Directionally-arranged low-adsorption auxiliary agent as well as preparation method and application thereof

Abstract

The invention discloses a low-adsorption auxiliary agent capable of being directionally arranged, which is specifically composed of a perfluoro straight carbon chain A, a carbamate group B and an alkyl group C, and forms an A-B-C molecular configuration, the A structure part has the lowest surface energy; the B structure part has the highest surface energy; and the surface energy of the C structure part is higher than that of the A structure part but obviously lower than that of the B structure part. The low-adsorption auxiliary agent with the molecular configuration realizes directional arrangement on the surface of a non-polar polymer material (such as polyethylene, polypropylene and the like), A points to one side of air, C points to one side of the material, and the material surface is endowed with an excellent hydrophobic effect. In addition, the invention also discloses a preparation method of the low-adsorption auxiliary agent. The low-adsorption assistant provided by the invention has the characteristics of high orientation and high hydrophobicity, and can obtain a static water contact angle of 120-130 degrees when being applied to non-polar high polymer materials such as PE (Polyethylene), PP (Polypropylene) and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material additives, and in particular relates to a directional low-adsorption additive and a preparation method and application thereof. Background Art

[0002] The hydrophobic effect on the surface of a material can give it the unique functions of self-cleaning, low adsorption or low adhesion, providing higher value for its application in related fields. For example, in the field of medical testing, a large number of high-molecular consumables such as polyethylene and polypropylene are used; when the surface of the consumable is highly hydrophobic, the adhesion of the consumable surface to the test agents and the components to be tested, such as DNA, can be significantly reduced, which can reduce the cost of testing and improve the accuracy of the test results. In terms of hydrophobic characteristics, the hydrophobic state of the material surface can be divided into general hydrophobicity and super hydrophobicity according to the size of the hydrophobic ability. Among them, a super hydrophobic surface usually refers to a surface with a static contact angle with water greater than 150° and a rolling angle less than 10°. The hydrophilicity and hydrophobicity of the material surface are related to its surface free energy, also known as surface tension. The lower the surface free energy, the more hydrophobic the surface.

[0003] At present, there are usually two strategies to achieve super-hydrophobicity on the surface of materials: one is to construct a micro-nano rough structure on a low surface energy material, and the other is to modify the rough structure using a low surface energy material. At present, the low surface energy materials used to prepare super-hydrophobic materials mainly include alkane compounds, organosilicon compounds, fluorine-containing compounds, etc., and the methods for constructing rough structures mainly include template method, sol-gel method, layer-by-layer assembly method, deposition method, etching method, phase separation method, spraying method, etc. The above methods either use a large amount of volatile organic solvents that are harmful to the environment and human body in the preparation process, or have high cost and complex process, or have poor adaptability, cannot be mass-produced, or expensive equipment and other shortcomings, which limit their application. That is, these methods are difficult to use for rapid, low-cost, large-scale hydrophobic functional modification of the surface of medical plastic consumables products.

[0004] In contrast, the most suitable hydrophobic functionalization method for the current production process of plastic consumables is to directly melt-extrude and blend low-surface energy substances, that is, low-adsorption additives, with polymer materials to achieve hydrophobic functionalization modification on the surface of plastic consumables. It is also a very economical and efficient hydrophobic functionalization approach. Among them, perfluorinated straight carbon chain compounds are the best low-adsorption additives in this method. The use of perfluorinated straight carbon chain compounds alone is not only expensive, but also because there are no structural components with surface energy gradient distribution in their structure, which makes it impossible to arrange in a directional manner on the surface of the material and cannot exert the best hydrophobic effect. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems in the related art to a certain extent. To this end, the main purpose of the present invention is to provide a directional low adsorption auxiliary agent and a preparation method thereof, aiming to solve the technical problems of the existing low adsorption auxiliary agents having high cost and poor hydrophobic effect.

[0006] The invention also provides the use of the directional arranged low adsorption auxiliary agent in the non-polar polymer material.

[0007] The objective of the present invention is achieved through the following technical solutions:

[0008] A directional low adsorption auxiliary agent, the molecular structure of which includes a perfluorinated straight carbon chain A, a carbamate group B and a hydrocarbon group C, forming an ABC molecular configuration.

[0009] In some specific embodiments, the molecular structure of the low adsorption auxiliary agent is:

[0010]

[0011] In the formula, n is an integer of 3-9, m is an integer of 1-2; and R1 is any one of an aryl group, a cycloalkyl group, and a chain alkyl group.

[0012] In another specific embodiment, the molecular structural formula of the low adsorption auxiliary agent is:

[0013]

[0014] In the formula, n is an integer of 3-9, m is an integer of 1-2; R2 is any one of hexamethylene, tolyl, and diphenylmethane; and R3 is any one of aryl, cycloalkyl, and chain alkyl.

[0015] In some specific embodiments, the perfluorinated straight carbon chain A is provided by a perfluorinated alcohol wherein n+1 is 4-10.

[0016] In some specific embodiments, the carbamate group B is provided by any one of a mono- or di-carbamate group.

[0017] In certain specific embodiments, the mono / diurethane group is any one of toluene isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

[0018] In certain specific embodiments, the hydrocarbon group C is provided by any one of toluene isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, and stearyl alcohol.

[0019] The present invention provides a method for preparing the above-mentioned directional low-adsorption auxiliary agent, comprising the following steps: placing 0.95 equivalents of perfluoroalcohol and 1 equivalent of monoisocyanate in a reaction system, protecting with nitrogen and stirring, reacting at 50°C for 0.5h, reacting at 80°C for 0.5h, reacting at 120°C for 0.5h, and finally reacting at 150°C for 2h.

[0020] The present invention also provides a method for preparing the aforementioned directional low-adsorption auxiliary agent, comprising the following steps: placing 1 equivalent of perfluoroalcohol and 5-15 equivalents of diisocyanate in a reaction system, protecting with nitrogen and stirring, reacting at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 1h; recovering excess diisocyanate by vacuum distillation; adding 0.95 equivalents of stearyl alcohol, protecting with nitrogen and stirring, reacting at 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h.

[0021] An application of the above-mentioned directional low-adsorption auxiliary agent in the surface hydrophobic modification of non-polar polymer materials.

[0022] Compared with the prior art, the present invention has at least the following advantages:

[0023] The directional low-adsorption auxiliary agent provided by the present invention is a low-adsorption auxiliary agent having a structural component with a surface energy gradient distribution in the molecule, by coupling perfluoroalcohol with monoisocyanate or coupling perfluoroalcohol and stearyl alcohol with diisocyanate at the same time. This not only reduces the cost of the low-adsorption auxiliary agent, but also can be directional arranged on the surface of a non-polar polymer material to form a hydrophobic film to give the material surface a high hydrophobic property. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the specific embodiments of the present invention, the drawings required for use in the specific embodiments or the description of the prior art will be briefly introduced below.

[0025] Figure 1 In Application Example 1 of the present invention, low adsorption auxiliary agent a ( Figure 1 -r)、d( Figure 1 -s), g( Figure 1 -t) Static contact angle test diagram of the obtained highly hydrophobic PP material surface and water;

[0026] Figure 2 In Application Example 1 of the present invention, low adsorption aid b( Figure 2 -r)、e( Figure 2 -s), h( Figure 2 -t) Static contact angle test diagram of the obtained highly hydrophobic PP material surface and water;

[0027] Figure 3In Application Example 1 of the present invention, low adsorption aid c( Figure 3 -r)、f( Figure 3 -s), i( Figure 3 -t) Static contact angle test diagram of the obtained highly hydrophobic PP material surface and water;

[0028] Figure 4 In Application Example 2 of the present invention, low adsorption auxiliary agent a ( Figure 4 -r)、d( Figure 4 -s), g( Figure 4 -t) Static contact angle test diagram of the obtained highly hydrophobic PE material surface and water;

[0029] Figure 5 In Application Example 2 of the present invention, low adsorption aid b( Figure 5 -r)、e( Figure 5 -s), h( Figure 5 -t) Static contact angle test diagram of the obtained highly hydrophobic PE material surface and water;

[0030] Figure 6 In Application Example 2 of the present invention, low adsorption aid c( Figure 6 -r)、f( Figure 6 -s), i( Figure 6 -t) Static contact angle test diagram of the obtained highly hydrophobic PE material surface and water;

[0031] Figure 7 This is a test diagram of the static contact angle between the hydrophobic PP material surface and water obtained in comparative application example 1;

[0032] Figure 8 This is a test diagram of the static contact angle between the hydrophobic PP material surface and water obtained in comparative application example 2;

[0033] Fig. 9 This is a test diagram of the static contact angle between the hydrophobic PP material surface and water obtained in comparative application example 3. DETAILED DESCRIPTION

[0034] The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. The following embodiments are only illustrative and not restrictive, and the protection scope of the present invention cannot be limited thereto.

[0035] When a certain amount, concentration or other value or parameter is expressed in the form of a range, a preferred range, or a preferred upper and lower numerical limit, it should be understood that it is equivalent to specifically revealing any range by combining any pair of upper range limits or preferred numerical values ​​with any lower range limit or preferred numerical value, regardless of whether the range is specifically disclosed. Unless otherwise indicated, the numerical range values ​​listed herein include the endpoints of the range, and all integers and fractions within the range.

[0036] Unless otherwise indicated, all percentages, parts, ratios, etc. herein are by weight.

[0037] The materials, methods, and examples herein are illustrative and are not to be construed as limiting unless specifically stated.

[0038] In the following embodiments, the purity of perfluorobutyl ethyl alcohol is 97%, the purity of perfluorohexyl ethyl alcohol is 97%, the purity of perfluorodecyl methyl alcohol is 95%, the purity of hexamethylene diisocyanate is 99%, the purity of toluene diisocyanate is 98%, and the purity of stearyl alcohol is 98%, all of which are purchased from Anage Chemical; the purity of octadecyl isocyanate is 98%, which is purchased from the exploration platform.

[0039] In the following application examples, the static water contact angle is used as a measurement indicator for the application effect of the hydrophobic efficiency of the low adsorption additive. The test is carried out with reference to the method in GB / T30693-2014. The test sample is a long strip sample of 80mm×10mm×4mm obtained by injection molding, and the test equipment is a JCY-2 contact angle meter.

[0040] Example 1

[0041] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0042] 0.95 equivalents of perfluorobutyl ethyl alcohol and 1 equivalent of octadecyl isocyanate were placed in a reaction system, protected by nitrogen and stirred, reacted at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to prepare a low adsorption auxiliary agent a-N-octadecylcarbamic acid perfluorobutyl ethyl ester, the specific structure of which is as follows:

[0043]

[0044] Example 2

[0045] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0046] 0.95 equivalents of perfluorohexylethyl alcohol and 1 equivalent of octadecyl isocyanate were placed in the reaction system, protected by nitrogen and stirred, reacted at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to prepare a low adsorption auxiliary agent b-N-octadecylcarbamic acid perfluorohexylethyl ester, the specific structure of which is as follows:

[0047]

[0048] Example 3

[0049] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0050] 0.95 equivalents of perfluorodecyl methyl alcohol and 1 equivalent of octadecyl isocyanate were placed in the reaction system, protected by nitrogen and stirred, reacted at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to prepare the low adsorption auxiliary c-N-octadecylcarbamic acid perfluorodecyl methyl ester, the specific structure of which is as follows:

[0051]

[0052] Example 4

[0053] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0054] 1 equivalent of perfluorobutyl ethyl alcohol and 10 equivalents of hexamethylene diisocyanate were placed in a reaction system, and the reaction was carried out under nitrogen protection and stirring, and the reaction was carried out at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 1h; the excess hexamethylene diisocyanate was recovered by vacuum distillation; 0.95 equivalents of stearyl alcohol were added, and the reaction was carried out under nitrogen protection and stirring at 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to obtain a directional low adsorption auxiliary agent d-hexamethylene biscarbamic acid (perfluorobutyl ethyl, stearyl) ester, the specific structure of which is as follows:

[0055]

[0056] Example 5

[0057] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0058] 1 equivalent of perfluorohexylethyl alcohol and 10 equivalents of hexamethylene diisocyanate were placed in a reaction system, protected by nitrogen and stirred, reacted at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 1h; excess hexamethylene diisocyanate was recovered by vacuum distillation; 0.95 equivalents of stearyl alcohol were added, protected by nitrogen and stirred, reacted at 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h, to obtain an oriented low adsorption auxiliary agent e-hexamethylene bisaminocarbamic acid (perfluorohexylethyl, stearyl) ester, the specific structure of which is as follows:

[0059]

[0060] Example 6

[0061] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0062] 1 equivalent of perfluorodecyl methyl alcohol and 10 equivalents of hexamethylene diisocyanate were placed in a reaction system, protected by nitrogen and stirred, reacted at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 1h; excess hexamethylene diisocyanate was recovered by vacuum distillation; 0.95 equivalents of stearyl alcohol were added, protected by nitrogen and stirred, reacted at 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h, to obtain a directional low adsorption auxiliary f-hexamethylene bisamino acid (perfluorodecyl methyl, stearyl) ester, the specific structure of which is as follows:

[0063]

[0064] Example 7

[0065] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0066] 1 equivalent of perfluorobutyl ethyl alcohol and 10 equivalents of toluene diisocyanate were placed in a reaction system, and the mixture was stirred under nitrogen protection, and the reaction was carried out at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally 150°C for 1h. The excess toluene diisocyanate was recovered by vacuum distillation. 0.95 equivalents of stearyl alcohol were added, and the mixture was stirred under nitrogen protection and the reaction was carried out at 80°C for 0.5h, 120°C for 0.5h, and finally 150°C for 2h to obtain a directional low adsorption auxiliary g-2,4-tolyl biscarbamic acid (perfluorobutyl ethyl, stearyl) ester, the specific structure of which is as follows:

[0067]

[0068] Example 8

[0069] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0070] 1 equivalent of perfluorohexylethyl alcohol and 10 equivalents of toluene diisocyanate were placed in a reaction system, and the reaction was carried out under nitrogen protection and stirring, and the reaction was carried out at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 1h; the excess toluene diisocyanate was recovered by vacuum distillation; 0.95 equivalents of stearyl alcohol were added, and the reaction was carried out under nitrogen protection and stirring at 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to obtain a directional low adsorption auxiliary agent h-2,4-tolylbisaminoacid (perfluorohexylethyl, stearyl) ester, the specific structure of which is as follows:

[0071]

[0072] Example 9

[0073] This embodiment provides a method for preparing a directional low-adsorption auxiliary agent, which comprises the following steps:

[0074] 1 equivalent of perfluorodecyl methyl alcohol and 10 equivalents of toluene diisocyanate were placed in a reaction system, and the reaction was carried out under nitrogen protection and stirring, and the reaction was carried out at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 1h; the excess toluene diisocyanate was recovered by vacuum distillation; 0.95 equivalents of stearyl alcohol were added, and the reaction was carried out under nitrogen protection and stirring at 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to obtain an oriented low adsorption auxiliary i-2,4-tolyl bisamino acid (perfluorodecyl methyl, stearyl) ester, the specific structure of which is as follows:

[0075]

[0076] Comparative Example 1

[0077] This comparative example provides a method for preparing a comparative low adsorption auxiliary agent, which comprises the following steps:

[0078] 1.95 equivalents of perfluorohexylethyl alcohol and 1 equivalent of hexamethylene diisocyanate were placed in the reaction system, protected by nitrogen and stirred, reacted at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally at 150°C for 2h to obtain a comparative low adsorption auxiliary agent - hexamethylene biscarbamic acid diperfluorohexylethyl ester, the specific structure of which is as follows:

[0079]

[0080] Application examples:

[0081] The directional low adsorption additive provided in this application is mainly used for surface hydrophobic modification of non-polar polymer materials. Specifically:

[0082] Application Example 1

[0083] This application example provides a method for preparing a highly hydrophobic material using the directional low-adsorption auxiliary agent prepared in the above-mentioned embodiment:

[0084] The directional low-adsorption additives a-i prepared in the example were respectively blended with PP at a ratio of 12:88 by twin-screw melt extrusion to prepare low-adsorption PP masterbatch. Then, the masterbatch and PP were mixed at a ratio of 3:97 by an injection molding machine to prepare a highly hydrophobic PP material.

[0085] In this application example, the static water contact angle of the material surface is measured by JCY-2 contact angle meter. The results are as follows: Figure 1 , Figure 2 and Figure 3 As shown, its static water contact angle is between 120° and 130°.

[0086] The static water contact angle of the original PP material surface tested was 93°.

[0087] Application Example 2

[0088] This application example provides a method for preparing a highly hydrophobic material using the directional low-adsorption auxiliary agent prepared in the above-mentioned embodiment:

[0089] The directional low adsorption additives a-i prepared in the example were respectively mixed with PE at a ratio of 12:88 by twin-screw melt extrusion to prepare low adsorption PE masterbatch. Then, the masterbatch and PE were mixed at a ratio of 3:97 by injection molding machine to prepare highly hydrophobic PE material.

[0090] In this application example, the static water contact angle of the material surface is measured by JCY-2 contact angle meter. The results are as follows: Figure 4 , Figure 5 and Figure 6 As shown, its static water contact angle is between 120° and 130°.

[0091] The static water contact angle of the original PE material surface tested was 91°.

[0092] Comparative application example 1:

[0093] This comparative application example provides a method for preparing a hydrophobic material, which is basically the same as that of Application Example 1, except that the low adsorption auxiliary agent used is paraffin wax commonly used in the art.

[0094] The hydrophobic material prepared in this comparative example was tested by a JCY-2 contact angle meter to obtain the static water contact angle of the material surface. The results are as follows: Figure 7 As shown, its static water contact angle is 106°.

[0095] Comparative application example 2:

[0096] This comparative application example provides a comparative material, and its preparation method is basically the same as that of application example 1, except that the auxiliary agent used is only perfluoroalcohol-perfluorodecyl methyl alcohol.

[0097] The comparative material prepared in this application comparative example was tested by a JCY-2 contact angle meter to obtain the static water contact angle of the material surface. The results are as follows Figure 8 As shown, its static water contact angle is 57°.

[0098] Comparative application example 3:

[0099] This comparative application example provides a method for preparing a hydrophobic material, which is basically the same as that of Application Example 1, except that the low adsorption auxiliary agent used is the low adsorption auxiliary agent corresponding to Comparative Example 1.

[0100] The hydrophobic material prepared in this comparative example was tested by a JCY-2 contact angle meter to obtain the static water contact angle of the material surface. The results are as follows: Fig. 9 As shown, its static water contact angle is 110°.

[0101] By comparing the application examples with the comparative application examples, it can be seen that the low adsorption auxiliary agent provided by the present invention has very excellent hydrophobic properties and can impart a higher static water contact angle to the surface of the non-polar polymer material.

[0102] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. A directional low adsorption auxiliary agent, characterized in that: Its molecular structure includes a perfluorinated straight carbon chain A, a carbamate group B and a hydrocarbon group C, forming an ABC molecular configuration.

2. The directional low adsorption auxiliary agent according to claim 1, characterized in that: The molecular structural formula of the low adsorption auxiliary agent is: In the formula, n is an integer of 3-9, m is an integer of 1-2; and R1 is any one of an aryl group, a cycloalkyl group, and a chain alkyl group.

3. The directional low adsorption auxiliary agent according to claim 1, characterized in that: The molecular structural formula of the low adsorption auxiliary agent is: In the formula, n is an integer of 3-9, m is an integer of 1-2; R2 is any one of hexamethylene, tolyl, and diphenylmethane; and R3 is any one of aryl, cycloalkyl, and chain alkyl.

4. The directional low adsorption auxiliary agent according to claim 1, characterized in that: The perfluorinated straight carbon chain A is provided by a perfluorinated alcohol wherein n+1 is 4-10.

5. The directional low adsorption auxiliary agent according to claim 4, characterized in that: The carbamate group B is provided by any one of a monocarbamate group and a dicarbamate group.

6. The directional low adsorption auxiliary agent according to claim 4, characterized in that: The mono / diurethane group is any one of toluene isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

7. The directional low adsorption auxiliary agent according to claim 5, characterized in that: The hydrocarbon group C is provided by any one of toluene isocyanate, cyclohexyl isocyanate, octadecyl isocyanate and stearyl alcohol.

8. A method for preparing a directional low-adsorption auxiliary agent according to any one of claims 2 and 4-7, characterized in that: The method comprises the following steps: placing 0.95 equivalents of perfluoroalcohol and 1 equivalent of monoisocyanate in a reaction system, protecting with nitrogen and stirring, reacting at 50° C. for 0.5 h, reacting at 80° C. for 0.5 h, reacting at 120° C. for 0.5 h, and finally reacting at 150° C. for 2 h.

9. A method for preparing a directional low-adsorption auxiliary agent according to any one of claims 3 and 4 to 7, characterized in that: The method comprises the following steps: placing 1 equivalent of perfluoroalcohol and 5-15 equivalents of diisocyanate in a reaction system, protecting with nitrogen and stirring, reacting at 50°C for 0.5h, 80°C for 0.5h, 120°C for 0.5h, and finally reacting at 150°C for 1h; recovering excess diisocyanate by vacuum distillation; adding 0.95 equivalents of stearyl alcohol, protecting with nitrogen and stirring, reacting at 80°C for 0.5h, 120°C for 0.5h, and finally reacting at 150°C for 2h.

10. Use of the directional low-adsorption auxiliary agent according to claim 1 in surface hydrophobic modification of non-polar polymer materials.

Images