ [ppm] = 5.27~5.07 (8H), 4.12~3.93 (4H), 3.77~3.49 (14H), 3.47~3.66 (2H), 3.28~3.14 (2H).

[0073] Step 2: In a 100 mL three-necked round-bottom flask equipped with a condenser and a thermometer, 5.0 g of the compound synthesized in the first step, 0.5 g of tetrabutylammonium bromide, 7.0 g of diethanolamine, and 1 mL of triethylamine were taken. They were mixed and stirred and gradually heated to 90 °C, and maintained at this temperature until the reaction was completed. The end point of the reaction was indicated by thin-layer chromatography (TLC). The mixture was extracted with the fluorinated solvent 3M-7300. The crude product was collected by solvent evaporation and purified by silica gel column chromatography to obtain 4.87 g of the F product.

[0074] (F) where m / n = 1.1 and x + y = 4.

[0075] The structure of the compound (F) was determined by 1 1H-NMR test results.

[0076] 1H-NMR: δ [ppm] = 5.27~5.07 (4H), 4.12~3.93 (4H), 3.88~3.77 (2H), 3.77~3.39 (30H), 2.8~2.59 (12H).

[0077] Example 7 6.0 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 7.0 g of diethanolamine in Step 2 of Example 6. Otherwise, the same operations as in Example 6 were carried out, and 4.85 g of Product G was obtained.

[0078] (G) where m / n = 1.1 and x + y = 4.

[0079] Compound (G) was subjected to 1 H-NMR test to determine the structure.

[0080] 1 H-NMR: δ [ppm] = 5.27~5.07 (4H), 4.33~4.22 (4H), 4.08~3.96 (4H), 3.91~3.78 (2H), 3.75~3.41 (26H), 2.90~2.71 (8H).

[0081] Example 8 7.5 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used instead of 7.0 g of diethanolamine in Step 2 of Example 6. Otherwise, the same operations as in Example 6 were carried out, and 2.85 g of Product H was obtained.

[0082] (H) where m / n = 1.1 and x + y = 4.

[0083] Compound (H) was subjected to 1 H-NMR test to determine the structure.

[0084] 1 H-NMR: δ [ppm] = 5.27~5.07 (8H), 4.12~3.93 (4H), 3.89~3.41 (28H), 3.22~3.10 (2H), 2.79~2.54 (12H), 1.25~1.12 (6H).

[0085] Example 9 8.0 g of 1,1'-azanediyldi(2-methylpropan-2-ol) was used instead of 7.0 g of diethanolamine in Step 2 of Example 6. Otherwise, the same operations as in Example 6 were carried out, and 3.98 g of Product I was obtained.

[0086] (I) where m / n = 1.1 and x + y = 4.

[0087] The structure of compound (I) was determined by 1 1H-NMR test results.

[0088] 1 1H-NMR: δ [ppm] = 5.27~5.07 (8H), 4.12~3.93 (4H), 3.88~3.41 (20H), 2.92~2.83 (4H), 2.78~2.64 (12H), 1.34~1.17 (24H).

[0089] Example 10 7.0 g of diisopropanolamine was used to replace 7.0 g of diethanolamine in Step 2 of Example 6. Otherwise, the same operations as in Example 6 were carried out, and 4.15 g of Product J was obtained.

[0090] (J) where m / n = 1.1 and x + y = 4.

[0091] The structure of compound (J) was determined by 1 1H-NMR test results.

[0092] 1 1H-NMR: δ [ppm] = 5.27~5.07 (14H), 4.09~3.93 (4H), 3.95~3.38 (24H), 3.26~3.07 (4H), 2.81~2.54 (12H), 1.27~1.09 (12H).

[0093] Example 11 Step 1: Add HO(CH 2 CH 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) n (CF 2 O) m CF 2 CH 2 (CH 2 CH 2 O) yOH (Mn = 2400 g / mol, where m / n = 1.1, x + y = 5.25) 24.0 g, 1,4-butanediol diglycidyl ether 21.0 g, and 10 mL of t-BuOH, 50 mL of a mixed solvent of 3M-7100 and diethylene glycol dimethyl ether. Stir at room temperature until homogeneous. Further add 0.9 g of t-BuOK and stir at 70 °C for 25 h for the reaction. Cool the resulting reaction product to 25 °C, neutralize with 0.5 mol / L hydrochloric acid, extract and purify using the fluorinated solvent 1,1,2-trifluorotrichloroethane, concentrate the solution, and purify by silica gel column chromatography to obtain 15.34 g of the compound shown as (K′).

[0094] (K′) Perform 1 1H-NMR test on the compound (K′) to determine the structure, and the NMR spectrum is as Figure 8 shown.

[0095] 1 1H-NMR: δ [ppm] = 5.24~5.11 (4H), 4.10~3.84 (6H), 3.78~3.38 (40H), 3.27~3.11 (4H), 1.71~1.53 (8H).

[0096] Step 2: Take 5.0 g of the compound synthesized in the first step, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer. Mix and stir, and gradually heat to 90 °C and maintain at this temperature until the reaction is complete. The end point of the reaction is indicated by thin-layer chromatography (TLC). Extract the mixture with the fluorinated solvent 3M-7300. The crude product is collected by solvent evaporation and purified by silica gel column chromatography to obtain 4.18 g of the K product.

[0097] (K) where m / n = 1.1 and x + y = 5.25.

[0098] Perform 1 1H-NMR test on the compound (K) to determine the structure.

[0099] 1 1H-NMR: δ [ppm] = 5.24~5.11 (4H), 4.10~3.78 (8H), 3.78~3.38 (50H), 3.27~3.09 (2H), 2.80~2.57 (12H), 1.71~1.53 (8H).

[0100] Example 12 Using 4.0 g of 2-[(hydroxymethyl)amino]ethanol instead of 5.0 g of diethanolamine in Step 2 of Example 11, and performing the same operations as in Example 11 otherwise, 3.85 g of Product L was obtained.

[0101] (L) where m / n = 1.1 and x + y = 5.25.

[0102] Performing 1 1H-NMR test on compound (L) to determine the structure.

[0103] 1 1H-NMR: δ [ppm] = 5.27~5.07 (4H), 4.38~4.17 (4H), 4.07~3.78 (8H), 3.78~3.38 (46H), 3.27~3.11 (2H), 2.88~2.72 (8H), 1.71~1.53 (8H).

[0104] Example 13 Using 5.5 g of 1-(2-hydroxy-ethylamino)-propan-2-ol instead of 5.0 g of diethanolamine in Step 2 of Example 11, and performing the same operations as in Example 11 otherwise, 2.99 g of Product M was obtained.

[0105] (M) where m / n = 1.1 and x + y = 5.25.

[0106] Performing 1 1H-NMR test on compound (M) to determine the structure.

[0107] 1 1H-NMR: δ [ppm] = 5.24~5.08 (4H), 4.29~4.14 (4H), 4.10~3.78 (10H), 3.78~3.38 (40H), 3.25~3.11 (2H), 2.90~2.58 (10H), 1.71~1.53 (8H), 1.28~1.09 (6H).

[0108] Example 14 Using 7.0 g of 1,1'-azanediyldi(2-methylpropan-2-ol) instead of 5.0 g of diethanolamine in Step 2 of Example 11, and performing the same operations as in Example 11 otherwise, 1.85 g of Product N was obtained.

[0109] (N) where m / n = 1.1 and x + y = 5.25.

[0110] Perform 1 H-NMR test on compound (N) to determine its structure.

[0111] 1 H-NMR: δ [ppm] = 5.24~5.11 (4H), 4.10~3.84 (8H), 3.78~3.33 (38H), 3.27~3.11 (2H), 3.10~3.03 (2H), 2.94~2.75 (8H), 2.38~2.26 (2H), 1.68~1.53 (8H), 1.53~1.41 (12H), 1.32~1.22 (12H).

[0112] Example 15 Use 6.0 g of diisopropanolamine to replace 5.0 g of diethanolamine in Step 2 of Example 11. Otherwise, perform the same operations as in Example 11 to obtain 2.85 g of product O.

[0113] (O) where m / n = 1.1 and x + y = 5.25.

[0114] Perform 1 H-NMR test on compound (O) to determine its structure.

[0115] 1 H-NMR: δ [ppm] = 5.24~5.11 (4H), 4.57~4.37 (2H), 4.10~3.80 (10H), 3.78~3.42 (38H), 3.38~3.25 (2H), 3.125~3.13 (2H), 3.04~2.91 (2H), 2.90~2.79 (4H), 2.79~2.65 (4H), 1.71~1.55 (8H), 1.45~1.32 (6H), 1.28~1.12 (6H).

[0116] Example 16 Step 1: Add HO(CH 2 to a 250 mL flask equipped with a condenser reflux tube, a thermometer and a vacuum pump under an anhydrous and anaerobic N 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) n (CF 2 O) m CF 2 CH 2 (CH2 CH 2 O) y OH (Mn = 1550 g / mol, where m / n = 1.1, x + y = 9) 15.5 g, polyethylene glycol glycidyl ether (550 g / mol) 55 g, and t-BuOH 10 mL were added to a mixed solvent of 50 mL of 3M-7100 and diethylene glycol dimethyl ether. The mixture was stirred at room temperature until homogeneous. Further, 0.9 g of t-BuOK was added, and the reaction was carried out by stirring at 100 °C for 18 h. The resulting reaction product was cooled to 25 °C, neutralized with 0.5 mol / L hydrochloric acid, extracted and purified using the fluorinated solvent 1,1,2-trifluorotrichloroethane, the solution was concentrated, and purified by silica gel column chromatography to obtain 11.2 g of the compound shown as (P′).

[0117] (P′) The structure of the compound (P′) was determined by 1 H-NMR test results, and the NMR spectrum is as Figure 9 shown.

[0118] 1H-NMR: δ [ppm] = 5.28~5.07 (16H), 4.09~3.81 (4H), 3.76~3.37 (98H), 3.27~3.16 (4H), 2.5~2.30 (2H).

[0119] Step 2: 5.0 g of the compound synthesized in the first step, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine were taken in a 100 mL three-necked round-bottom flask equipped with a condenser and a thermometer. The mixture was stirred and gradually heated to 90 °C and maintained at this temperature until the reaction was complete. The end point of the reaction was indicated by thin-layer chromatography (TLC). The mixture was extracted with the hydrofluoroether solvent 3M-7300. The crude product was collected by solvent evaporation and purified by silica gel column chromatography to obtain 2.88 g of the P product.

[0120] (P) where m / n = 1.1, x + y = 9, f = 9.

[0121] The structure of the compound (P) was determined by 1 H-NMR test results.

[0122] 1H-NMR: δ [ppm] = 5.28~5.07 (12H), 4.09~3.96 (2H), 3.96~3.76 (4H), 3.76~3.41 (112H), 3.27~3.16 (2H), 2.77~2.61 (12H), 2.5~2.30 (2H).

[0123] Example 17 Using 6.0 g of 2-[(hydroxymethyl)amino]ethanol to replace 5.0 g of diethanolamine in Step 2 of Example 16, and performing the same operations as in Example 16 otherwise, 1.85 g of Product Q was obtained.

[0124] (Q) where m / n = 1.1, x + y = 9, f = 9.

[0125] Performing 1 1H-NMR test on compound (Q) to determine the structure.

[0126] 1 1H-NMR: δ [ppm] = 5.28~5.07 (12H), 4.31~4.21 (4H), 4.09~3.96 (2H), 3.96~3.76 (4H), 3.76~3.41 (108H), 3.27~3.11 (2H), 2.87~2.72 (8H), 2.5~2.30 (2H).

[0127] Example 18 Using 7.0 g of 1-(2-hydroxy-ethylamino)-propan-2-ol to replace 5.0 g of diethanolamine in Step 2 of Example 16, and performing the same operations as in Example 16 otherwise, 3.05 g of Product R was obtained.

[0128] (R) where m / n = 1.1, x + y = 9, f = 9.

[0129] Performing 1 1H-NMR test on compound (R) to determine the structure.

[0130] 1 1H-NMR: δ [ppm] = 5.28~5.07 (12H), 4.09~3.96 (2H), 3.96~3.76 (6H), 3.76~3.41 (104H), 3.27~3.16 (4H), 2.77~2.61 (12H), 2.5~2.30 (2H), 1.25~1.10 (6H).

[0131] Example 19 Using 9.0 g of 1,1'-azanediyldi(2-methylpropan-2-ol) to replace 5.0 g of diethanolamine in Step 2 of Example 16, and performing the same operations as in Example 16 otherwise, 2.85 g of Product S was obtained.

[0132] (S) where m / n = 1.1, x + y = 9, and f = 9.

[0133] Perform 1 H-NMR tests on the compound (S) to determine its structure.

[0134] 1 H-NMR: δ [ppm] = 5.28~5.07 (12H), 4.09~3.96 (2H), 3.96~3.76 (4H), 3.76~3.41 (100H), 3.27~3.16 (2H), 2.92~2.84 (4H), 2.77~2.61 (12H), 2.5~2.30 (2H), 1.34~1.19 (24H).

[0135] Example 20 Use 8.0 g of diisopropanolamine to replace 5.0 g of diethanolamine in Step 2 of Example 16. Otherwise, perform the same operations as in Example 16 to obtain 2.15 g of Product T.

[0136] (T) where m / n = 1.1, x + y = 9, and f = 9.

[0137] Perform 1 H-NMR tests on the compound (T) to determine its structure.

[0138] 1 H-NMR: δ [ppm] = 5.28~5.07 (12H), 4.09~3.96 (2H), 3.96~3.76 (8H), 3.76~3.35 (100H), 3.27~3.08 (6H), 2.80~2.57 (12H), 2.5~2.30 (2H), 1.25~1.10 (12H).

[0139] Example 21 Step 1: Add HO(CH 2 to a 250 mL flask under an anhydrous and anaerobic N 2 CH 2 O) p CH 2 CF 2 O(CF 2 CF 2 O) n (CF 2 O) m CF 2 CH 2 (CH 2 CH 2O) q 17 g of OH (Mn = 1700 g / mol, where m / n = 1.1 and x + y = 2), 25.6 g of 1,4-bis[(glycidyloxy)methyl]cyclohexane, and 10 mL of t-BuOH were added to a mixed solvent of 50 mL of 3M-7100 and diethylene glycol dimethyl ether. The mixture was stirred at room temperature until homogeneous. Further, 0.9 g of t-BuOK was added, and the reaction was carried out by stirring at 100 °C for 18 h. The resulting reaction product was cooled to 25 °C, neutralized with 0.5 mol / L hydrochloric acid, extracted and purified using the fluorinated solvent 1,1,2-trifluorotrichloroethane, the solution was concentrated, and purified by silica gel column chromatography to obtain 13.12 g of the compound shown as (U′).

[0140] (U′) The structure of compound (U′) was determined by 1 1H-NMR test results, and the NMR spectrum is as Figure 10 shown.

[0141] 1 1H-NMR: δ [ppm] = 4.73~4.58 (4H), 3.97~3.83 (2H), 3.75~3.49 (22H), 3.46~3.39 (2H), 3.39~3.23 (10H), 3.23~3.16 (2H), 1.85~1.68 (4H), 1.49~1.23 (16H).

[0142] Step 2: 5.0 g of the compound synthesized in the first step, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine were placed in a 100 mL three-necked round-bottom flask equipped with a condenser and a thermometer. The mixture was stirred and gradually heated to 90 °C and maintained at this temperature until the reaction was complete. The end point of the reaction was indicated by thin-layer chromatography (TLC). The mixture was extracted with the fluorinated solvent 3M-7300 (3 × 30 mL). The crude product was collected by solvent evaporation and purified by silica gel column chromatography to obtain 2.88 g of U product.

[0143] (U) where m / n = 1.1 and x + y = 2.

[0144] The structure of compound (U) was determined by 1 1H-NMR test results.

[0145] 1H-NMR: δ [ppm] = 4.09~3.95 (4H), 3.97~3.78 (4H), 3.75~3.42 (34H), 3.37~3.29 (8H), 3.23~3.15 (2H), 2.76~2.62 (12H), 1.85~1.68 (4H), 1.49~1.23 (16H).

[0146] Example 22 Using 5.0 g of 2-[(hydroxymethyl)amino]ethanol to replace 5.0 g of diethanolamine in Step 2 of Example 21, and performing the same operations as in Example 21 otherwise, 2.85 g of Product V was obtained.

[0147] (V) where m / n = 1.1 and x + y = 2.

[0148] Performing 1 H-NMR test on compound (V) to determine the structure.

[0149] 1 H-NMR: δ [ppm] = 4.33~4.22 (4H), 4.09~3.95 (4H), 3.97~3.78 (4H), 3.75~3.42 (30H), 3.37~3.29 (8H), 3.23~3.15 (2H), 2.87~2.72 (8H), 1.85~1.68 (4H), 1.49~1.23 (16H).

[0150] Example 23 Using 5.5 g of 1-(2-hydroxy-ethylamino)-propan-2-ol to replace 5.0 g of diethanolamine in Step 2 of Example 21, and performing the same operations as in Example 21 otherwise, 3.85 g of Product W was obtained.

[0151] (W) where m / n = 1.1 and x + y = 2.

[0152] Performing 1 H-NMR test on compound (W) to determine the structure.

[0153] 1 H-NMR: δ [ppm] = 4.09~3.95 (4H), 3.97~3.78 (6H), 3.75~3.42 (28H), 3.37~3.29 (8H), 3.23~3.15 (4H), 2.76~2.62 (12H), 1.85~1.68 (4H), 1.49~1.29 (16H), 1.24~1.15 (6H).

[0154] Example 23 9.0 g of 1,1'-azobis(2-methylpropan-2-ol) was used to replace 5.0 g of diethanolamine in Step 2 of Example 21. Otherwise, the same operations as in Example 21 were carried out, and 2.97 g of Product X was obtained.

[0155] (X) where m / n = 1.1 and x + y = 2.

[0156] The compound (X) was subjected to 1 1H-NMR test to determine the structure.

[0157] 1 1H-NMR: δ [ppm] = 4.09~3.95 (4H), 3.97~3.78 (4H), 3.75~3.42 (22H), 3.37~3.29 (8H), 3.23~3.15 (2H), 2.91~2.84 (4H), 2.76~2.62 (12H), 1.85~1.68 (4H), 1.49~1.23 (16H), 1.30~1.21 (24H).

[0158] Example 25 7.0 g of diisopropanolamine was used to replace 5.0 g of diethanolamine in Step 2 of Example 21. Otherwise, the same operations as in Example 21 were carried out, and 2.95 g of Product Y was obtained.

[0159] (Y) where m / n = 1.1 and x + y = 2.

[0160] The compound (Y) was subjected to 1 1H-NMR test to determine the structure.

[0161] 1 1H-NMR: δ [ppm] = 4.09~3.95 (4H), 3.97~3.78 (8H), 3.75~3.42 (22H), 3.37~3.29 (8H), 3.23~3.11 (6H), 2.78~2.62 (12H), 1.85~1.68 (4H), 1.49~1.23 (16H), 1.23~1.14 (12H).

[0162] Example 26 Step 1: Add HO(CH 2 to a 250 mL flask under an anhydrous and anaerobic N 2 CH 2O) x CH 2 CF 2 O(CF 2 CF 2 O) n (CF 2 O) m CF 2 CH 2 (CH 2 CH 2 O) y OH (Mn = 2300 g / mol, where m / n = 0.92, x + y = 5.5) 23.0 g, neopentyl glycol diglycidyl ether 22.0 g, and 10 mL of t-BuOH, 50 mL of a mixed solvent of 3M-7100 and diethylene glycol dimethyl ether. Stir at room temperature until homogeneous. Further add 0.9 g of t-BuOK and stir at 85 °C for 21 h for the reaction. Cool the resulting reaction product to 25 °C, neutralize with 0.5 mol / L hydrochloric acid, extract and purify using the fluorinated solvent 1,1,2-trifluorotrichloroethane, concentrate the solution, and purify by silica gel column chromatography to obtain 13 g of the compound shown as (Z′).

[0163] (Z′) Perform 1 H-NMR test on the compound (Z′) to determine the structure, and the NMR spectrum is as Figure 11 shown.

[0164] 1 H-NMR: δ [ppm] = 5.23~5.11 (2H), 4.55~4.38 (2H), 4.11~3.85 (6H), 3.77~3.13 (48H), 1.01~0.87 (12H).

[0165] Step 2: In a 100 mL three-necked round-bottom flask equipped with a condenser and a thermometer, take 5.0 g of the compound synthesized in the first step, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine. Mix and stir, and gradually heat to 90 °C and maintain at this temperature until the reaction is complete. The end point of the reaction is indicated by thin-layer chromatography (TLC). Extract the mixture with the fluorinated solvent 3M-7300 (3 × 30 mL). The crude product is collected by solvent evaporation and purified by silica gel column chromatography to obtain 3.88 g of the Z product.

[0166] (Z) where m / n = 0.92 and x + y = 5.5.

[0167] Perform 1The structure was determined by the H-NMR test results.

[0168] 1 H-NMR: δ [ppm] = 5.23~5.11 (2H), 4.52~4.42 (2H), 4.11~3.07 (62H), 2.81~2.58 (12H), 1.01~0.87 (12H).

[0169] Example 27 Using 4.5 g of 2-[(hydroxymethyl)amino]ethanol instead of 5.0 g of diethanolamine in Step 2 of Example 26, and performing the same operations as in Example 26 otherwise, 3.35 g of AA product was obtained.

[0170] (AA) Where m / n = 0.92 and x + y = 5.5.

[0171] For the compound (AA), 1 The structure was determined by the H-NMR test results.

[0172] 1 H-NMR: δ [ppm] = 5.23~5.11 (2H), 4.52~4.42 (2H), 4.36~4.19 (4H), 4.11~3.77 (8H), 3.76~3.12 (50H), 2.91~2.72 (8H), 1.04~0.87 (12H).

[0173] Example 28 Using 5.0 g of 1-(2-hydroxy-ethylamino)-propan-2-ol instead of 5.0 g of diethanolamine in Step 2 of Example 26, and performing the same operations as in Example 26 otherwise, 2.85 g of AB product was obtained.

[0174] (AB) Where m / n = 0.92 and x + y = 5.5.

[0175] For the compound (AB), 1 The structure was determined by the H-NMR test results.

[0176] 1 H-NMR: δ [ppm] = 5.23~5.11 (2H), 4.52~4.42 (2H), 4.11~3.07 (60H), 2.81~2.58 (12H), 1.25~1.12 (6H), 1.01~0.87 (12H).

[0177] Example 29 Using 6.0 g of 1,1'-azobis(2-methylpropan-2-ol) to replace 5.0 g of diethanolamine in Step 2 of Example 26, and performing the same operations as in Example 26 otherwise, 3.05 g of AC product was obtained.

[0178] (AC) Where m / n = 0.92 and x + y = 5.5.

[0179] Performing 1 1H-NMR test on the compound (AC) to determine the structure.

[0180] 1 1H-NMR: δ [ppm] = 5.23~5.11 (2H), 4.52~4.42 (2H), 4.11~3.12 (50H), 2.93~2.83 (4H), 2.81~2.58 (12H), 1.33~1.17 (24H), 1.01~0.87 (12H).

[0181] Example 30 Using 5.5 g of diisopropanolamine to replace 5.0 g of diethanolamine in Step 2 of Example 26, and performing the same operations as in Example 26 otherwise, 3.85 g of AD product was obtained.

[0182] (AD) Where m / n = 0.92 and x + y = 5.5.

[0183] Performing 1 1H-NMR test on the compound (AD) to determine the structure.

[0184] 1 1H-NMR: δ [ppm] = 5.23~5.11 (2H), 4.52~4.42 (2H), 4.11~3.12 (58H), 2.81~2.58 (12H), 1.25~1.12 (12H), 1.01~0.87 (12H).

[0185] Comparative Example 1 Synthesizing the compound shown in the following formula (AE) according to the method described in Japanese Patent Application Laid-Open No. 2018-521183.

[0186] (AE) The mk and nk representing the average degree of polymerization in the formula (AE) are 4 and 5 respectively.

[0187] Comparative Example 2 Synthesize the compound shown by the following formula (AF) according to the method described in CN 101878249B.

[0188] (AF) In formula (AF), it is indicated that the average degree of polymerization p / q = 1.

[0189] Use the above perfluoropolyether polyol as a crosslinking agent to prepare a resin, and test its adhesion grade.

[0190] The resin is prepared according to the following steps. Among them, the hydroxyl equivalent of the perfluoropolyether polyol is the same in different examples and comparative examples: Add polyether diol (650 g / mol) to a reaction kettle with an anhydrous and oxygen-free N 2 atmosphere, equipped with a condenser reflux tube, a thermometer and a vacuum pump. Raise the temperature of the kettle to 120 °C, and pump with the vacuum pump for 2 h. After completion, cool down to room temperature. Slowly dropwise add isophorone diisocyanate, and observe the temperature change in the kettle. It is advisable that the temperature does not exceed 30 °C. After the dropwise addition, stir for 30 min. If the viscosity increases during this period, a solvent can be added to reduce the viscosity. Maintain a heating rate of 10 °C every 30 min, and raise the temperature to 80 °C and then react for 6 h. Cool the temperature of the kettle to room temperature, add perfluoropolyether polyol (dilute the perfluoropolyether polyol to about 10 wt% with a fluorinated solvent), raise the temperature of the kettle to 80 °C and react until the end. During this period, if the viscosity becomes larger, add a mixed solution of a fluorinated solvent and ethyl acetate. The end time is based on the titration of the isocyanate group content. Fill the reactant with nitrogen and store it in a dry place at room temperature.

[0191] Table 1 Indexes and properties of perfluoropolyether polyol

[0192] Test the adhesion of the obtained resin. The adhesion test method is carried out according to the standard of GB / T 9286-1998 "Crosshatch test for adhesion of paint and varnish films". Among them, the test panel is a steel plate, and the coating thickness is 60 μm. The results are shown in Table 1, and the R value is the molar ratio of isocyanate group to hydroxyl group.

[0193] It can be seen from the data in Table 1 that the adhesion test results of Comparative Example 1 and Comparative Example 2 are weak. Compared with Comparative Example 1 or Comparative Example 2, the perfluoropolyether polyol provided by the present invention contains 6 or 8 symmetrically distributed hydroxyl groups, has strong network uniformity, can provide sufficient crosslinking sites and the crosslinking points are concentrated, effectively reducing stress concentration and forming a dense three-dimensional network structure, thereby improving the cohesive strength and adhesion strength of the material. The contained tertiary amine group can improve its wetting performance, enhance the wettability to the surface of metal or oxide layer, make the liquid coating more easily penetrate into the microscopic pores of the substrate, and form a physical anchoring effect. In practical applications, excellent adhesion can directly enhance the durability (resistance to vibration and temperature difference changes) and reliability (reduce the risk of corrosion penetration) of the coating.

[0194] In the present invention, the perfluoropolyether polyol has excellent physical and chemical properties due to its unique molecular structure. These properties enable the synthesized perfluoropolyether polyol to exhibit broad prospects in multiple application fields, including but not limited to high-performance coatings, optical fiber coatings, lubricants, and sealing materials. In addition, considering the development of modern technology, the perfluoropolyether polyol also has potential application value.

Claims

1. A perfluoropolyether polyol, characterized in that It is represented by the following formula (1): R4-R3-R2-R1-R′2-R3-R4(1) Wherein, R1 is a perfluoropolyether chain; R2 is -O-CF2-CH2-(CH2CH2O) x -, R′2 is -CF2-CH2-(OCH2CH2) y -, wherein x or y represents the same or different average degree of polymerization, ranging from 0 to 50; R3 is a divalent linking group connecting R4 and R2 or R4 and R′2 through an ethereal alkyl group; R4 is a trihydroxyalkane group containing a tertiary amine group.

2. The perfluoropolyether polyol according to claim 1, characterized in that R1 in the formula (1) is any one of the following formulas (2-1) to (2-4): - (CF2CF2O) n - (CF2O) m -(2-1) In formula (2-1), n ​​and m represent the average degree of polymerization, m represents 0 to 20, n represents 0.1 to 20, and m / n = 0.2 to 5.0; - (CF2CF2CF2O) k -CF2CF2-(2-2) In formula (2-2), k represents the average degree of polymerization, which is 0.1 to 20; - (CF2CF2CF2CF2O) d -CF2CF2CF2-(2-3) In formula (2-3), d represents the average degree of polymerization, which is 0.1 to 10; - (CF2CF(CF3)O) r -CF(CF3) -(2-4) In formula (2-4), r represents an average degree of polymerization and is 0.1 to 20.

3. The perfluoropolyether polyol according to claim 1, characterized in that Formula R3 is a group represented by any one of the following formulas (3-1) to (3-5): (3-1)； (3-2) f represents an integer from 1 to 20; (3-3) z represents an integer from 1 to 10; (3-4)； (3-5)。 4. The perfluoropolyether polyol according to claim 1, characterized in that Formula R4 is a terminal group represented by any one of the following formulas (4-1), (4-2), (4-3), and (4-4): (4-1) (4-2) (4-3) (4-4)， In formula (4-1), p and q are any integers of 1 to 5 which are the same or different; in formula (4-4), b and c are any integers of 1 to 5 which are the same or different.

5. The method for preparing the perfluoropolyether polyol according to any one of claims 1 to 4, characterized in that: The steps include: (a) using an epoxy compound having at least one epoxy group and at most one halogenated hydrocarbon to react with a perfluoropolyether alcohol under alkaline conditions to produce a perfluoropolyether having an epoxy group; (b) using a diol or triol having a primary or secondary amine to undergo a ring-opening reaction with the perfluoropolyether having an epoxy group in step (a) under alkaline conditions to generate a perfluoropolyether polyol having an amino group.

6. The method for preparing perfluoropolyether polyol according to claim 5, characterized in that: The epoxy compound in step (a) is selected from epichlorohydrin, diallyl ether oxide, and ethylene glycol glycidyl ether.

7. The method for preparing perfluoropolyether polyol according to claim 5, characterized in that: The epoxy compound in step (a) is selected from epichlorohydrin, diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,4-bis[(glycidyloxy)methyl]cyclohexane; In step (b), the diol or triol compound having a primary or secondary amine is selected from diethanolamine, 2-[(hydroxymethyl)amino]ethanol, 1-(2-hydroxy-ethylamino)-propane-2-ol, 1,1'-azadiylbis(2-methylpropan-2-ol), diisopropanolamine, and trishydroxymethylaminomethane.

8. The method for preparing perfluoropolyether polyol according to claim 5, characterized in that: In step (a), the molar ratio of the epoxy compound to the perfluoropolyether alcohol is 2-20:1, the reaction temperature is 50-150° C., and the reaction time is 5-80 h; In step (b), the molar ratio of the diol or triol with primary or secondary amine to the perfluoropolyether with epoxy group is 10-40:1, and the reaction temperature is 55-125°C.

9. The method for preparing perfluoropolyether polyol according to claim 8, characterized in that: The mass ratio of the diol containing secondary amine to the perfluoropolyether with epoxy group is 0.8:1-1.8:1, and the reaction temperature is 85-95°C.

10. The method for preparing perfluoropolyether polyol according to claim 8, characterized in that: In step (a), the molar ratio of the epoxy compound to the perfluoropolyether alcohol is 10-15:1, the reaction temperature is 70-100° C., and the reaction time is 18-25 h; In step (b), the mass ratio of the diol containing secondary amine to the perfluoropolyether with epoxy group is 0.8:1-1.8:1, and the reaction temperature is 85-95°C.

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