A perfluoropolyether amine compound and its preparation method and application

Abstract

The present invention relates to a perfluoropolyether amine compound and a preparation method and application thereof. The structural formula of the perfluoropolyether amine compound is: #imgabs0# wherein Rf is F-(CF 2 ) m ‑(OCF 2 ) p ‑(OC 2 F 4 ) q ‑(OC 3 F 6 ) r ‑O(CF 2 ) n ‑, wherein m, n, p, q and r are independent and are integers between 0‑100, the sum of p, q and r is at least 1, the order and number of the repeating units with p, q and r enclosed in brackets are arbitrary, m and n are integers between 0‑20, the molecular weight of Rf is 500‑10000; X is an alkyl, phenyl or phenyl with a substituent. After the perfluoropolyether amine compound is mixed with a conventional anti-fingerprint agent and evaporated on the surface of a polycarbonate substrate, an anti-fingerprint coating with excellent wear resistance can be formed, and its performance is better than that of commercially available anti-fingerprint agents.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer compound synthesis, and in particular to a perfluoropolyether amine compound and a preparation method and application thereof. Background Art

[0002] The perfluoropolyether chain segment at one end of the perfluoropolyether amine compound has high lubricity, hydrophobicity and oleophobicity, and has good waterproof and antifouling properties. The amine group at the other end is a hydrophilic group, which can be treated to obtain ammonium salt or quaternary ammonium salt cationic surfactants, which are easily adsorbed on solid surfaces and can be used as waterproof and oil-proof agents, fabric softeners, antistatic agents, bactericides, etc.

[0003] In the prior art, there is a method of reducing perfluoropolyether acrylic acid cyanide compounds to prepare perfluoropolyether amine compounds. The terminal amine group can form hydrogen bonds with the surface of part of the plastic substrate, so the perfluoropolyether amine compound can be better used as a surface coating component of the plastic substrate and show excellent performance.

[0004] The existing patent CN114957646A reports a surfactant of a perfluoropolyether amine compound, which has a water contact angle of 113° on a plastic substrate, has better adhesion to the plastic substrate, and has excellent friction resistance. However, we found that in actual operation, the post-processing of lithium aluminum hydride reduction is difficult, and the fluorine phase and non-fluorine phase are easy to emulsify but difficult to separate. The present invention creatively adopts a one-step method, with mild reaction conditions, no catalyst required, simple post-processing, and higher yield. It is an economical and efficient method for preparing perfluoropolyether amine compounds. Summary of the invention

[0005] Technical problem to be solved: In view of the shortcomings of the prior art, the present invention provides a perfluoropolyether amine compound and a preparation method and application thereof. The synthesis route of the perfluoropolyether amine compound is simple, no catalyst is required, and the product yield is high.

[0006] Technical solution: A perfluoropolyether amine compound, the structural formula of the perfluoropolyether amine compound is:

[0007]

[0008] Where Rf is F-(CF2) m -(OCF2) p -(OC2F4) q -(OC3F6) r -O(CF2) n-, wherein m, n, p, q and r are independently integers between 0 and 100, the sum of p, q and r is at least 1, the order and number of the repeating units with p, q and r enclosed in brackets are arbitrary, m and n are integers between 0 and 20, and the molecular weight of Rf is 500-10000;

[0009] X is an alkyl group, a phenyl group, or a phenyl group having a substituent.

[0010] The repeating unit -OC3F6- mentioned above is one or both of -OCF2CF2CF2- and -OCF(CF3)CF2-.

[0011] The preparation method of the above-mentioned perfluoropolyether amine compound comprises the following steps:

[0012] The first step: dissolving the diamine compound in a solvent to obtain a mixed solution A, wherein the solvent is one or both of a fluorinated solvent and an organic solvent, wherein the weight ratio of the diamine compound to the solvent is 1:(1-50);

[0013] Step 2: dissolving the perfluoropolyether ester in a fluorinated solvent to obtain a mixed solution B, wherein the weight ratio of the perfluoropolyether ester to the fluorinated solvent is 1:(1-10);

[0014] Step 3: Add the mixed solution B dropwise into the mixed solution A, react at a temperature of 20°C to 70°C for 0.5 to 4 hours, and then remove the solvent by extraction and reduced pressure distillation to obtain a perfluoropolyether amine compound, wherein the molar ratio of the perfluoropolyether ester in the mixed solution B to the diamine compound in the mixed solution A is 1: (1.1 to 10).

[0015] The structural formula of the diamine compound described above is NH2XNH2, wherein X is an alkyl group, a phenyl group or a phenyl group with a substituent.

[0016] The structural formula of the perfluoropolyether ester described above is Rf-COOR, wherein R is a C1-C4 alkyl group, preferably a methyl group.

[0017] The fluorine-containing solvents in the first and second steps are one or more of m-ditrifluorotoluene, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, perfluorohexane, tridecafluorooctane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and trichlorotrifluoroethane.

[0018] The organic solvent in the first step described above is an ether solvent, an alcohol solvent or a ketone solvent, the ether solvent is diethyl ether or tetrahydrofuran, the alcohol solvent is methanol or ethanol, and the ketone solvent is acetone.

[0019] In the first step described above, the weight ratio of the diamine compound to the solvent is 1:(5-20).

[0020] In the second step described above, the weight ratio of perfluoropolyether ester to fluorine-containing solvent is 1:(2-5).

[0021] The molar ratio of the perfluoropolyether ester in the mixed solution B in the third step to the diamine compound in the mixed solution A is 1:(3-10).

[0022] Application of the above-mentioned perfluoropolyether amine compound in the preparation of anti-fingerprint coating.

[0023] The use of the above-mentioned perfluoropolyether amine compound in the preparation of an anti-fingerprint coating is as follows: the perfluoropolyether amine compound is mixed with a conventional anti-fingerprint agent and evaporated on the surface of a polycarbonate substrate to form an anti-fingerprint coating with wear resistance and durability.

[0024] The synthesis formula of the present invention is as follows:

[0025]

[0026] Beneficial effects: The present invention provides a perfluoropolyether amine compound and its preparation method and application, which have the following beneficial effects: after the perfluoropolyether amine compound is mixed with a conventional anti-fingerprint agent and evaporated on the surface of a polycarbonate substrate, an anti-fingerprint coating with excellent wear resistance can be formed, and its performance is better than that of commercially available anti-fingerprint agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the HNMR spectrum of the perfluoropolyether amine compound Q1 prepared in Example 1.

[0028] Figure 2 This is the HNMR spectrum of the perfluoropolyether amine compound Q2 prepared in Example 2.

[0029] Figure 3 This is the HNMR spectrum of the perfluoropolyether amine compound Q3 prepared in Example 3.

[0030] Figure 4 This is the HNMR spectrum of the perfluoropolyether amine compound Q4 prepared in Example 4. DETAILED DESCRIPTION

[0031] In order to make the purpose of the present invention, technical operation and advantages clearer, the synthesis steps and application operations in the embodiments of the present invention will be clearly and completely described below. It should be noted that the described embodiments are part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments in the present invention, ordinary staff of this field, without making creative work premise, all other embodiments operated, belong to the scope of protection of the present invention.

[0032] The sources of the raw materials used in the following examples are as follows:

[0033] Ethylenediamine monohydrate, tetrahydrofuran, and propylenediamine were purchased from Shanghai Titan Technology Co., Ltd.

[0034] The fluorinated solvent HFE-7200 was purchased from 3M Company.

[0035] Perfluoropolyether methyl ester (type K, molecular weight 3000) was purchased from Chenzhou Fluorine Chemical Co., Ltd.

[0036] Perfluoropolyether methyl ester (Z type, molecular weight 2000) was purchased from Solvay.

[0037] The anti-fingerprint agent (OPTOOLUD509) was purchased from Daikin Corporation.

[0038] The polycarbonate (PC) substrate film was purchased from Silk Packaging Materials Co., Ltd. and had a thickness of 0.3 mm.

[0039] Example 1

[0040] This embodiment provides a method for preparing a perfluoropolyether amine compound (Q1), and the specific steps are as follows:

[0041] In a 100mL round-bottom flask equipped with a thermometer, a constant pressure dropping funnel, and a magnetic stirrer, add 1.0g of ethylenediamine monohydrate, and dissolve it with 10mL of HFE-7200 and 10mL of tetrahydrofuran to obtain a mixed solution A1. Dissolve 10.0g of perfluoropolyether methyl ester (type K, molecular weight 3000) in 10mL of HFE-7200 to obtain a mixed solution B1, and place it in a constant pressure dropping funnel. Add the mixed solution B1 dropwise into the round-bottom flask where the mixed solution A1 is located, and stir the reaction at 50°C for 0.5 to 2h. The TLC spot plate determines that the reaction is complete. After treatment, wash three times with 5mL of water, and then remove the solvent by rotary evaporation to obtain 10.2g of a colorless to light yellow transparent liquid, which is the perfluoropolyether amino compound Q1. 1 H-NMR spectrum Figure 1 shown.

[0042] Example 2

[0043] This embodiment provides a method for preparing a perfluoropolyether amine compound (Q2), and the specific steps are as follows:

[0044] In a 100mL round-bottom flask equipped with a thermometer, a constant pressure dropping funnel, and a magnetic stirrer, add 1.0g of propylenediamine, and dissolve it with 10mL of HFE-7200 and 10mL of tetrahydrofuran to obtain a mixed solution A2. Dissolve 10.0g of perfluoropolyether methyl ester (type K, molecular weight 3000) in 10mL of HFE-7200 to obtain a mixed solution B2, and place it in a constant pressure dropping funnel. Add the mixed solution B2 dropwise into the round-bottom flask where the mixed solution A2 is located, and stir the reaction at 50°C for 0.5 to 2h. The TLC spot plate determines that the reaction is complete. After post-treatment, wash three times with 5mL of water, and then remove the solvent by rotary evaporation to obtain 10.1g of a colorless to light yellow transparent liquid, which is the perfluoropolyether amino compound Q3. Its 1 H-NMR spectrum Figure 2 shown.

[0045] Example 3

[0046] This embodiment provides a method for preparing a perfluoropolyether amine compound (Q3), and the specific steps are as follows:

[0047] In a 100mL round-bottom flask equipped with a thermometer, a constant pressure dropping funnel, and a magnetic stirrer, add 1.5g of propylenediamine, and dissolve it with 10mL of HFE-7200 and 10mL of tetrahydrofuran to obtain a mixed solution A3. Dissolve 10.0g of perfluoropolyether methyl ester (Z type, molecular weight 2000) in 10mL of HFE-7200 to obtain a mixed solution B3, and place it in a constant pressure dropping funnel. Add the mixed solution B3 dropwise into the round-bottom flask where the mixed solution A3 is located, and stir the reaction at 50°C for 0.5 to 2h. The TLC spot plate determines that the reaction is complete. After post-treatment, wash three times with 5mL of water, and then rotary evaporate to remove the solvent to obtain 9.8g of a colorless to light yellow transparent liquid, which is the perfluoropolyether amino compound Q3. Its 1 H-NMR spectrum Figure 3 shown.

[0048] Example 4

[0049] This embodiment provides a method for preparing a perfluoropolyether amine compound (Q4), and the specific steps are as follows:

[0050] In a 100mL round-bottom flask equipped with a thermometer, a constant pressure dropping funnel, and a magnetic stirrer, add 2.7g of p-phenylenediamine, and dissolve it with 10mL of HFE-7200 and 10mL of tetrahydrofuran to obtain a mixed solution A4. Dissolve 10.0g of perfluoropolyether methyl ester (Z type, molecular weight 2000) in 10mL of HFE-7200 to obtain a mixed solution B4, and place it in a constant pressure dropping funnel. Add the mixed solution B4 dropwise into the round-bottom flask where the mixed solution A4 is located, and stir the reaction at 60°C for 0.5 to 2h. The TLC spot plate determines that the reaction is complete. After post-treatment, wash three times with 5mL of water, and then rotary evaporate to remove the solvent to obtain 10.4g of a colorless transparent liquid, which is the perfluoropolyether amino compound Q4. Its 1 H-NMR spectrum Figure 4 shown.

[0051] According to the perfluoropolyether amine compounds Q1, Q2, Q3, Q4 of Examples 1-4 1 H-NMR spectrum, the following chemical shifts and integrals were obtained.

[0052] Compound Q1: δ3.44 (-CONH-C H2 -CH2-NH2)2H; δ2.92(-CONH-CH2-C H2 -NH2)2H.

[0053] Compound Q2: δ3.59 (-CONH-C H2 -CH2-CH2-NH2)2H; δ2.97(-CONH-CH2-CH2-C H2 -NH2)2H;δ1.67(-CONH-CH2-C H2 -CH2-NH2)2H.

[0054] Compound Q3: δ3.54 (-CONH-C H2 -CH2-CH2-NH2)2H; δ2.97(-CONH-CH2-CH2-C H2 -NH2)2H;δ1.67(-CONH-CH2-C H2 -CH2-NH2)2H.

[0055] Compound Q4: δ7.20 (-CONH-CH2-C6 H4 -CH2-NH2)4H; δ4.43(-CONH-C H2 -C6H4-CH2-NH2)2H; δ3.77(-CONH-CH2-C6H4-C H2 -NH2)2H.

[0056] From the attached Figure 1-4It can be seen that the perfluoropolyether-based amino compound prepared by the preparation method of the present invention has a high reaction conversion rate and a high product purity.

[0057] The anti-fingerprint coating was prepared using the perfluoropolyether amine compounds Q1, Q2, Q3, and Q4 prepared in Examples 1-4, and the corresponding preparation process is as follows: Application Examples 1-4.

[0058] Application Example 1

[0059] The perfluoropolyether amine compound Q1 was prepared with HFE-7200 (nonafluorobutyl ethyl ether) to a mass concentration of 20%, and mixed with an anti-fingerprint agent (OPTOOLUD509) at a mass ratio of 1:2 to obtain a surface treatment agent S1. The surface was deposited on a polycarbonate (PC) substrate film (thickness 0.3 mm) by vacuum evaporation, and the film thickness was controlled to be about 20 nm by a film thickness meter. The film with the deposited film was then placed at 70°C for 2 hours for curing to form an anti-fingerprint coating.

[0060] Application Example 2

[0061] The difference between Application Example 2 and Application Example 1 is that the perfluoropolyether amine compound Q1 is replaced by the perfluoropolyether amine compound Q2.

[0062] Application Example 3

[0063] The difference between Application Example 3 and Application Example 1 is that the perfluoropolyether amine compound Q1 is replaced by the perfluoropolyether amine compound Q3.

[0064] Application Example 4

[0065] The difference between Application Example 4 and Application Example 1 is that the perfluoropolyether amine compound Q1 is replaced by the perfluoropolyether amine compound Q4.

[0066] Comparative Example 1

[0067] The anti-fingerprint agent (OPTOOLUD509) commercially available from Daikin Corporation was deposited onto a film (thickness 0.3 mm) on a polycarbonate (PC) substrate by vacuum evaporation. The film thickness was controlled to be approximately 20 nm by a film thickness meter. The film with the deposited film was then placed at 70°C for 2 hours for curing to form an anti-fingerprint coating.

[0068] The performance of the anti-fingerprint coating obtained in Examples 1-4 and Comparative Example 1 was tested and evaluated, and the process and results are as follows.

[0069] 1. Water contact angle measurement

[0070] The anti-fingerprint coatings of Example 1-4 and Comparative Example 1 were tested for static water contact angle using a contact angle tester (SDC-100, Dongguan Shengding Precision Instrument Co., Ltd.): a water droplet with a volume of 2uL was dropped on the PC membrane using an injection needle, and the angle was measured using drop shape analysis technology and equipment software, and the average value was calculated by measuring 5 points.

[0071] 2. Friction durability test

[0072] First, when the anti-fingerprint coating is formed and there is no contact (i.e. the number of frictions is zero), the angle measured is the initial angle, and then the wool felt friction durability evaluation is implemented. The specific method is: using a wear tester (DZ-204-1, Dongguan Dazhong Instrument Co., Ltd.), using wool felt (size 3mm*10mm*10mm) as the friction medium, and applying a load of 1000g on it, reciprocating at a frequency of 40 times / min, and moving a distance of 4cm. After every 1000 reciprocating times, the water contact angle is tested until the contact angle is less than 100° and the test is terminated.

[0073] 3. Test results

[0074] As shown in Table 1 below.

[0075] Table 1

[0076]

[0077] As can be seen from Table 1, the anti-fingerprint coating obtained by mixing the synthesized perfluoropolyether amine compound with a conventional anti-fingerprint agent and acting on a polycarbonate (PC) substrate has good friction resistance and durability, which cannot be achieved by a single conventional anti-fingerprint agent. The main reason is that the amine group of the perfluoropolyether amine compound can form a hydrogen bond with the carbonyl group of the polycarbonate structure and have a certain binding force, while the active Si-O bond of the single anti-fingerprint agent cannot be firmly combined with it.

[0078] The embodiments of the present invention are described in detail above. For those skilled in the art, according to the ideas of the embodiments of the present invention, there may be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. A perfluoropolyether amine compound, characterized in that The structural formula of the perfluoropolyether amine compound is: Where Rf is F-(CF2) m -(OCF2) p -(OC2F4) q -(OC3F6) r -O(CF2) n -, wherein m, n, p, q and r are independently integers between 0 and 100, the sum of p, q and r is at least 1, the order and number of the repeating units with p, q and r enclosed in brackets are arbitrary, m and n are integers between 0 and 20, and the molecular weight of Rf is 500-10000; X is an alkyl group, a phenyl group, or a phenyl group having a substituent.

2. A perfluoropolyether amine compound according to claim 1, characterized in that: The repeating unit -OC3F6- is one or both of -OCF2CF2CF2- and -OCF(CF3)CF2-.

3. The method for preparing a perfluoropolyether amine compound according to claim 1, characterized in that The preparation steps are as follows: The first step: dissolving the diamine compound in a solvent to obtain a mixed solution A, wherein the solvent is one or both of a fluorinated solvent and an organic solvent, wherein the weight ratio of the diamine compound to the solvent is 1:(1-50); Step 2: dissolving the perfluoropolyether ester in a fluorinated solvent to obtain a mixed solution B, wherein the weight ratio of the perfluoropolyether ester to the fluorinated solvent is 1:(1-10); Step 3: Add the mixed solution B dropwise into the mixed solution A, react at a temperature of 20°C to 70°C for 0.5 to 4 hours, and then remove the solvent by extraction and reduced pressure distillation to obtain a perfluoropolyether amine compound, wherein the molar ratio of the perfluoropolyether ester in the mixed solution B to the diamine compound in the mixed solution A is 1: (1.1 to 10).

4. The method for preparing a perfluoropolyether amine compound according to claim 3, characterized in that: The structural formula of the diamine compound is NH2XNH2, wherein X is an alkyl group, a phenyl group or a phenyl group with a substituent.

5. The method for preparing a perfluoropolyether amine compound according to claim 3, characterized in that: The structural formula of the perfluoropolyether ester is Rf-COOR, wherein R is a C1-C4 alkyl group, preferably a methyl group.

6. The method for preparing a perfluoropolyether amine compound according to claim 3, characterized in that: The fluorine-containing solvents in the first step and the second step are one or more of m-ditrifluorotoluene, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, perfluorohexane, tridecafluorooctane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and trichlorotrifluoroethane.

7. The method for preparing a perfluoropolyether amine compound according to claim 3, characterized in that: The organic solvent in the first step is an ether solvent, an alcohol solvent or a ketone solvent, the ether solvent is diethyl ether or tetrahydrofuran, the alcohol solvent is methanol or ethanol, and the ketone solvent is acetone.

8. The method for preparing a perfluoropolyether amine compound according to claim 3, characterized in that: The weight ratio of the diamine compound to the solvent in the first step is 1:(5-20); the weight ratio of the perfluoropolyether ester to the fluorine-containing solvent in the second step is 1:(2-5); and the molar ratio of the perfluoropolyether ester in the mixed solution B and the diamine compound in the mixed solution A in the third step is 1:(3-10).

9. Use of a perfluoropolyether amine compound as claimed in claim 1 in the preparation of an anti-fingerprint coating.

10. Use of a perfluoropolyether amine compound according to claim 9 in the preparation of an anti-fingerprint coating, characterized in that The method is as follows: the perfluoropolyether amine compound is mixed with a conventional anti-fingerprint agent, and evaporated on the surface of a polycarbonate substrate to form an anti-fingerprint coating.

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