A perfluoropolyether polyol and its preparation method

Abstract

The present invention belongs to the field of fluorine-containing ether compounds, and specifically relates to a perfluoropolyether polyol and a preparation method thereof. The perfluoropolyether polyol has R4-R3-R2-R1-R′2-R3-R 4 The structure shown in FIG, wherein R1 is a perfluoropolyether chain; R2 is ‑O‑CF2‑CH2‑(CH2CH2O) x ‑, R′2 is ‑CF2‑CH2‑(OCH2CH2) y ‑, where 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, via an ethereal alkyl group; and R4 is a trihydroxyalkane group containing a tertiary amine group. The resin prepared using the perfluoropolyether polyol provided in the present invention as a crosslinking agent exhibits excellent substrate adhesion after curing and significantly enhances the durability and reliability of the coating.

Description

Technical Field

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

[0002] Perfluoropolyethers are widely used as lubricants and coatings. Derivatives with terminal -CH2OH groups are well known for their wide range of applications. Ausimont (New fluorinated thermoplastic elastomers. J. Appl. Polym. Sci. 1996;59:311-327) disclosed their structure:

[0003] HO-CH2CF2O-(CF2CF2O) m -(CF2O) n -CF2-CH2-OH

[0004] Wherein, m and n represent integers ≥ 1, and m / n = 0.9~1.1.

[0005] Perfluoropolyether alcohols, an important member of the perfluoropolyether family, and their reactive end-group functional derivatives have long been favored by researchers. By utilizing the reactivity of the perfluoropolyether alcohol end groups, researchers have creatively prepared a wide variety of perfluoropolyether polyol structures.

[0006] For example, CN101878249A proposes reacting at least one triol containing two protected hydroxyl groups and one free hydroxyl group with an activator. The activated, protected triol is then reacted with a perfluoropolyether polyol, followed by deprotection to produce a perfluoropolyether tetraol or even a perfluoropolyether octaol. This patent prepares perfluoropolyether tetraols and octaols by reacting specific triols with perfluoropolyether polyols and then deprotecting them. However, the structure and properties of the products are limited by the starting materials and the number of reaction steps.

[0007] Chinese patent literature CN118201983A and CN118382611A introduce the structure of various perfluoropolyether polyol derivatives and their application in magnetic recording media, but these structures have long synthetic routes, and there are a large number of side reactions, the post-processing process is complicated, and the overall synthesis difficulty is relatively large. And it is only applicable to the preparation of perfluoropolyether polyols with smaller molecular weights. The synthesis difficulty for high molecular weight perfluoropolyether polyols will be greater, which limits its application. In addition, perfluoropolyether alcohols are relatively rigid due to their strong molecular chain and relatively lack of polar functional groups. When participating in film formation as a cross-linking agent, they often lead to insufficient chemical bonding between the coating and the substrate, and there is a local stress concentration phenomenon in the cured network. This structural characteristic limits the interfacial adhesion and long-term chemical stability of the coating to a certain extent. Summary of the Invention

[0008] In order to solve the above problems in the prior art, the present invention provides a linear perfluoropolyether polyol and a preparation method thereof.

[0009] In order to achieve the above object, the present invention adopts the following technical solutions:

[0010] A perfluoropolyether polyol represented by the following formula (1):

[0011] R4-R3-R2-R1-R′2-R3-R4(1)

[0012] In formula (1), R1 is a perfluoropolyether chain; R2 is -O-CF2-CH2-(CH2CH2O) x -, R'2 is -CF2-CH2-(OCH2CH2) y -, where 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 to R2 or R4 to R'2 via an ethereal alkyl group; and R4 is a trihydroxyalkane group containing a tertiary amino group. Preferably, x+y = 1 to 20, and more preferably, x+y = 2 to 9.

[0013] The average degree of polymerization is defined as the average number of repeating units or structural units contained in each polymer molecule in the polymer chain.

[0014] Preferably, R1 in the formula (1) is any one of the following formulas (2-1) to (2-4):

[0015] - (CF2CF2O) n - (CF2O) m -(2-1)

[0016] 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;

[0017] - (CF2CF2CF2O) k -CF2CF2-(2-2)

[0018] In formula (2-2), k represents the average degree of polymerization and is 0.1 to 20;

[0019] - (CF2CF2CF2CF2O) d -CF2CF2CF2-(2-3)

[0020] In formula (2-3), d represents the average degree of polymerization and is 0.1 to 10;

[0021] - (CF2CF(CF3)O) r -CF(CF3) -(2-4)

[0022] In formula (2-4), r represents an average degree of polymerization and is in the range of 0.1 to 20.

[0023] Further preferably, the R1 is -(CF2CF2O) n - (CF2O) m -, m / n=0.9~1.1.

[0024] Preferably, formula R3 is a group represented by any one of the following formulas (3-1) to (3-5):

[0025] (3-1);

[0026] (3-2)

[0027] f represents an integer from 1 to 20;

[0028] (3-3)

[0029] z represents an integer from 1 to 10;

[0030] (3-4);

[0031] (3-5).

[0032] More preferably, R3 contains a hydroxyl group, and R3 is preferably a group represented by formula (3-2) to (3-5).

[0033] Preferably, formula R4 is a terminal group represented by any one of the following formulas (4-1), (4-2), (4-3), and (4-4):

[0034] (4-1) (4-2)

[0035] (4-3) (4-4)

[0036] In formula (4-1), p and q are any integers of 1 to 5 that are the same or different; in formula (4-4), b and c are any integers of 1 to 5 that are the same or different; in formulas (4-1) to (4-4), there are three hydroxyl groups of any structure that are the same or different and connected to nitrogen atoms.

[0037] Preferably, R4 in the formula (1) contains 3 hydroxyl groups.

[0038] Preferably, the number average molecular weight of the perfluoropolyether polyol is in the range of 500 to 50,000 g / mol, and more preferably, the number average molecular weight of the perfluoropolyether polyol is in the range of 1,000 to 5,000 g / mol.

[0039] Preferably, the compound of formula (1) is represented by any one of the following formulas A to AD:

[0040] (A)

[0041] wherein m and n represent integers of 1 to 10, and x and y represent any integer of 0 to 50; preferably, m / n=1.1, x+y=3.5.

[0042] (B)

[0043] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=3.5;

[0044] (C)

[0045] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=3.5;

[0046] (D)

[0047] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=3.5;

[0048] (E)

[0049] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=3.5;

[0050] (F)

[0051] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=4;

[0052] (G)

[0053] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=4;

[0054] (H)

[0055] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=4;

[0056] (I)

[0057] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=4;

[0058] (J)

[0059] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=4;

[0060] (K)

[0061] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=5.25;

[0062] (L)

[0063] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=5.25;

[0064] (M)

[0065] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=5.25;

[0066] (N)

[0067] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=5.25;

[0068] (O)

[0069] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=5.25;

[0070] (P)

[0071] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=9, and f=9;

[0072] (Q)

[0073] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=9, and f=9;

[0074] (R)

[0075] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=9, and f=9;

[0076] (S)

[0077] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=9, and f=9;

[0078] (T)

[0079] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=9, and f=9;

[0080] (U)

[0081] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=2;

[0082] (V)

[0083] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=2;

[0084] (W)

[0085] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=2;

[0086] (X)

[0087] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=2;

[0088] (Y)

[0089] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=1.1, x+y=2;

[0090] (Z)

[0091] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=0.92, x+y=5.5;

[0092] (AA)

[0093] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=0.92, x+y=5.5;

[0094] (AB)

[0095] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=0.92, x+y=5.5;

[0096] (AC)

[0097] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50; preferably, m / n=0.92, x+y=5.5;

[0098] (AD)

[0099] wherein m and n represent integers of 1 to 10, and x or y represents any integer of 0 to 50. Preferably, m / n=0.92, and x+y=5.5.

[0100] The present invention also provides a method for preparing the above-mentioned perfluoropolyether polyol, comprising the following steps:

[0101] (a) reacting an epoxy compound having at least one epoxy group and at most one halogenated hydrocarbon with a perfluoropolyether alcohol under alkaline conditions to produce a perfluoropolyether having an epoxy group;

[0102] The structural formula of perfluoropolyether alcohol is: HO-R2-R1-R′2-OH.

[0103] (b) using a diol or triol containing a primary or secondary amine to undergo a ring-opening reaction with the perfluoropolyether containing an epoxy group in step (a) under alkaline conditions to generate a perfluoropolyether polyol containing an amino group, namely, formula (1).

[0104] This method can produce polyol functionalized end groups, and each step has good reaction activity, fewer side reactions and by-products, and simple and convenient post-processing.

[0105] Preferably, the epoxy compound in step (a) is selected from one of epichlorohydrin, diallyl ether oxide, and ethylene glycol glycidyl ether. Further preferably, non-limiting examples of the compound having at least one oxirane group and at most one halogenated hydrocarbon are:

[0106] Epichlorohydrin has the formula:

[0107] (5-1);

[0108] Diglycidyl ether having the formula:

[0109] (5-2);

[0110] Ethylene glycol diglycidyl ether having the formula:

[0111] (5-3);

[0112] Polyethylene glycol diglycidyl ether having the formula:

[0113] (5-4),

[0114] The value range of f is 1~20, and the preferred value is 9;

[0115] 1,4-Butanediol diglycidyl ether having the formula:

[0116] (5-5);

[0117] 1,6-Hexanediol diglycidyl ether having the formula:

[0118] (5-6);

[0119] Neopentyl glycol diglycidyl ether having the formula:

[0120] (5-7);

[0121] 1,4-bis[(glycidyloxy)methyl]cyclohexane having the formula

[0122] (5-8).

[0123] Preferably, the alkaline conditions in step (a) are 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, when the hydroxyl group reacts with the epoxy group, an organic base, preferably potassium tert-butoxide, is preferred; when the hydroxyl group reacts with the halogenated hydrocarbon, an inorganic base, preferably NaOH or KOH, is preferred.

[0124] Preferably, step (a) is carried out in a mixed solvent of a fluorine-containing solvent and a non-fluorine-containing solvent.

[0125] The non-fluorinated solvent is one of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethylene glycol methyl ether, and ethylene glycol dimethyl ether, preferably diethylene glycol dimethyl ether. The fluorinated solvent in this step is used to dissolve the perfluoropolyether alcohol and reduce the viscosity of the reaction system. It is selected from one or more of 3M-7100, m-ditrifluorotoluene, perfluorohexane, and HT-110, preferably 3M-7100.

[0126] Preferably, 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 hours. Further preferably, 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 hours. The amount of base added is 0.5-10 wt% of the perfluoropolyether alcohol. More preferably, the amount of base added is 2-7 wt%.

[0127] Preferably, after the reaction in step (a) is completed, the reactants are cooled to room temperature, neutralized with acid, extracted and purified using a fluorinated solvent, concentrated, and separated and purified using a chromatographic column to obtain a perfluoropolyether with epoxy groups. 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.

[0128] Preferred, non-limiting examples of the diol or triol compound with a primary or secondary amine used in step (b) are:

[0129] Diethanolamine having the formula

[0130] (6-1);

[0131] 2-[(hydroxymethyl)amino]ethanol having the formula

[0132] (6-2);

[0133] 1-(2-Hydroxy-ethylamino)-propan-2-ol having the formula

[0134] (6-3);

[0135] 1,1'-azadiylbis(2-methylpropan-2-ol) having the formula

[0136] (6-4);

[0137] Diisopropanolamine having the formula

[0138] (6-5);

[0139] Tris(hydroxymethyl)aminomethane having the formula

[0140] (6-6).

[0141] Diols bearing secondary amines are further preferred.

[0142] Preferably, the alkaline conditions in step (b) are carried out in the presence of a base soluble in the reaction medium. Furthermore, preferably, the organic base triethylamine is preferably used for the reaction between the primary or secondary amine and the epoxy group. The molar ratio of triethylamine to the perfluoropolyether obtained in step (a) can be between 2 and 10:1.

[0143] 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 a perfluoropolyether polyol. The fluorinated solvent is selected from one or more of 3M-7300, 1,1,2-trifluorotrichloroethane, and 3M-7200, preferably 3M-7300.

[0144] Preferably, in step (b), the molar ratio of the diol or triol containing a primary or secondary amine to the perfluoropolyether containing an epoxy group is 10-40:1, and the reaction temperature is 55-125°C.

[0145] More preferably, in step (b), the molar ratio of the diol containing a secondary amine to the perfluoropolyether containing an epoxy group is 10-40:1, the reaction temperature is 85-125°C, and thin-layer chromatography (TLC) is used as the endpoint indicator (developing solvent 3M-7300:F113 = 1:10-10:1). More preferably, the mass ratio of the diol containing a secondary amine to the perfluoropolyether containing an epoxy group is 0.8:1-1.8:1, and the reaction temperature is 85-95°C.

[0146] Step (b) generally involves a two-phase reaction involving an organic phase and an organic fluorine phase (the intermediate product, a perfluoropolyether bearing epoxy groups). The organic phase is comprised of a diol or triol bearing a primary or secondary amine. The perfluoropolyether bearing epoxy groups has poor solubility in the organic phase. Therefore, the use of a phase catalyst can promote the forward reaction. Examples include tetrabutylammonium bromide, tetraalkylammonium hydroxide, tetrabutylammonium hydrogen sulfate, and tetrabutylammonium fluoride. Tetrabutylammonium bromide is preferred. The amount of tetrabutylammonium bromide added is approximately 5-20% of the weight of the organic fluorine phase.

[0147] Compared with the prior art, the present invention has at least the following beneficial effects or advantages:

[0148] (1) This invention focuses on the modification of perfluoropolyether polyols, specifically changing their structure and improving their performance by introducing nitrogen and increasing the number of hydroxyl groups. The resulting resin, which acts as a crosslinker, exhibits excellent substrate adhesion after curing and significantly enhances the durability and reliability of the coating, such as resistance to vibration and temperature changes, and reduced risk of corrosion penetration.

[0149] (2) The method of the present invention is more flexible in product structure design and can accurately synthesize perfluoropolyether polyols with specific properties according to specific needs. In addition, the synthesis method is simple and convenient for post-processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0150] Figure 1 is the NMR of compound A′ 1 H-NMR spectrum.

[0151] Figure 2 is the NMR of compound A 1 H-NMR spectrum.

[0152] Figure 3 NMR of compound B 1 H-NMR spectrum.

[0153] Figure 4 The NMR of compound C 1 H-NMR spectrum.

[0154] Figure 5 is the NMR of compound D1 H-NMR spectrum.

[0155] Figure 6 The NMR of compound E 1 H-NMR spectrum.

[0156] Figure 7 is the NMR of compound F′ 1 H-NMR spectrum.

[0157] Figure 8 is the NMR of compound K′ 1 H-NMR spectrum.

[0158] Figure 9 is the NMR of compound P′ 1 H-NMR spectrum.

[0159] Figure 10 is the NMR of compound U′ 1 H-NMR spectrum.

[0160] Figure 11 is the NMR of compound Z′ 1 H-NMR spectrum. DETAILED DESCRIPTION

[0161] The present invention is further described in detail below by way of examples. The present invention is not limited to the following examples. The perfluoropolyether alcohols used in the examples were purchased or prepared with reference to CN1031064C and CN100487020C, and the other raw materials were all commercially available products.

[0162] Example 1

[0163] Step 1: Add HO(CH2CH2O) to a 250 mL reaction flask in anhydrous and oxygen-free atmosphere with N2 atmosphere, a condenser reflux tube, a thermometer, and a vacuum pump. x CH2CF2O(CF2CF2O) n (CF2O) m CF2CH2(CH2CH2O) y OH compound (Mn = 2600g / mol, m / n = 1.1, x + y = 3.5) 26.0g, ethylene glycol diglycidyl ether 18g and t-BuOH 10mL, 50mL 3M-7100 and diethylene glycol dimethyl ether mixed solvent. Stir at room temperature until it becomes uniform. Further add t-BuOK 0.9g, stir at 70 ° C for 18h to react. The resulting reaction product is cooled to 25 ° C, neutralized with 0.5mol / L hydrochloric acid, extracted and purified with fluorinated solvent 1,1,2-trifluorotrichloroethane, the solution is concentrated, and refined by silica gel column chromatography to obtain 17.1g of compound (A') shown.

[0164] (A′)

[0165] Compound (A') 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 1 shown.

[0166] 1 H-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).

[0167] Step 2: In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, 5.0 g of the compound synthesized in step 1, 0.5 g of tetrabutylammonium bromide, 4.0 g of diethanolamine, and 1 mL of triethylamine were added. The mixture was stirred and gradually heated to 90°C. This temperature was maintained for 5 hours, with the reaction endpoint indicated by thin-layer chromatography (TLC) (developing solvent: 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 yield 3.88 g of product A.

[0168] (A)

[0169] Compound (A) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 2 shown.

[0170] 1 H-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).

[0171] Example 2

[0172] The same operation as in Example 1 was carried out except that 5.5 g of diisopropanolamine was used instead of 4.0 g of diethanolamine in Step 2 of Example 1, to obtain 2.81 g of Product B.

[0173] (B)

[0174] Where m / n=1.1, x+y=3.5.

[0175] Compound (B) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 3 shown.

[0176] 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).

[0177] Example 3

[0178] The same procedures as in Example 1 were carried out except that 5.0 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used instead of 4.0 g of diethanolamine in Step 2 of Example 1 to obtain 2.85 g of Product C.

[0179] (C)

[0180] Where m / n=1.1, x+y=3.5.

[0181] Compound (C) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 4 shown.

[0182] 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).

[0183] Example 4

[0184] The same procedures as in Example 1 were carried out except that 8.0 g of 1,1′-azadiylbis(2-methylpropan-2-ol) was used instead of 4.0 g of diethanolamine in Step 2 of Example 1 to obtain 1.88 g of Product D.

[0185] (D)

[0186] Where m / n=1.1, x+y=3.5.

[0187] Compound (D) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 5 shown.

[0188] 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).

[0189] Example 5

[0190] The same procedures as in Example 1 were carried out except that 7.0 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 4.0 g of diethanolamine in Step 2 of Example 1 to obtain 2.85 g of product E.

[0191] (E)

[0192] Where m / n=1.1, x+y=3.5.

[0193] Compound (E) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 6 shown.

[0194] 1 H-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).

[0195] Example 6

[0196] Step 1: Add 5 mL of 3 mol / L NaOH solution, 13.4 g of epichlorohydrin, 50 mL of a mixed solvent of 3M-7100 and diethylene glycol dimethyl ether to a 250 mL reaction flask in anhydrous and oxygen-free atmosphere with a N2 atmosphere and equipped with a condenser reflux tube, a thermometer, and a vacuum pump, and stir evenly. x CH2CF2O(CF2CF2O) n (CF2O) m CF2CH2(CH2CH2O) y 24.0 g of OH (Mn = 2400 g / mol, where m / n = 1.1, x + y = 4) was slowly and uniformly added dropwise over 3 hours. After the addition, the mixture was stirred at low temperature until uniform. After two hours of stirring, the temperature was raised to 80°C at a rate of 10°C / 30 min and the reaction was continued for 18 hours. The resulting reaction product was cooled to 25°C, neutralized with 0.5 mol / L hydrochloric acid, and extracted and purified with the fluorinated solvent 1,1,2-trifluorotrichloroethane. The solution was concentrated and purified by silica gel column chromatography to obtain 18.9 g of compound (F′).

[0197] (F′)

[0198] Compound (F') 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 7 shown.

[0199] 1 H-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).

[0200] Step 2: In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, add 5.0 g of the compound synthesized in Step 1, 0.5 g of tetrabutylammonium bromide, 7.0 g of diethanolamine, and 1 mL of triethylamine. Mix and stir, then gradually heat to 90°C and maintain this temperature until the reaction is complete, as indicated by thin-layer chromatography (TLC). The mixture is extracted with the fluorinated solvent 3M-7300. The crude product is collected by solvent evaporation and purified by silica gel column chromatography to yield 4.87 g of product F.

[0201] (F)

[0202] Where m / n=1.1, x+y=4.

[0203] Compound (F) was 1 The structure was confirmed by H-NMR test results.

[0204] 1 H-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).

[0205] Example 7

[0206] The same procedures as in Example 6 were carried out except that 6.0 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 7.0 g of diethanolamine in Step 2 of Example 6 to obtain 4.85 g of Product G.

[0207] (G)

[0208] Where m / n=1.1, x+y=4.

[0209] Compound (G) was 1 The structure was confirmed by H-NMR test results.

[0210] 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).

[0211] Example 8

[0212] The same procedures as in Example 6 were carried out except that 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 to obtain 2.85 g of H product.

[0213] (H)

[0214] Where m / n=1.1, x+y=4.

[0215] Compound (H) 1 The structure was confirmed by H-NMR test results.

[0216] 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).

[0217] Example 9

[0218] The same procedures as in Example 6 were carried out except that 8.0 g of 1,1′-azadiylbis(2-methylpropan-2-ol) was used instead of 7.0 g of diethanolamine in Step 2 of Example 6 to obtain 3.98 g of Product I.

[0219] (I)

[0220] Where m / n=1.1, x+y=4.

[0221] Compound (I) 1 The structure was confirmed by H-NMR test results.

[0222] 1 H-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).

[0223] Example 10

[0224] The same procedures as in Example 6 were carried out except that 7.0 g of diisopropanolamine was used instead of 7.0 g of diethanolamine in Step 2 of Example 6, to obtain 4.15 g of Product J.

[0225] (J)

[0226] Where m / n=1.1, x+y=4.

[0227] Compound (J) was 1 The structure was confirmed by H-NMR test results.

[0228] 1 H-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).

[0229] Example 11

[0230] Step 1: Add HO(CH2CH2O) to a 250 mL flask in anhydrous and oxygen-free atmosphere with a N2 atmosphere, a condenser reflux tube, a thermometer, and a vacuum pump. x CH2CF2O(CF2CF2O) n (CF2O) m CF2CH2(CH2CH2O) y OH (Mn = 2400g / mol, where m / n = 1.1, x + y = 5.25) 24.0g, 1,4-butanediol diglycidyl ether 21.0g and t-BuOH 10mL, 50mL 3M-7100 and diethylene glycol dimethyl ether mixed solvent. Stir at room temperature until it becomes uniform. Further add t-BuOK 0.9g, stir at 70 ° C for 25h to react. The resulting reaction product is cooled to 25 ° C, neutralized with 0.5mol / L hydrochloric acid, and extracted and purified with fluorinated solvent 1,1,2-trifluorotrichloroethane. The solution is concentrated and purified by silica gel column chromatography to obtain 15.34g of the compound (K') shown.

[0231] (K′)

[0232] Compound (K′) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 8 shown.

[0233] 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).

[0234] Step 2: In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, combine 5.0 g of the compound synthesized in Step 1, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine. Mix and stir, then gradually heat to 90°C and maintain this temperature until the reaction is complete, as indicated by thin-layer chromatography (TLC). The mixture is extracted with the fluorinated solvent 3M-7300. The crude product is collected by solvent evaporation and purified by silica gel column chromatography to yield 4.18 g of product K.

[0235] (K)

[0236] Where m / n=1.1, x+y=5.25.

[0237] Compound (K) 1 The structure was confirmed by H-NMR test results.

[0238] 1 H-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).

[0239] Example 12

[0240] The same procedures as in Example 11 were carried out except that 4.0 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 5.0 g of diethanolamine in Step 2 of Example 11 to obtain 3.85 g of the product.

[0241] (L)

[0242] Where m / n=1.1, x+y=5.25.

[0243] Compound (L) 1 The structure was confirmed by H-NMR test results.

[0244] 1 H-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).

[0245] Example 13

[0246] The same procedures as in Example 11 were carried out except that 5.5 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used instead of 5.0 g of diethanolamine in Step 2 of Example 11 to obtain 2.99 g of M product.

[0247] (M)

[0248] Where m / n=1.1, x+y=5.25.

[0249] Compound (M) 1 The structure was confirmed by H-NMR test results.

[0250] 1 H-NMR: δ[ppm]=5.24~5.08(4H),4.29~4.14(4H),4.10~3.78(10H),3.78~3.3 8(40H), 3.25~3.11(2H), 2.90~2.58(10H), 1.71~1.53(8H), 1.28~1.09(6H).

[0251] Example 14

[0252] The same procedures as in Example 11 were carried out except that 7.0 g of 1,1′-azadiylbis(2-methylpropan-2-ol) was used instead of 5.0 g of diethanolamine in Step 2 of Example 11 to obtain 1.85 g of N product.

[0253] (N)

[0254] Where m / n=1.1, x+y=5.25.

[0255] Compound (N) 1 The structure was confirmed by H-NMR test results.

[0256] 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),3.10~3.0 3(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).

[0257] Example 15

[0258] The same procedures as in Example 11 were carried out except that 6.0 g of diisopropanolamine was used instead of 5.0 g of diethanolamine in Step 2 of Example 11, to obtain 2.85 g of product O.

[0259] (O)

[0260] Where m / n=1.1, x+y=5.25.

[0261] Compound (O) 1 The structure was confirmed by H-NMR test results.

[0262] 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).

[0263] Example 16

[0264] Step 1: Add HO(CH2CH2O) to a 250 mL flask in anhydrous and oxygen-free atmosphere with a N2 atmosphere, a condenser reflux tube, a thermometer, and a vacuum pump. x CH2CF2O(CF2CF2O) n (CF2O) m CF2CH2(CH2CH2O) y 15.5 g of OH (Mn = 1550 g / mol, where m / n = 1.1, x+y = 9), 55 g of polyethylene glycol glycidyl ether (550 g / mol), 10 mL of t-BuOH, and 50 mL of a mixed solvent of 3M-7100 and diethylene glycol dimethyl ether were added. Stirring was carried out at room temperature until uniform. 0.9 g of t-BuOK was further added, and the mixture was stirred at 100 ° C for 18 hours to react. The resulting reaction product was cooled to 25 ° C, neutralized with 0.5 mol / L hydrochloric acid, and extracted and purified with a 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 (P′) shown.

[0265] (P′)

[0266] Compound (P') 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 9 shown.

[0267] 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).

[0268] Step 2: In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, add 5.0 g of the compound synthesized in Step 1, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine. Mix and stir, then gradually heat to 90°C and maintain this temperature until the reaction is complete, as indicated by thin-layer chromatography (TLC). The mixture is extracted with a hydrofluoroether solvent, 3M-7300. The crude product is collected by solvent evaporation and purified by silica gel column chromatography to yield 2.88 g of product P.

[0269] (P)

[0270] Where m / n=1.1, x+y=9, f=9.

[0271] Compound (P) 1 The structure was confirmed by H-NMR test results.

[0272] 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).

[0273] Example 17

[0274] The same procedures as in Example 16 were carried out except that 6.0 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 5.0 g of diethanolamine in Step 2 of Example 16 to obtain 1.85 g of product Q.

[0275] (Q)

[0276] Where m / n=1.1, x+y=9, f=9.

[0277] Compound (Q) 1 The structure was confirmed by H-NMR test results.

[0278] 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).

[0279] Example 18

[0280] The same procedures as in Example 16 were carried out except that 7.0 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used instead of 5.0 g of diethanolamine in Step 2 of Example 16 to obtain 3.05 g of R product.

[0281] (R)

[0282] Where m / n=1.1, x+y=9, f=9.

[0283] Compound (R) 1 The structure was confirmed by H-NMR test results.

[0284] 1 H-NMR: δ[ppm]=5.28~5.07(12H),4.09~3.96(2H),3.96~3.76(6H),3.76~3.4 1(104H),3.27~3.16(4H),2.77~2.61(12H),2.5~2.30(2H),1.25~1.10(6H).

[0285] Example 19

[0286] The same procedures as in Example 16 were carried out except that 9.0 g of 1,1′-azadiylbis(2-methylpropan-2-ol) was used instead of 5.0 g of diethanolamine in Step 2 of Example 16 to obtain 2.85 g of S product.

[0287] (S)

[0288] Where m / n=1.1, x+y=9, f=9.

[0289] Compound (S) 1 The structure was confirmed by H-NMR test results.

[0290] 1H-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).

[0291] Example 20

[0292] The same procedures as in Example 16 were carried out except that 8.0 g of diisopropanolamine was used instead of 5.0 g of diethanolamine in Step 2 of Example 16, to obtain 2.15 g of T product.

[0293] (T)

[0294] Where m / n=1.1, x+y=9, f=9.

[0295] Compound (T) 1 The structure was confirmed by H-NMR test results.

[0296] 1 H-NMR: δ[ppm]=5.28~5.07(12H),4.09~3.96(2H),3.96~3.76(8H),3.76~3.3 5(100H),3.27~3.08(6H),2.80~2.57(12H),2.5~2.30(2H),1.25~1.10(12H).

[0297] Example 21

[0298] Step 1: Add HO(CH2CH2O) to a 250 mL flask in anhydrous and oxygen-free atmosphere with a N2 atmosphere, a condenser reflux tube, a thermometer, and a vacuum pump. p CH2CF2O(CF2CF2O) n (CF2O) m CF2CH2(CH2CH2O) qOH (Mn = 1700g / mol, where m / n = 1.1, x + y = 2) 17g, 1,4-bis [(glycidyloxy) methyl] cyclohexane 25.6g and t-BuOH 10mL, 50mL3M-7100 and diethylene glycol dimethyl ether mixed solvent. Stir at room temperature until it becomes uniform. Further add t-BuOK 0.9g, stir at 100 ° C for 18h to react. The resulting reaction product is cooled to 25 ° C, neutralized with 0.5mol / L hydrochloric acid, and extracted and purified with a fluorinated solvent 1,1,2-trifluorotrichloroethane. The solution is concentrated and purified by silica gel column chromatography to obtain 13.12g of the compound (U ') shown.

[0299] (U′)

[0300] Compound (U′) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 10 shown.

[0301] 1 H-NMR: δ[ppm]=4.73~4.58(4H),3.97~3.83(2H),3.75~3.49(22H),3.46~3.3 9(2H),3.39~3.23(10H),3.23~3.16(2H),1.85~1.68(4H),1.49~1.23(16H).

[0302] Step 2: In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, combine 5.0 g of the compound synthesized in Step 1, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine. Mix and stir, then gradually heat to 90°C and maintain this temperature until the reaction is complete, as indicated by thin-layer chromatography (TLC). The mixture is extracted 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 yield 2.88 g of product U.

[0303] (U)

[0304] Where m / n=1.1, x+y=2.

[0305] Compound (U) 1 The structure was confirmed by H-NMR test results.

[0306] 1H-NMR: δ[ppm]=4.09~3.95(4H),3.97~3.78(4H),3.75~3.42(34H),3.37~3.2 9(8H), 3.23~3.15(2H), 2.76~2.62(12H), 1.85~1.68(4H), 1.49~1.23(16H).

[0307] Example 22

[0308] The same procedures as in Example 21 were carried out except that 5.0 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 5.0 g of diethanolamine in Step 2 of Example 21 to obtain 2.85 g of product V.

[0309] (V)

[0310] Where m / n=1.1, x+y=2.

[0311] Compound (V) 1 The structure was confirmed by H-NMR test results.

[0312] 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).

[0313] Example 23

[0314] The same procedures as in Example 21 were carried out except that 5.5 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used instead of 5.0 g of diethanolamine in Step 2 of Example 21 to obtain 3.85 g of product W.

[0315] (W)

[0316] Where m / n=1.1, x+y=2.

[0317] Compound (W) 1 The structure was confirmed by H-NMR test results.

[0318] 1H-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).

[0319] Example 23

[0320] The same procedures as in Example 21 were carried out except that 9.0 g of 1,1′-azadiylbis(2-methylpropan-2-ol) was used instead of 5.0 g of diethanolamine in Step 2 of Example 21 to obtain 2.97 g of Product X.

[0321] (X)

[0322] Where m / n=1.1, x+y=2.

[0323] Compound (X) 1 The structure was confirmed by H-NMR test results.

[0324] 1 H-NMR: δ[ppm]=4.09~3.95(4H),3.97~3.78(4H),3.75~3.42(22H),3.37~3.29(8H),3.23~3.1 5(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).

[0325] Example 25

[0326] The same procedures as in Example 21 were carried out except that 7.0 g of diisopropanolamine was used instead of 5.0 g of diethanolamine in Step 2 of Example 21, to obtain 2.95 g of product Y.

[0327] (Y)

[0328] Where m / n=1.1, x+y=2.

[0329] Compound (Y) 1 The structure was confirmed by H-NMR test results.

[0330] 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).

[0331] Example 26

[0332] Step 1: Add HO(CH2CH2O) to a 250 mL flask in anhydrous and oxygen-free atmosphere with a N2 atmosphere, a condenser reflux tube, a thermometer, and a vacuum pump. x CH2CF2O(CF2CF2O) n (CF2O) m CF2CH2(CH2CH2O) y OH (Mn = 2300g / mol, wherein m / n = 0.92, x + y = 5.5) 23.0g, neopentyl glycol diglycidyl ether 22.0g and t-BuOH 10mL, 50mL 3M-7100 and diethylene glycol dimethyl ether mixed solvent. Stir at room temperature until it becomes uniform. Further add t-BuOK 0.9g, stir at 85 ° C for 21h to react. The resulting reaction product is cooled to 25 ° C, neutralized with 0.5mol / L hydrochloric acid, and extracted and purified with fluorinated solvent 1,1,2-trifluorotrichloroethane. The solution is concentrated and refined by silica gel column chromatography to obtain 13g of compound (Z ') shown.

[0333] (Z′)

[0334] Compound (Z′) 1 The H-NMR test results confirmed the structure, and the NMR spectrum was as follows: Figure 11 shown.

[0335] 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).

[0336] Step 2: In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, combine 5.0 g of the compound synthesized in Step 1, 0.5 g of tetrabutylammonium bromide, 5.0 g of diethanolamine, and 1 mL of triethylamine. Mix and stir, then gradually heat to 90°C and maintain this temperature until the reaction is complete, as indicated by thin-layer chromatography (TLC). The mixture is extracted 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 yield 3.88 g of product Z.

[0337] (Z)

[0338] Where m / n=0.92, x+y=5.5.

[0339] Compound (Z) 1 The structure was confirmed by H-NMR test results.

[0340] 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).

[0341] Example 27

[0342] The same procedures as in Example 26 were carried out except that 4.5 g of 2-[(hydroxymethyl)amino]ethanol was used instead of 5.0 g of diethanolamine in Step 2 of Example 26 to obtain 3.35 g of AA product.

[0343] (AA)

[0344] Where m / n=0.92, x+y=5.5.

[0345] Compound (AA) was 1 The structure was confirmed by H-NMR test results.

[0346] 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).

[0347] Example 28

[0348] The same procedures as in Example 26 were carried out except that 5.0 g of 1-(2-hydroxy-ethylamino)-propan-2-ol was used instead of 5.0 g of diethanolamine in Step 2 of Example 26 to obtain 2.85 g of AB product.

[0349] (AB)

[0350] Where m / n=0.92, x+y=5.5.

[0351] Compound (AB) 1 The structure was confirmed by H-NMR test results.

[0352] 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).

[0353] Example 29

[0354] The same procedures as in Example 26 were carried out except that 6.0 g of 1,1′-azadiylbis(2-methylpropan-2-ol) was used instead of 5.0 g of diethanolamine in Step 2 of Example 26 to obtain 3.05 g of AC product.

[0355] (AC)

[0356] Where m / n=0.92, x+y=5.5.

[0357] Compound (AC) was 1 The structure was confirmed by H-NMR test results.

[0358] 1 H-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).

[0359] Example 30

[0360] The same procedures as in Example 26 were carried out except that 5.5 g of diisopropanolamine was used instead of 5.0 g of diethanolamine in Step 2 of Example 26, to obtain 3.85 g of AD product.

[0361] (AD)

[0362] Where m / n=0.92, x+y=5.5.

[0363] Compound (AD) was 1 The structure was confirmed by H-NMR test results.

[0364] 1 H-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).

[0365] Comparative Example 1

[0366] The compound represented by the following formula (AE) was synthesized according to the method described in JP-A-2018-521183.

[0367] (AE)

[0368] In formula (AE), mk and nk indicating the average degree of polymerization are 4 and 5, respectively.

[0369] Comparative Example 2

[0370] The compound represented by the following formula (AF) was synthesized according to the method described in CN 101878249B.

[0371] (AF)

[0372] In formula (AF), p / q represents an average degree of polymerization of 1.

[0373] The above perfluoropolyether polyol was used as a crosslinking agent to prepare a resin, and its adhesion level was tested.

[0374] The resin was prepared according to the following steps, where the hydroxyl equivalent weight of the perfluoropolyether polyol in the various examples and comparative examples was the same: Add polyether diol (650 g / mol) to a reaction kettle equipped with a condenser reflux tube, thermometer, and vacuum pump under an anhydrous and oxygen-free nitrogen atmosphere. Raise the kettle temperature to 120°C and vacuum pump for 2 hours. After completion, cool the reaction to room temperature. Slowly add isophorone diisocyanate dropwise, observing the temperature change in the kettle; it should not exceed 30°C. Stir for 30 minutes after addition. If viscosity increases, add solvent to reduce it. Raise the temperature by 10°C every 30 minutes until it reaches 80°C and react for 6 hours. Cool the kettle to room temperature, add perfluoropolyether polyol (dilute the perfluoropolyether polyol to approximately 10 wt% using a fluorinated solvent), and raise the kettle temperature to 80°C until the reaction is complete. If viscosity increases, add a mixture of fluorinated solvent and ethyl acetate. The end time is determined by titration of the isocyanate content. Store the reaction mixture in a dry place under nitrogen atmosphere at room temperature.

[0375] Table 1 Indexes and properties of perfluoropolyether polyols

[0376]

[0377] The adhesion of the obtained resin was tested. The adhesion test method was carried out in accordance with GB / T 9286-1998 "Paint and varnish film adhesion test grid method". The test plate was a steel plate and the coating thickness was 60 μm. The results are shown in Table 1. The R value is the molar ratio of isocyanate to hydroxyl.

[0378] As can be seen from the data in Table 1, the adhesion test results of Comparative Example 1 and Comparative Example 2 are relatively 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 a strong network uniformity, can provide sufficient cross-linking sites and the cross-linking 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 tertiary amine groups contained can improve its wetting properties, increase the wettability to the surface of the metal or oxide layer, and make the liquid coating more easily penetrate into the microscopic pores of the substrate, forming a physical anchoring effect. In practical applications, excellent adhesion can directly enhance the durability (resistance to vibration and temperature changes) and reliability (reducing the risk of corrosion penetration) of the coating.

[0379] In the present invention, the unique molecular structure of the perfluoropolyether polyols imparts excellent physical and chemical properties. These properties make the synthesized perfluoropolyether polyols promising for a variety of applications, including but not limited to high-performance coatings, optical fiber coatings, lubricants, and sealing materials. Furthermore, considering the development of modern technology, the perfluoropolyether polyols also have potential applications.

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 -, where x or y represents the same or different average degree of polymerization, ranging from 0 to 50; Formula R3 is a group represented by any one of the following formulas (3-2) to (3-5): (3-2) f represents an integer from 1 to 20; (3-3) z represents an integer from 1 to 10; (3-4)； (3-5)； 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 that are the same or different; in formula (4-4), b and c are any integers of 1 to 5 that are the same or different.

2. The perfluoropolyether polyol according to claim 1, wherein 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 and is 0.1 to 20; - (CF2CF2CF2CF2O) d -CF2CF2CF2-(2-3) In formula (2-3), d represents the average degree of polymerization and 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 in the range of 0.1 to 20.

3. The method for preparing the perfluoropolyether polyol according to any one of claims 1 to 2, characterized in that: The steps include: (a) reacting an epoxy compound having at least one epoxy group and at most one halogenated hydrocarbon with a perfluoropolyether alcohol under alkaline conditions to produce a perfluoropolyether having an epoxy group; (b) using a diol having a 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.

4. The method for preparing perfluoropolyether polyol according to claim 3, wherein: The epoxy compound in step (a) is selected from diallyl ether oxide and ethylene glycol glycidyl ether.

5. The method for preparing perfluoropolyether polyol according to claim 3, wherein: The epoxy compound in step (a) is selected from 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 compound with a secondary amine is selected from diethanolamine, 2-[(hydroxymethyl)amino]ethanol, 1-(2-hydroxy-ethylamino)-propane-2-ol, 1,1'-azadiylbis(2-methylpropan-2-ol), and diisopropanolamine.

6. The method for preparing perfluoropolyether polyol according to claim 3, wherein: 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 hours; In step (b), the molar ratio of the diol with a secondary amine to the perfluoropolyether with an epoxy group is 10-40:1, and the reaction temperature is 55-125°C.

7. The method for preparing perfluoropolyether polyol according to claim 3, wherein: 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.

8. The method for preparing perfluoropolyether polyol according to claim 3, wherein: 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 hours; 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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