A preparation method of antistatic agent and antistatic agent

Abstract

The present application relates to the technical field of antistatic agents, and specifically provides a method for preparing an antistatic agent and an antistatic agent. The method for preparing the antistatic agent of the present application comprises the following steps: S1, graphene oxide and a diamino compound to obtain amino-modified graphene oxide; S2, the amino-modified graphene oxide described in step S1 reacts with a double-terminal epoxy polyether polysiloxane block copolymer to obtain modified graphene oxide; S3, the modified graphene oxide described in step S2 reacts with a fatty alcohol polyoxyethylene ether, and is reduced to obtain. The antistatic agent of the present application has good antistatic properties and can improve the yellowing resistance of fabrics.

Description

Technical Field

[0001] The present application relates to the technical field of antistatic agents, and in particular to a preparation method of an antistatic agent and the antistatic agent. Background Art

[0002] Synthetic fibers tend to accumulate static electricity. Finishing synthetic fibers with antistatic agents can provide them with an antistatic effect.

[0003] The antistatic agent used in post-finishing is generally an external antistatic agent, which generally adopts a surfactant with good hydrophilicity or a material with good conductivity, such as graphene. It is a major trend to give the antistatic agent other properties, such as softness and full feel, so that multiple properties can be concentrated in one material, and the fabric can achieve multiple properties after one post-finishing. Summary of the invention

[0004] Combining amino silicone oil with graphene to prepare an antistatic agent not only has antistatic properties, but also provides a smooth, plump, soft and other hand feel, but amino silicone oil is prone to yellowing. In order to solve the problem of yellowing of fabric finishing agents containing amino silicone oil and graphene in the prior art, the present application proposes a preparation method of an antistatic agent and an antistatic agent.

[0005] This application adopts the following technical solutions:

[0006] A method for preparing an antistatic agent comprises the following steps:

[0007] S1, graphene oxide and a diamino compound to obtain amino-modified graphene oxide;

[0008] S2, reacting the amino-modified graphene oxide described in step S1 with the double-terminal epoxy polyether polysiloxane block copolymer to obtain modified graphene oxide;

[0009] S3, the modified graphene oxide in step S2 is reacted with fatty alcohol polyoxyethylene ether and reduced to obtain the antistatic agent.

[0010] Preferably, the general structural formula of the diamino compound in step S1 is NH2R 1 NH2, where R 1 Selected from C2-C18 alkylene or C2-C18 substituted alkylene.

[0011] Preferably, in step S2, the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminated epoxy polyether polysiloxane block copolymer is 1:0.6-7.

[0012] Preferably, the double-terminal epoxy-terminated polyether-polysiloxane block copolymer in step S2 is obtained by a hydrosilylation reaction of epoxy-terminated allyl-terminated polyether and double-terminal hydrogen-terminated polysiloxane.

[0013] More preferably, the general structural formula of the epoxy-terminated allyl-terminated polyether is CH2=CHCH2O(CH2CH2O) a (CH2CHCH3O) b (CH2CHCH2O), wherein a=5-100, b=0-100, a≥b.

[0014] More preferably, the general structural formula of the double-end hydrogen-terminated polysiloxane is HSiMe2O(SiMeR 2 O) c SiMe2H, where R 2 One or more selected from C1-C8 alkyl or substituted C1-C8 alkyl, phenyl and derivatives thereof, Me represents methyl, 10≤c≤300.

[0015] Preferably, the ratio of the molar number of epoxy groups to the molar number of fatty alcohol polyoxyethylene ether in the modified graphene oxide in step S3 is 1:0.5-3.

[0016] Preferably, the structural formula of the fatty alcohol polyoxyethylene ether in step S3 is R 3 O(CH2CH2O) d H, where R 3 A hydrocarbon group selected from C12-C18, d=1-25.

[0017] Preferably, the reducing agent used for the reduction in step S3 is selected from one or more of sodium borohydride, hydrazine hydrate, reducing sugar, ascorbic acid, isoascorbic acid, dimethylhydrazine, hydroquinone, hydroiodic acid and phenylhydrazine.

[0018] An antistatic agent is prepared by the method for preparing an antistatic agent described in any of the above embodiments.

[0019] In summary, the present application has the following beneficial effects: the present application combines amino polyether silicone oil with graphene, and the obtained antistatic agent has good antistatic performance. However, even if the primary amino group in the amino polyether silicone oil reacts to become a secondary amino group and / or a tertiary amine group, it is more likely to turn yellow. The applicant has found that the introduction of fatty alcohol polyoxyethylene ether on the basis of the above structure can reduce the yellowing of the antistatic agent and has little effect on the antistatic performance. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below.

[0021] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In the event of a conflict, the present specification takes precedence.

[0022] On the one hand, the present application provides a method for preparing an antistatic agent, comprising the following steps:

[0023] S1, graphene oxide and a diamino compound to obtain amino-modified graphene oxide;

[0024] S2, reacting the amino-modified graphene oxide described in step S1 with the double-terminal epoxy polyether polysiloxane block copolymer to obtain modified graphene oxide;

[0025] S3, the modified graphene oxide in step S2 is reacted with fatty alcohol polyoxyethylene ether and reduced to obtain the antistatic agent.

[0026] The surface of graphene oxide contains active groups such as epoxy, carboxyl and hydroxyl. In the present application, graphene oxide is not particularly limited and can be selected from Hummers graphene or modified Hummers graphene.

[0027] In a preferred embodiment of the present application, the general structural formula of the diamino compound in step S1 is NH2R 1 NH2, where R 1 Selected from C2-C18 alkylene or C2-C18 substituted alkylene, specifically, ethylenediamine, 1,4-butylene diamine, 1,6-hexanediamine, 1,8-octanediamine, 1,12-dodecyl diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. In step S1, the weight ratio of graphene oxide to the bisamino compound can be 1:0.03-0.2. By controlling the weight ratio of graphene oxide to the bisamino compound within the above range, the epoxy groups on the surface of the graphene oxide can react more completely with the bisamino compound.

[0028] In a preferred embodiment of the present application, the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminated epoxy polyether polysiloxane block copolymer in step S2 is 1:0.6-7.

[0029] In the above technical scheme, the number of moles of amino groups in amino-modified graphene oxide refers to the number of moles of primary amino groups. Amino groups include primary amino groups and secondary amino groups. For example, the amino-modified graphene oxide obtained by the reaction of 1,8-octanediamine with the epoxy groups on the surface of graphene oxide contains primary amino groups (derived from 1,8-octanediamine) and secondary amino groups (derived from the secondary amino groups after the ring-opening of 1,8-octanediamine and epoxy groups), and the amino-modified graphene oxide obtained by the reaction of divinyltriamine with the epoxy groups on the surface of graphene oxide contains primary amino groups (derived from divinyltriamine) and secondary amino groups (derived from the secondary amino groups in divinyltriamine and the secondary amino groups after the ring-opening of divinyltriamine and epoxy groups).

[0030] In the present application, more preferably, when R 1 is selected from C2-C18 alkylene, and the ratio of the number of moles of amino groups in the amino-modified graphene oxide to the number of moles of the double-terminal epoxy polyether polysiloxane block copolymer in step S2 is 1:2-4. 1 The group is selected from C2-C18 substituted alkylene, especially amino substituted alkylene, and the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer in step S2 is 1:4-7.

[0031] In a preferred embodiment of the present application, the double-terminal epoxy-polyether-polysiloxane block copolymer in step S2 is obtained by hydrosilylation reaction of epoxy-terminated allyl polyether and double-terminal hydrogen-terminated polysiloxane. The double-terminal epoxy-polyether-polysiloxane block copolymer is prepared by hydrosilylation reaction of epoxy-terminated allyl polyether and double-terminal hydrogen-terminated polysiloxane, and the reaction conditions are relatively mild, the conversion rate is high, and the purity is high.

[0032] In a more preferred embodiment of the present application, the general structural formula of the epoxy-terminated allyl-terminated polyether is CH2=CHCH2O(CH2CH2O) a (CH2CHCH3O) b CH2(CHCH2O), wherein a=5-100, b=0-100, a≥b. In order to improve the antistatic performance and hydrophilicity of the antistatic agent, the epoxy-terminated allyl polyether of the present application is hydrophilic. Further preferably, b≤0.5a.

[0033] In a more preferred embodiment of the present application, the general structural formula of the double-terminal hydrogen-terminated polysiloxane is HSiMe2O(SiMeR 2 O) c SiMe2H, where R 2 is selected from one or more of C1-C8 alkyl or substituted C1-C8 alkyl, phenyl and derivatives thereof, Me represents methyl, 10≤c≤300. Specifically, R 2It may be methyl, phenyl, 3,3,3-trifluoropropyl, ethyl, propyl, 3-chloropropyl, etc. More preferably, 20≤c≤150.

[0034] In a preferred embodiment of the present application, the ratio of the number of moles of epoxy groups in the modified graphene oxide to the number of moles of fatty alcohol polyoxyethylene ether in step S3 is 1:0.5-3. The epoxy groups of the modified graphene oxide in step S3 mainly come from the double-ended epoxy polyether polysiloxane block copolymer, and the two epoxy groups in the double-ended epoxy polyether polysiloxane block copolymer can be one epoxy group reacting with the amino group, or part of the two epoxy groups reacting with the amino group. After the epoxy group reacts with the fatty alcohol polyoxyethylene ether, the fatty alcohol polyoxyethylene ether is grafted to the end group of the polyether polysiloxane block copolymer to form a graphene-polyether-polysiloxane-polyether-polyether-alkyl structure. In the present application, the long-chain alkyl and polyether structure in the fatty alcohol polyoxyethylene ether can have a certain shielding effect on the secondary amino and / or tertiary amine groups in the graphene-polyether polysiloxane block copolymer, reducing the yellowing of the secondary amino and / or tertiary amine groups. More preferably, the ratio of the molar number of epoxy groups to the molar number of fatty alcohol polyoxyethylene ether in the modified graphene oxide is 1:0.8-1.5.

[0035] In the preferred embodiment of the present application, the general structural formula of the fatty alcohol polyoxyethylene ether in step S3 is R 3 O(CH2CH2O) d H, where R 3 A hydrocarbon group selected from C12-C18, d=1-25. More preferably, d=9-25. The hydrophilicity of fatty alcohol polyoxyethylene ether is good, which can further improve the antistatic performance of the antistatic agent, and the molecular chain is longer, and the shielding effect is better. 3 The hydrocarbon group selected from C12-C18 is a long-chain hydrocarbon group and can provide a better shielding effect.

[0036] In a preferred embodiment of the present application, the reducing agent used for reduction in step S3 is selected from one or more of sodium borohydride, hydrazine hydrate, reducing sugar, ascorbic acid, isoascorbic acid, dimethylhydrazine, hydroquinone, hydroiodic acid and phenylhydrazine. The amount of the reducing agent can be 2-10 times the weight of the modified graphene oxide in step S3, the reduction temperature is 60-130° C., and the reduction time is 1-5 hours.

[0037] On the other hand, the present application provides an antistatic agent, which is prepared by the preparation method of the antistatic agent described in any of the above embodiments.

[0038] The antistatic agent of the present application can be directly dissolved in water to form a dispersion, and the concentration can be 1-30 wt %. The pH of the dispersion can be adjusted to 5-6 by using an acid.

[0039] The technical solution of the present application will be described in detail below with reference to embodiments, comparative examples and experimental data.

[0040] Preparation Example 1-4 Preparation of double-terminal epoxy polyether polysiloxane block copolymer

[0041] Ingredients

[0042] Polyether 1: CH2=CHCH2O(CH2CH2O) 57.3 (CH2CHCH3O) 10.6 CH2(CHCH2O);

[0043] Polyether 2: CH2=CHCH2O(CH2CH2O) 33.8 (CH2CHCH2O);

[0044] Double-terminal hydrogen-terminated polysiloxane 1: HSiMe2O (SiMe2O) 67.1 SiMe2H;

[0045] Double-terminal hydrogen-terminated polysiloxane 2: HSiMe2O (SiMe2O) 41.5 SiMe2H;

[0046] Preparation Example 1

[0047] Polyether 1 and double-end hydrogen-terminated polysiloxane 1 were added to a reaction vessel in a molar ratio of 2:1, the temperature was raised to 85°C, nitrogen was passed through, Karstedt catalyst (based on the amount of Pt, the amount added was 12 ppm), and the reaction was carried out at a constant temperature of 130-135°C for 3 hours to obtain a double-end epoxy polyether polysiloxane block copolymer.

[0048] Preparation Example 2

[0049] Polyether 1 and double-end hydrogen-terminated polysiloxane 2 were added to a reaction vessel in a molar ratio of 2.02:1, the temperature was raised to 85°C, nitrogen was passed through, Karstedt catalyst (based on the amount of Pt, the amount added was 12 ppm), and the reaction was carried out at a constant temperature of 130-135°C for 3 hours to obtain a double-end epoxy polyether polysiloxane block copolymer.

[0050] Preparation Example 3

[0051] Polyether 2 and double-end hydrogen-terminated polysiloxane 1 were added to a reaction vessel in a molar ratio of 2.01:1, the temperature was raised to 85°C, nitrogen was passed through, Karstedt catalyst (based on the amount of Pt, the amount added was 12 ppm), and the reaction was carried out at a constant temperature of 130-135°C for 3 hours to obtain a double-end epoxy polyether polysiloxane block copolymer.

[0052] Preparation Example 4

[0053] Polyether 2 and double-end hydrogen-terminated polysiloxane 2 were added to a reaction vessel in a molar ratio of 2:1, the temperature was raised to 85°C, nitrogen was passed through, Karstedt catalyst (based on the amount of Pt, the amount added was 12 ppm), and the reaction was carried out at a constant temperature of 130-135°C for 3 hours to obtain a double-end epoxy polyether polysiloxane block copolymer.

[0054] Example 1

[0055] Disperse 10 parts of Hummers graphene oxide in 1000 parts of anhydrous ethanol, add 0.6 parts of 1,4-butanediamine, stir and react for 3 hours, centrifuge, wash the solid with anhydrous ethanol once, and dry at 60°C overnight to obtain amino-modified graphene oxide; add the above-mentioned amino-modified graphene oxide and the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 1 into a container according to the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer of 1:2.5, add anhydrous ethanol 20 times the weight of the double-terminal epoxy polyether polysiloxane block copolymer, stir and react for 2 hours after ultrasonic dispersion, heat to 50°C and continue to react for 2 hours, filter, wash the solid with anhydrous ethanol once, and dry at 60°C overnight to obtain modified graphene oxide;

[0056] The modified graphene oxide and fatty alcohol polyoxyethylene ether C 12 H 25 O(CH2CH2O) 12.6 H is added into a reaction container according to the molar ratio of epoxy groups in the modified graphene oxide to the molar ratio of fatty alcohol polyoxyethylene ether of 1:1.2, 20 times the weight of the modified graphene oxide and fatty alcohol polyoxyethylene ether and 1% of 2-methylimidazole are added, the temperature is raised to 90° C. for reaction for 3 hours, ascorbic acid is added in an amount of 2 times the weight of the modified graphene oxide, the temperature is raised to 100° C. for reaction for 2 hours, the temperature is lowered, the solid is centrifuged, the solid is washed twice with anhydrous ethanol, and dried at 60° C. overnight to obtain an antistatic agent.

[0057] Example 2

[0058] Disperse 10 parts of Hummers graphene oxide in 1000 parts of anhydrous ethanol, add 0.12 parts of 1,8-octanediamine, stir and react for 3 hours, centrifuge, wash the solid with anhydrous ethanol once, and dry at 60°C overnight to obtain amino-modified graphene oxide;

[0059] The amino-modified graphene oxide and the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 2 are added into a container at a ratio of 1:3 between the molar number of amino groups in the amino-modified graphene oxide and the molar number of the double-terminal epoxy polyether polysiloxane block copolymer, and anhydrous ethanol in an amount of 25 times the weight of the double-terminal epoxy polyether polysiloxane block copolymer is added, and stirred for reaction for 2 hours after ultrasonic dispersion, and the temperature is raised to 50° C. and the reaction is continued for 2 hours, filtered, and the solid is washed once with anhydrous ethanol, and dried at 60° C. overnight to obtain modified graphene oxide;

[0060] The modified graphene oxide and fatty alcohol polyoxyethylene ether C 18 H 37 O(CH2CH2O) 15.1 H is added into a reaction container at a molar ratio of 1:0.9 between the number of moles of epoxy groups in the modified graphene oxide and the number of moles of fatty alcohol polyoxyethylene ether, and 20 times the weight of the modified graphene oxide and fatty alcohol polyoxyethylene ether and 1% of 2-methylimidazole are added. The temperature is raised to 90° C. for reaction for 3 hours. Ascorbic acid is added in an amount of 3 times the weight of the modified graphene oxide, and the temperature is maintained at 90° C. for reaction for 2 hours. The temperature is lowered, the mixture is centrifuged, and the solid is washed twice with anhydrous ethanol and dried overnight at 60° C. to obtain an antistatic agent.

[0061] Example 3

[0062] Disperse 10 parts of Hummers graphene oxide in 1000 parts of anhydrous ethanol, add 1.5 parts of diethylenetriamine, stir and react for 2.5 hours, centrifuge, wash the solid with anhydrous ethanol once, and dry at 60°C overnight to obtain amino-modified graphene oxide;

[0063] The amino-modified graphene oxide and the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 3 are added into a container according to the molar ratio of the amino group in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer of 1:4, and anhydrous ethanol in an amount of 25 times the weight of the double-terminal epoxy polyether polysiloxane block copolymer is added, and stirred for reaction for 2 hours after ultrasonic dispersion, and the temperature is raised to 50° C. and the reaction is continued for 2 hours, and filtered, and the solid is washed once with anhydrous ethanol, and dried at 60° C. overnight to obtain modified graphene oxide;

[0064] The modified graphene oxide and fatty alcohol polyoxyethylene ether C 12 H 25 O(CH2CH2O) 9.2H is added into a reaction container at a molar ratio of 1:1.4 between the number of moles of epoxy groups in the modified graphene oxide and the number of moles of fatty alcohol polyoxyethylene ether, and 30 times the weight of the modified graphene oxide and fatty alcohol polyoxyethylene ether and 1% of 2-methylimidazole are added. The temperature is raised to 80° C. for reaction for 4 hours. Hydrazine hydrate in an amount of 3 times the weight of the modified graphene oxide is added. The temperature is maintained at 80° C. for reaction for 3 hours. The temperature is lowered and centrifuged. The solid is washed twice with anhydrous ethanol and dried overnight at 60° C. to obtain an antistatic agent.

[0065] Example 4

[0066] Disperse 10 parts of Hummers graphene oxide in 1000 parts of anhydrous ethanol, add 1 part of 1,6-hexanediamine, stir and react for 3 hours, centrifuge, wash the solid with anhydrous ethanol once, and dry at 60°C overnight to obtain amino-modified graphene oxide; add the above-mentioned amino-modified graphene oxide and the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 4 into a container according to the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer of 1:3.5, add anhydrous ethanol 25 times the weight of the double-terminal epoxy polyether polysiloxane block copolymer, stir and react for 2 hours after ultrasonic dispersion, heat to 50°C and continue to react for 2 hours, filter, wash the solid with anhydrous ethanol once, and dry at 60°C overnight to obtain modified graphene oxide;

[0067] The modified graphene oxide and fatty alcohol polyoxyethylene ether C 12 H 25 O(CH2CH2O) 6.5 H is added into a reaction container at a molar ratio of 1:1.1 between the number of moles of epoxy groups in the modified graphene oxide and the number of moles of fatty alcohol polyoxyethylene ether, and 30 times the weight of the modified graphene oxide and fatty alcohol polyoxyethylene ether and 1% of 2-methylimidazole are added. The temperature is raised to 80° C. for reaction for 4 hours. Hydrazine hydrate in an amount of 3 times the weight of the modified graphene oxide is added. The temperature is maintained at 80° C. for reaction for 3 hours. The temperature is lowered and centrifuged. The solid is washed twice with anhydrous ethanol and dried overnight at 60° C. to obtain an antistatic agent.

[0068] Example 5

[0069] Disperse 10 parts of Hummers graphene oxide in 1000 parts of anhydrous ethanol, add 2 parts of triethylenetetramine, stir and react for 2.5 hours, centrifuge, wash the solid once with anhydrous ethanol, and dry at 60°C overnight to obtain amino-modified graphene oxide;

[0070] The amino-modified graphene oxide and the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 1 are added into a container at a ratio of 1:4.5 between the molar number of amino groups in the amino-modified graphene oxide and the molar number of the double-terminal epoxy polyether polysiloxane block copolymer, and anhydrous ethanol in an amount of 25 times the weight of the double-terminal epoxy polyether polysiloxane block copolymer is added, and stirred for reaction for 2 hours after ultrasonic dispersion, and the temperature is raised to 50° C. and the reaction is continued for 2 hours, and filtered, and the solid is washed once with anhydrous ethanol, and dried at 60° C. overnight to obtain modified graphene oxide;

[0071] The modified graphene oxide and fatty alcohol polyoxyethylene ether C 12 H 25 O(CH2CH2O) 12.6 H is added into a reaction container at a molar ratio of 1:1.1 between the number of moles of epoxy groups in the modified graphene oxide and the number of moles of fatty alcohol polyoxyethylene ether, and 30 times the weight of the modified graphene oxide and fatty alcohol polyoxyethylene ether and 1% of 2-methylimidazole are added. The temperature is raised to 80° C. for reaction for 4 hours. Hydrazine hydrate in an amount of 3 times the weight of the modified graphene oxide is added. The temperature is maintained at 80° C. for reaction for 3 hours. The temperature is lowered and centrifuged. The solid is washed twice with anhydrous ethanol and dried overnight at 60° C. to obtain an antistatic agent.

[0072] Example 6

[0073] In Example 5, the ratio of the amino-modified graphene oxide to the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 1 is adjusted to: the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer is 1:3, and the other steps remain unchanged.

[0074] Example 7

[0075] In Example 5, the ratio of the amino-modified graphene oxide to the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 1 is adjusted to: the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer is 1:4, and the other steps remain unchanged.

[0076] Example 8

[0077] In Example 5, the ratio of the amino-modified graphene oxide to the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 1 is adjusted to: the ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminal epoxy polyether polysiloxane block copolymer is 1:5, and the other steps remain unchanged.

[0078] Example 9

[0079] In Example 5, fatty alcohol polyoxyethylene ether C 12 H 25O(CH2CH2O) 12.6 H was replaced by an equimolar amount of C 18 H 37 O(CH2CH2O) 15.1 H, the rest of the steps remain unchanged.

[0080] Comparative Example 1

[0081] The amino-modified graphene oxide of Example 5 and the double-terminal epoxy polyether polysiloxane block copolymer of Preparation Example 1 were added into a container at a ratio of 1:4.5 between the molar number of amino groups in the amino-modified graphene oxide and the molar number of the double-terminal epoxy polyether polysiloxane block copolymer, and anhydrous ethanol in an amount of 25 times the weight of the double-terminal epoxy polyether polysiloxane block copolymer was added, and the mixture was stirred and reacted for 2 hours after ultrasonic dispersion, and the temperature was raised to 50° C. and the reaction was continued for 2 hours, and hydrazine hydrate in an amount of 3 times the weight of the modified graphene oxide was added, and the temperature was raised to 80° C. and the reaction was continued for 3 hours, and the temperature was lowered, and the mixture was filtered, and the solid was washed twice with anhydrous ethanol and dried at 60° C. overnight to obtain modified graphene oxide.

[0082] Comparative Example 2

[0083] In Example 5, fatty alcohol polyoxyethylene ether C 12 H 25 O(CH2CH2O) 12.6 H was replaced with an equimolar amount of C5H 11 O(CH2CH2O) 12.1 H, the rest of the steps remain unchanged.

[0084] Comparative Example 3

[0085] In Example 5, fatty alcohol polyoxyethylene ether C 12 H 25 O(CH2CH2O) 12.6 H was replaced by an equimolar amount of n-dodecanol, and the rest of the steps remained unchanged.

[0086] Application Testing

[0087] 80 parts of water with a pH value of 5.0 were gradually added to 20 parts of the antistatic agents of Examples 1-9 and Comparative Examples 1-3 which were stirred at high speed, respectively, and after being stirred and dispersed uniformly, the pH value was adjusted to 5.5-6.0 to obtain an antistatic agent emulsion.

[0088] Fabric treatment: The above antistatic agent emulsion was formulated into a 20g / L finishing agent, and pure cotton bleached cloth was finished by a two-immersion and two-binding process, dried at 100°C for 5 minutes, and fixed at 180°C for 30 seconds.

[0089] Antistatic performance: Tested in accordance with the method of GB / T 12703.4-2010 "Evaluation of electrostatic properties of textiles Part 4: Resistivity".

[0090] Yellowing test: Use ColorQuest colorimeter to test the whiteness value of the finished fabric and compare it with the whiteness value of the fabric before finishing. Whiteness ratio = whiteness value of the fabric after finishing / whiteness value of the fabric before finishing × 100%.

[0091] Irradiation yellowing degree: According to the method of GB / T30669-2014, the colorimeter of ColorQuest is used for testing, with a wavelength of 340nm and an irradiance of 0.8W / (m 2 ·nm) ultraviolet light irradiation for 60h, test the whiteness value after irradiation, and use color cards to test the yellowing level. Yellowing level: 5 points, no yellowing at all; 4 points, slight yellowing (yellowing is not obvious); 3 points, slight yellowing (yellowing is slightly obvious); 2 points, slightly serious yellowing (yellowing is obvious); 1 point, very serious yellowing (yellowing is very obvious). Each test piece is tested with 10 pieces, and 10 trained volunteers each take 1 piece to evaluate the score, and retain it to one decimal place. The average of the 10 scores is retained to one decimal place.

[0092] The results are shown in Table 1 below.

[0093] Table 1

[0094] Resistivity / Ω·m Whiteness ratio / % Yellowing grade / points Example 1 6.3×106 80.2 4.5 Example 2 2.7×106 83.5 4.8 Example 3 7.1×105 81.8 4.5 Example 4 1.2×106 79.6 4.4 Example 5 3.6×105 81.7 4.4 Example 6 7.9×105 78.4 4.1 Example 7 5.5×105 80.1 4.3 Example 8 2.4×105 83.6 4.7 Example 9 5.1×105 84.5 4.7 Comparative Example 1 4.3×105 77.3 4.0 Comparative Example 2 3.1×105 78.5 4.2 Comparative Example 3 7.5×105 78.1 4.1

[0095] It can be seen from the data results in Table 1 that the antistatic agent of the present application has a good antistatic effect, and the fatty alcohol polyoxyethylene ether structure is introduced into the antistatic agent structure, which improves the inhibitory effect on the yellowing of amino groups (including secondary amino groups and tertiary amino groups). After the fabric is finished, the yellowing resistance of the fabric is improved.

[0096] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A method for preparing an antistatic agent, characterized in that: The following steps are involved: S1, graphene oxide and a diamino compound to obtain amino-modified graphene oxide; S2, the amino-modified graphene oxide described in step S1 reacts with a double-terminal epoxy polyether polysiloxane block copolymer to obtain modified graphene oxide; S3, the modified graphene oxide described in step S2 reacts with a fatty alcohol polyoxyethylene ether, and is reduced to obtain the antistatic agent.

2. The method for preparing an antistatic agent according to claim 1, characterized in that: The general structural formula of the diamino compound in step S1 is NH2R 1 NH2, where R 1 Selected from C2-C18 alkylene or C2-C18 substituted alkylene.

3. The method for preparing an antistatic agent according to claim 1, characterized in that: The ratio of the molar number of amino groups in the amino-modified graphene oxide to the molar number of the double-terminated epoxy polyether polysiloxane block copolymer in step S2 is 1:0.6-7.

4. The method for preparing an antistatic agent according to claim 1, characterized in that: The double-terminal epoxy polyether polysiloxane block copolymer in step S2 is obtained by a hydrosilylation reaction of epoxy-terminated allyl polyether and double-terminal hydrogen-terminated polysiloxane.

5. The method for preparing an antistatic agent according to claim 4, characterized in that: The general structural formula of the epoxy-terminated allyl-terminated polyether is CH2=CHCH2O(CH2CH2O) a (CH2CHCH3O) b (CH2CHCH2O), where a=5-100, b=0-100, a≥b.

6. The method for preparing an antistatic agent according to claim 4, characterized in that: The general structural formula of the double-end hydrogen-terminated polysiloxane is HSiMe2O(SiMeR 2 O) c SiMe2H, where R 2 One or more selected from C1-C8 alkyl or substituted C1-C8 alkyl, phenyl and derivatives thereof, Me represents methyl, 10≤c≤300.

7. The method for preparing an antistatic agent according to claim 1, characterized in that: The ratio of the molar number of epoxy groups to the molar number of fatty alcohol polyoxyethylene ether in the modified graphene oxide in step S3 is 1:0.5-3.

8. The method for preparing an antistatic agent according to claim 1, characterized in that: The general structural formula of the fatty alcohol polyoxyethylene ether in step S3 is R 3 O(CH2CH2O) d H, where R 3 Selected from C12-C18 hydrocarbon groups, d=1-25.

9. The method for preparing an antistatic agent according to claim 1, characterized in that: The reducing agent used for the reduction in step S3 is selected from one or more of sodium borohydride, hydrazine hydrate, reducing sugar, ascorbic acid, isoascorbic acid, dimethylhydrazine, hydroquinone, hydroiodic acid and phenylhydrazine.

10. An antistatic agent, characterized in that The antistatic agent is prepared by the preparation method of the antistatic agent according to any one of claims 1 to 9.