A composite antistatic additive, preparation method and application in spinning nylon filament

Abstract

The present invention relates to the field of polymer material technology, and discloses a composite antistatic auxiliary agent, preparation method and application in spinning nylon filament. The composite antistatic auxiliary agent is obtained by mixing an organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether, and nano carbon black with a mass ratio of (4-6): (2-4): (1-2); the organic-inorganic hybrid antistatic agent of the present invention is obtained by copolymerization of grafted modified nano zinc oxide, intermediate product B, and composite modified quaternary ammonium salt compound, and can be coordinated from multiple aspects to play excellent antistatic, antibacterial, and anti-ultraviolet effects, for spinning nylon filament, can be firmly adhered to nylon filament, with good water resistance, the organic-inorganic hybrid antistatic agent is then compounded with octylphenol polyoxyethylene ether and nano carbon black, and better antistatic effect can be played.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a composite antistatic auxiliary agent, a preparation method and application in spinning nylon filaments. Background Art

[0002] Nylon (polyamide) filaments have a range of excellent properties, such as elasticity, wear resistance, and corrosion resistance, but they also suffer from the disadvantages of poor light fastness, antistatic properties, and antibacterial properties. To improve their antistatic properties, adding an antistatic agent during the preparation process is a common method. Polyether is a polymer antistatic agent widely used in various fields. For example, Chinese patent application CN103131158A discloses an antistatic masterbatch. Its formula is composed of the following weight percentages: 50-72% masterbatch base material, 9-13% carbon black, 8-13% antistatic agent, 7-15% maleic anhydride grafted compatibilizer, 9-15% soap solution, and 7-13% antioxidant. The antistatic agent is fatty alcohol polyoxyethylene ether. The masterbatch is simple to prepare, has low production costs, and has strong antistatic properties. However, due to the low polarity of the ether bond, the antistatic performance of polyether antistatic agent is weak. Only by adding a large amount of it can a good antistatic effect be achieved. Moreover, when it is used alone in nylon material, it cannot solve the problem of poor light resistance and antibacterial properties of nylon material. Summary of the Invention

[0003] In order to solve the above technical problems, the present invention provides a method for preparing a composite antistatic additive, comprising the following steps:

[0004] Step (1), using zinc nitrate as a metal precursor and sucrose as a porogen to prepare mesoporous nano zinc oxide; the mesoporous nano zinc oxide is modified with 3-glycidyloxypropyltrimethoxysilane and then loaded with 1-allyl-3-ethylimidazolium chloride to obtain loaded modified nano zinc oxide;

[0005] Step (2), after allyl polyoxyethylene ether is modified with maleic anhydride, it is grafted onto the supported modified nano zinc oxide to obtain grafted modified nano zinc oxide;

[0006] Step (3), glucose and thiourea react to obtain intermediate product A; intermediate product A reacts with thionyl chloride, and then reacts with 4-penten-1-amine to obtain intermediate product B;

[0007] Graft-modified nano zinc oxide, intermediate product B, and composite modified quaternary ammonium salt compound are copolymerized to obtain an organic-inorganic hybrid antistatic agent;

[0008] The organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether and nano carbon black are mixed to obtain a composite antistatic auxiliary agent;

[0009] The preparation method of the composite modified quaternary ammonium salt compound comprises the following steps:

[0010] Step S1: 1,3-bis(dimethylamino)-2-propanol reacts with oxalyl chloride to obtain an intermediate product C; and the intermediate product C reacts with chloropropane to obtain a quaternary ammonium salt compound;

[0011] Step S2: After the quaternary ammonium salt compound is grafted with mercaptoethylamine, it reacts with magnolol to obtain a composite modified quaternary ammonium salt compound.

[0012] Preferably, in the step (1), the preparation method of the mesoporous nano zinc oxide is as follows: zinc nitrate hexahydrate, sucrose, ammonium chloride, ethanol, deionized water, and 25% ammonia water are mixed in a mass ratio of (8.9-17.8): (10.3-20.6): (1.6-3.2): (8-16): (10-20): (9.1-18.2), and stirred until uniform to obtain an aqueous phase; Span 80, Tween 80, and kerosene are mixed in a mass ratio of (3.5-7): (1.9-3.8): (39.5-79) The mixture was mixed and stirred until uniform to obtain an oil phase; at room temperature, the aqueous phase was dropwise added to the oil phase at a rate of 1-1.5 mL / min, and stirred to obtain a transparent water-in-oil microemulsion; the mixture was then stirred at 79-81° C. and 0.01 MPa for 4.5-5.5 hours, naturally cooled to room temperature, and centrifuged; the resulting precipitate was added to cyclohexane, and maintained at 89-91° C. for 70-75 hours to obtain a sucrose / ZnO composite material; and the sucrose / ZnO composite material was extracted with ethanol Soxhlet for 20-30 hours to obtain mesoporous nano-zinc oxide with an average particle size of 150 nm.

[0013] Preferably, in step (1), the preparation method of the loaded modified nano zinc oxide is as follows: 3-glycidyloxypropyltrimethoxysilane and mesoporous nano zinc oxide are dispersed in ethanol, and then refluxed for 4-6 hours at a temperature of 75-80°C and a pH value of 4-5, centrifuged, washed, and dried to obtain surface-modified nano zinc oxide; wherein the mass ratio of 3-glycidyloxypropyltrimethoxysilane, mesoporous nano zinc oxide, and ethanol is (1-3):(10-15):(100-120);

[0014] 1-allyl-3-ethylimidazolium chloride is added to ethanol, and after ultrasonic treatment for 20-40 minutes, surface-modified nano-zinc oxide is added, and the mixture is stirred at room temperature for 8-12 hours, filtered, washed, and dried to obtain loaded modified nano-zinc oxide; wherein the mass ratio of 3-glycidyloxypropyltrimethoxysilane, mesoporous nano-zinc oxide, and ethanol is (5-10):(60-80):(3-5);

[0015] In the above process, zinc nitrate is used as a metal precursor and sucrose is used as a porogen, and the reverse microemulsion evaporation-induced self-assembly technology is adopted to synthesize mesoporous nano-zinc oxide; then the surface of the mesoporous nano-zinc oxide is modified by 3-glycidyloxypropyltrimethoxysilane, and epoxy groups are introduced on the surface of the mesoporous nano-zinc oxide; then the ionic liquid 1-allyl-3-ethylimidazolium chloride is loaded into the mesoporous nano-zinc oxide by the impregnation method to obtain loaded modified nano-zinc oxide.

[0016] Preferably, in step (2), the preparation method of the grafted modified nano zinc oxide is:

[0017] Add allyl polyoxyethylene ether to chloroform, then add maleic anhydride and 4-dimethylaminopyridine, and react at room temperature for 60-80 hours. After the reaction is completed, evaporate the solvent to obtain modified allyl polyoxyethylene ether; wherein the mass ratio of allyl polyoxyethylene ether, chloroform, maleic anhydride, and 4-dimethylaminopyridine is (10-12):(80-100):(2.5-3):(0.05-0.1);

[0018] Add modified allyl polyoxyethylene ether and tetrabutylammonium bromide to deionized water and stir until uniform to obtain a mixed solution A; add the loaded modified nano zinc oxide to deionized water, ultrasonically disperse for 20-40 minutes, and then dropwise add the mixed solution A at a rate of 1-1.5 mL / min. After the dropwise addition, heat to reflux and stir to react for 2-3 hours. After the reaction is completed, centrifuge, wash, and dry to obtain grafted modified nano zinc oxide; wherein the mass ratio of modified allyl polyoxyethylene ether, tetrabutylammonium bromide, and loaded modified nano zinc oxide is (8-12):(0.2-0.5):(4-6);

[0019] In the above process, maleic anhydride ring-opening reacts with the hydroxyl group of allyl polyoxyethylene ether to generate carboxyl group, thereby obtaining carboxylated modified allyl polyoxyethylene ether; the carboxyl group of the modified allyl polyoxyethylene ether reacts with the epoxy group on the surface of the loaded modified nano-zinc oxide to encapsulate the loaded modified nano-zinc oxide, thereby preventing the leakage of the ionic liquid during subsequent treatment and controlling the release rate of the ionic liquid.

[0020] Preferably, in step (3), the preparation method of the intermediate product B is as follows: glucose, thiourea and deionized water are mixed to obtain a reaction solution, wherein the concentration of glucose in the reaction solution is 50 g / L, and the mass ratio of glucose to thiourea is 1:(0.8-1.7); the pH of the reaction solution is adjusted to 12-12.5 by adding a 3 mol / L sodium hydroxide aqueous solution, reacting at 88-92° C. for 100-150 min, distilling, washing and drying to obtain the intermediate product A;

[0021] Add intermediate product A and thionyl chloride to N,N-dimethylformamide, heat to 55-65°C for reaction for 20-28 hours, raise the temperature to 85-92°C, add 4-penten-1-amine, continue to react at 85-92°C for 20-28 hours, and rotary evaporate to obtain intermediate product B; wherein the mass ratio of intermediate product A, thionyl chloride, N,N-dimethylformamide, and 4-penten-1-amine is (2-5):(6-10):(120-150):(3-5);

[0022] In the above process, glucose and thiourea react to form a Maillard product, namely intermediate product A; the carboxyl group in intermediate product A reacts with thionyl chloride to convert into an acyl chloride, which then reacts with the amino group of 4-penten-1-amine to form an amide bond, and introduces a carbon-carbon double bond into intermediate product B.

[0023] Preferably, in the step (3), the preparation method of the organic-inorganic hybrid antistatic agent is as follows: adding the grafted modified nano zinc oxide, the intermediate product B, and the composite modified quaternary ammonium salt compound to N,N-dimethylformamide, stirring for 40-60 minutes, then adding azobisisobutyronitrile, heating to 75-80°C, continuing to stir for 5-6 hours, filtering, washing, and drying to obtain the organic-inorganic hybrid antistatic agent; wherein the mass ratio of the grafted modified nano zinc oxide, the intermediate product B, the composite modified quaternary ammonium salt compound, N,N-dimethylformamide, and azobisisobutyronitrile is (2-5):(1.5-3.5):(6-10):(120-150):(0.08-0.12);

[0024] In the above process, the intermediate product B containing a carbon-carbon double bond and the composite modified quaternary ammonium salt compound copolymerize with the double bond in the allyl polyoxyethylene ether grafted onto the surface of the nano-zinc oxide to form an organic polymer cross-linked network structure on the surface of the nano-zinc oxide to obtain an organic-inorganic hybrid antistatic agent;

[0025] Preferably, in step (3), the mass ratio of the organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether, and nano carbon black is (4-6):(2-4):(1-2).

[0026] Furthermore, in step (3), the preparation method of the composite modified quaternary ammonium salt compound comprises the following steps:

[0027] Step S1, adding 1,3-bis(dimethylamino)-2-propanol to N,N-dimethylformamide, and adding dropwise a 9.5% mass fraction of oxalyl chloride / N,N-dimethylformamide mixture at a rate of 0.8-1.2 mL / min in an ice-water bath with stirring, stirring for 1.5-2.5 hours, and then continuing the reaction at room temperature for 3.5-4.5 hours. After the reaction is completed, rotary evaporation is performed to obtain an intermediate product C; wherein the mass ratio of 1,3-bis(dimethylamino)-2-propanol, N,N-dimethylformamide, and oxalyl chloride / N,N-dimethylformamide mixture is (1.5-3):(50-80):(20-35);

[0028] Under stirring conditions, the intermediate product C and acetone are mixed, and then chloropropane is added dropwise at a rate of 0.8-1.2 mL / min. After the addition is completed, the mixture is stirred and reacted at 38-42° C. for 20-28 hours. After the reaction is completed, the mixture is evaporated to obtain a quaternary ammonium salt compound; wherein the mass ratio of the intermediate product C, acetone, and chloropropane is (2.4-3.6):(50-80):(1.8-4.2);

[0029] In the above process, the hydroxyl group in 1,3-bis(dimethylamino)-2-propanol undergoes an esterification reaction with the acyl chloride at one end of oxalyl chloride to obtain an intermediate product C; the intermediate product C combines with chloropropane through a quaternization reaction to form a quaternary ammonium compound containing two quaternary ammonium groups;

[0030] Step S2, adding a quaternary ammonium salt compound to tetrahydrofuran, stirring for 20-40 minutes, and adding dropwise a 6.3% mass fraction of mercaptoethylamine / methanol mixture at a rate of 1-2 mL / min in a nitrogen atmosphere. After the addition is complete, stirring and reacting at room temperature for 10-14 hours, and evaporating to obtain a grafted modified quaternary ammonium salt compound; wherein the mass ratio of the quaternary ammonium salt compound, tetrahydrofuran, and mercaptoethylamine / methanol mixture is (3.2-6.4):(30-50):(12.7-21.1);

[0031] Add magnolol to ethanol, ultrasonically treat for 20-40 minutes, heat to 60-70°C, then add the grafted modified quaternary ammonium salt compound and a 0.5% by mass fraction azobisisobutyronitrile / ethanol solution, stir and react for 3-5 hours. After the reaction is completed, filter, wash, and dry to obtain a composite modified quaternary ammonium salt compound, wherein the mass ratio of magnolol, ethanol, grafted modified quaternary ammonium salt compound, and azobisisobutyronitrile / ethanol solution is (2.7-5.4):(50-80):(3.6-7.2):(15-20). The composite antistatic additive prepared by the preparation method of the composite antistatic additive;

[0032] In the above process, the acyl chloride in the quaternary ammonium salt compound reacts with the amino group of mercaptoethylamine to form an amide bond, thereby obtaining a grafted modified quaternary ammonium salt compound containing a thiol group. The thiol group then combines with the carbon-carbon double bond at one end of magnolol through a thiol-ene click reaction to obtain a composite modified quaternary ammonium salt compound.

[0033] Application of the composite antistatic auxiliary agent in spinning nylon filaments.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The organic-inorganic hybrid antistatic agent of the present invention is obtained by copolymerizing graft-modified nano zinc oxide, intermediate product B, and a composite modified quaternary ammonium salt compound, wherein:

[0036] (1) Graft-modified nano zinc oxide is obtained by grafting modified allyl polyoxyethylene ether on the surface of mesoporous nano zinc oxide loaded with ionic liquid 1-allyl-3-ethylimidazolium chloride. Nano zinc oxide has excellent conductivity, antibacterial properties, UV absorption and non-toxicity. Allyl polyoxyethylene ether and ionic liquid also have excellent antistatic properties. Encapsulating the ionic liquid in the mesoporous nano zinc oxide can achieve the sustained release of the ionic liquid. Moreover, the imidazolium cation in the ionic liquid forms a hydrogen bond with the C=O of the amide group in the polyamide structure of the nylon filament, and the chloride anion interacts with the NH of the amide group, thereby exerting a long-lasting and excellent antistatic property. Therefore, the graft-modified nano zinc oxide of the present invention has long-lasting antistatic, antibacterial and anti-UV effects.

[0037] (2) Intermediate product B is obtained by the reaction of the Maillard product (intermediate product A) with 4-penten-1-amine. The π bond (CN and CS) in intermediate product A has good UV absorption properties and can form NH + The electron-rich sulfur element is easy to bind to the cell wall and exhibits a bactericidal effect by reducing bacterial activity. Therefore, the intermediate product A of the present invention has anti-ultraviolet and antibacterial properties; more importantly, the intermediate product A has high adhesion and can firmly adhere to the nylon filament, and the aldehyde group therein can also form a covalent bond with the nylon filament containing amino groups (such as PA6, etc.), thereby improving the wash resistance.

[0038] (3) The composite modified quaternary ammonium salt compound contains two quaternary ammonium salt groups and an anti-ultraviolet magnolol structure, so it has antistatic, antibacterial and anti-ultraviolet effects. It also contains an amide group, which can form hydrogen bonds with C=O and NH in the polyamide structure in nylon, thereby improving the compatibility between the organic-inorganic hybrid antistatic agent and nylon filament.

[0039] In summary, organic-inorganic hybrid antistatic agents work synergistically in multiple aspects and have excellent antistatic, antibacterial and anti-UV effects. When used in spinning nylon filaments, they have good water wash resistance. When combined with octylphenol polyoxyethylene ether and nano-carbon black, they can exert better antistatic effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a process flow chart of the preparation method of the composite antistatic additive of the present invention;

[0041] Figure 2 Schematic diagram of the synthesis of intermediate product A of the present invention;

[0042] Figure 3 It is a schematic diagram of the synthesis of the quaternary ammonium salt compound of the present invention;

[0043] Figure 4 Schematic diagram of the synthesis of the composite modified quaternary ammonium salt compound of the present invention;

[0044] Figure 5 This is a comparison chart of surface resistivity tests of samples obtained by using the composite antistatic agents prepared in Examples 2-4 of the present invention and Comparative Examples 1-5 in nylon filaments;

[0045] Figure 6 It is a comparison chart of UPF test of samples obtained by using the composite antistatic agents prepared in Examples 2-4 of the present invention and Comparative Examples 1-5 in nylon filaments. DETAILED DESCRIPTION

[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0047] Example 1

[0048] This embodiment discloses a method for preparing a composite modified quaternary ammonium salt compound, comprising the following steps:

[0049] Step S1, adding 2.3 g of 1,3-bis(dimethylamino)-2-propanol to 65 g of N,N-dimethylformamide, and adding dropwise 27.5 g of a 9.5% by mass oxalyl chloride / N,N-dimethylformamide mixture at a rate of 1 mL / min in an ice-water bath with stirring, stirring for 2 h, and then continuing the reaction at room temperature for 4 h. After the reaction is completed, the solvent and excess oxalyl chloride are removed by rotary evaporation at 80° C. to obtain intermediate product C;

[0050] Under stirring conditions, 3 g of intermediate product C and 65 g of acetone were mixed, and then 3 g of chloropropane was added dropwise at a rate of 1 mL / min. After the addition, the mixture was stirred at 40°C for 24 hours. After the reaction was completed, the solvent and excess chloropropane were evaporated to obtain a quaternary ammonium salt compound;

[0051] Step S2, adding 4.8 g of the quaternary ammonium salt compound to 40 g of tetrahydrofuran, stirring for 30 min, and adding dropwise 16.9 g of a 6.3% mass fraction of mercaptoethylamine / methanol mixture at a rate of 1.5 mL / min in a nitrogen atmosphere. After the addition is complete, stirring and reacting at room temperature for 12 h, and evaporating the solvent to obtain a grafted modified quaternary ammonium salt compound;

[0052] 4.1 g of magnolol was added to 65 g of ethanol, ultrasonically treated for 30 min, heated to 65° C., and then 5.4 g of the grafted modified quaternary ammonium salt compound and 17.5 g of a 0.5% mass fraction of azobisisobutyronitrile / ethanol solution were added. The mixture was stirred and reacted for 4 h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a composite modified quaternary ammonium salt compound.

[0053] Example 2

[0054] This embodiment discloses a method for preparing a composite antistatic additive, comprising the following steps:

[0055] Step (1), 8.9g zinc nitrate hexahydrate, 10.3g sucrose, 1.6g ammonium chloride, 8g ethanol, 10g deionized water, and 9.1g ammonia water with a mass fraction of 25% are mixed and stirred until uniform to obtain an aqueous phase; 3.5g Span 80, 1.9g Tween 80, and 39.5g kerosene are mixed and stirred until uniform to obtain an oil phase; at room temperature, the aqueous phase is added dropwise to the oil phase at a rate of 1mL / min, and stirred to obtain a transparent water-in-oil microemulsion, and then stirred at 79°C and 0.01MPa for 5.5h, naturally cooled to room temperature, centrifuged, and the resulting precipitate is added to cyclohexane and maintained at 89°C for 75h to obtain a sucrose / ZnO composite material, and the sucrose / ZnO composite material is extracted with ethanol Soxhlet for 20h to obtain mesoporous nano-zinc oxide with an average particle size of 150nm;

[0056] 1 g of 3-glycidyloxypropyltrimethoxysilane and 10 g of mesoporous nano-zinc oxide were dispersed in 100 g of ethanol, and then refluxed at 75° C. and pH 4 for 6 h, followed by centrifugation, washing, and drying to obtain surface-modified nano-zinc oxide.

[0057] 5 g of 1-allyl-3-ethylimidazolium chloride was added to 60 g of ethanol, and after ultrasonic treatment for 20 min, 3 g of surface-modified nano-zinc oxide was added, and the mixture was stirred at room temperature for 8 h, filtered, washed, and dried to obtain loaded modified nano-zinc oxide;

[0058] Step (2), adding 10g of allyl polyoxyethylene ether to 80g of chloroform, and then adding 2.5g of maleic anhydride and 0.05g of 4-dimethylaminopyridine, reacting at room temperature for 60h, and after the reaction is completed, evaporating the solvent to obtain modified allyl polyoxyethylene ether;

[0059] 8 g of modified allyl polyoxyethylene ether and 0.2 g of tetrabutylammonium bromide were added to 30 g of deionized water and stirred until uniform to obtain a mixed solution A; 4 g of loaded modified nano-zinc oxide was added to 100 g of deionized water and ultrasonically dispersed for 20 min, and then the mixed solution A was added dropwise at a rate of 1 mL / min. After the addition, the temperature was raised to reflux and stirred for reaction for 2 h. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain grafted modified nano-zinc oxide;

[0060] Step (3), mixing glucose, thiourea, and deionized water to obtain a reaction solution, wherein the concentration of glucose in the reaction solution is 50 g / L, and the mass ratio of glucose to thiourea is 1:0.8; adjusting the pH of the reaction solution to 12 with a 3 mol / L sodium hydroxide aqueous solution, reacting at 88° C. for 150 min, distilling, washing the crude product with ethanol, and vacuum drying at 50° C. to obtain an intermediate product A;

[0061] 2 g of intermediate product A and 6 g of thionyl chloride were added to 120 g of N,N-dimethylformamide, heated to 55°C for reaction for 28 h, then raised to 85°C to remove excess thionyl chloride, and then 3 g of 4-penten-1-amine was added. The reaction was continued at 85°C for another 28 h, and the solvent and excess 4-penten-1-amine were removed by rotary evaporation to obtain intermediate product B.

[0062] 2 g of grafted modified nano zinc oxide, 1.5 g of intermediate product B, and 6 g of composite modified quaternary ammonium salt compound were added to 120 g of N,N-dimethylformamide and stirred for 40 min. 0.08 g of azobisisobutyronitrile was then added and the temperature was raised to 75° C. The mixture was stirred for 6 h, filtered, washed, and dried to obtain an organic-inorganic hybrid antistatic agent.

[0063] An organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether and nano carbon black are mixed in a mass ratio of 4:2:1 to obtain a composite antistatic auxiliary agent.

[0064] Example 3

[0065] This embodiment discloses a method for preparing a composite antistatic additive, comprising the following steps:

[0066] Step (1), 17.8g zinc nitrate hexahydrate, 20.6g sucrose, 3.2g ammonium chloride, 16g ethanol, 20g deionized water, and 18.2g ammonia water with a mass fraction of 25% are mixed and stirred until uniform to obtain an aqueous phase; 7g Span 80, 3.8g Tween 80, and 79g kerosene are mixed and stirred until uniform to obtain an oil phase; at room temperature, the aqueous phase is added dropwise to the oil phase at a rate of 1.5mL / min, and stirred to obtain a transparent water-in-oil microemulsion, and then stirred at 81°C and 0.01MPa for 5.5h, naturally cooled to room temperature, centrifuged, and the resulting precipitate is added to cyclohexane and maintained at 91°C for 70h to obtain a sucrose / ZnO composite material, and the sucrose / ZnO composite material is extracted with ethanol Soxhlet for 30h to obtain mesoporous nano-zinc oxide with an average particle size of 150nm;

[0067] 3 g of 3-glycidyloxypropyltrimethoxysilane and 15 g of mesoporous nano-zinc oxide were dispersed in 120 g of ethanol, and then refluxed for 4 h at 80° C. and pH 5, followed by centrifugation, washing, and drying to obtain surface-modified nano-zinc oxide.

[0068] 10 g of 1-allyl-3-ethylimidazolium chloride was added to 80 g of ethanol, and after ultrasonic treatment for 40 min, 5 g of surface-modified nano-zinc oxide was added, and the mixture was stirred at room temperature for 12 h, filtered, washed, and dried to obtain loaded modified nano-zinc oxide;

[0069] Step (2), adding 12g of allyl polyoxyethylene ether to 100g of chloroform, then adding 3g of maleic anhydride and 0.1g of 4-dimethylaminopyridine, and reacting at room temperature for 60h. After the reaction is completed, evaporating the solvent to obtain modified allyl polyoxyethylene ether;

[0070] 12 g of modified allyl polyoxyethylene ether and 0.5 g of tetrabutylammonium bromide were added to 40 g of deionized water and stirred until uniform to obtain a mixed solution A; 6 g of loaded modified nano-zinc oxide was added to 120 g of deionized water and ultrasonically dispersed for 40 min, and then the mixed solution A was added dropwise at a rate of 1.5 mL / min. After the addition, the temperature was raised to reflux and stirred for reaction for 3 h. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain grafted modified nano-zinc oxide;

[0071] Step (3), mixing glucose, thiourea, and deionized water to obtain a reaction solution, wherein the concentration of glucose in the reaction solution is 50 g / L, and the mass ratio of glucose to thiourea is 1:1.7; adjusting the pH of the reaction solution to 12.5 with a 3 mol / L sodium hydroxide aqueous solution, reacting at 92° C. for 100 min, distilling, washing the crude product with ethanol, and vacuum drying at 60° C. to obtain an intermediate product A;

[0072] 5 g of intermediate product A and 10 g of thionyl chloride were added to 150 g of N,N-dimethylformamide, heated to 65°C for 20 h, then raised to 92°C to remove excess thionyl chloride, and then 5 g of 4-penten-1-amine was added. The reaction was continued at 92°C for 20 h, and the solvent and excess 4-penten-1-amine were removed by rotary evaporation to obtain intermediate product B.

[0073] 5 g of grafted modified nano zinc oxide, 3.5 g of intermediate product B, and 10 g of composite modified quaternary ammonium salt compound were added to 150 g of N,N-dimethylformamide and stirred for 60 min. 0.12 g of azobisisobutyronitrile was then added and the temperature was raised to 80° C. The mixture was stirred for 5 h, filtered, washed, and dried to obtain an organic-inorganic hybrid antistatic agent.

[0074] An organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether and nano carbon black are mixed in a mass ratio of 6:4:2 to obtain a composite antistatic auxiliary agent.

[0075] Example 4

[0076] This embodiment discloses a method for preparing a composite antistatic additive, comprising the following steps:

[0077] Step (1), 13.4g zinc nitrate hexahydrate, 15.5g sucrose, 2.4g ammonium chloride, 12g ethanol, 15g deionized water, and 13.7g ammonia water with a mass fraction of 25% are mixed and stirred until uniform to obtain an aqueous phase; 5.3g Span 80, 2.9g Tween 80, and 59.3g kerosene are mixed and stirred until uniform to obtain an oil phase; at room temperature, the aqueous phase is added dropwise to the oil phase at a rate of 1.2mL / min, and stirred to obtain a transparent water-in-oil microemulsion, and then stirred at 80°C and 0.01MPa for 5h, naturally cooled to room temperature, centrifuged, and the resulting precipitate is added to cyclohexane and maintained at 89-91°C for 72h to obtain a sucrose / ZnO composite material, and the sucrose / ZnO composite material is extracted with ethanol Soxhlet for 25h to obtain mesoporous nano-zinc oxide with an average particle size of 150nm;

[0078] 2 g of 3-glycidyloxypropyltrimethoxysilane and 12.5 g of mesoporous nano-zinc oxide were dispersed in 110 g of ethanol, and then refluxed at 78° C. and pH 4.5 for 5 h, centrifuged, washed, and dried to obtain surface-modified nano-zinc oxide.

[0079] 7.5 g of 1-allyl-3-ethylimidazolium chloride was added to 70 g of ethanol, and after ultrasonic treatment for 30 min, 4 g of surface-modified nano-zinc oxide was added, and the mixture was stirred at room temperature for 8-12 h, filtered, washed, and dried to obtain loaded modified nano-zinc oxide;

[0080] Step (2), adding 11 g of allyl polyoxyethylene ether to 90 g of chloroform, and then adding 2.8 g of maleic anhydride and 0.08 g of 4-dimethylaminopyridine, reacting at room temperature for 70 h. After the reaction is completed, evaporating the solvent to obtain modified allyl polyoxyethylene ether;

[0081] 10 g of modified allyl polyoxyethylene ether and 0.3 g of tetrabutylammonium bromide were added to 35 g of deionized water and stirred until uniform to obtain a mixed solution A; 5 g of loaded modified nano-zinc oxide was added to 110 g of deionized water and ultrasonically dispersed for 30 min, and then the mixed solution A was added dropwise at a rate of 1.2 mL / min. After the addition, the temperature was raised to reflux and stirred for reaction for 2.5 h. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain grafted modified nano-zinc oxide;

[0082] Step (3), mixing glucose, thiourea, and deionized water to obtain a reaction solution, wherein the concentration of glucose in the reaction solution is 50 g / L, and the mass ratio of glucose to thiourea is 1:1.3; adjusting the pH of the reaction solution to 12.3 with a 3 mol / L sodium hydroxide aqueous solution, reacting at 90° C. for 120 min, distilling, washing the crude product with ethanol, and vacuum drying at 55° C. to obtain an intermediate product A;

[0083] 3.5 g of intermediate product A and 8 g of thionyl chloride were added to 135 g of N,N-dimethylformamide, heated to 60°C for reaction for 24 h, then raised to 89°C to remove excess thionyl chloride, and then 4 g of 4-penten-1-amine was added. The reaction was continued at 89°C for another 24 h, and the solvent and excess 4-penten-1-amine were removed by rotary evaporation to obtain intermediate product B.

[0084] 3.5 g of grafted modified nano zinc oxide, 2.5 g of intermediate product B, and 8 g of composite modified quaternary ammonium salt compound were added to 135 g of N,N-dimethylformamide and stirred for 50 min. 0.1 g of azobisisobutyronitrile was then added and the temperature was raised to 78° C. The mixture was stirred for 5.5 h, filtered, washed, and dried to obtain an organic-inorganic hybrid antistatic agent.

[0085] An organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether and nano carbon black are mixed in a mass ratio of 5:3:1.5 to obtain a composite antistatic auxiliary agent.

[0086] The composite modified quaternary ammonium salt compound used in the above Examples 2-4 is the composite modified quaternary ammonium salt compound prepared in Example 1.

[0087] Comparative Example 1

[0088] Compared with Example 4, in the process of preparing grafted modified nano zinc oxide in Comparative Example 1, surface modified nano zinc oxide was used instead of modified loaded modified nano zinc oxide, and other conditions remained unchanged.

[0089] Comparative Example 2

[0090] Compared with Example 4, in the process of preparing the organic-inorganic hybrid antistatic agent in Comparative Example 2, modified allyl polyoxyethylene ether was used instead of grafted modified nano zinc oxide, while other conditions remained unchanged.

[0091] Comparative Example 3

[0092] Compared with Example 4, in the process of preparing the organic-inorganic hybrid antistatic agent in Comparative Example 3, no grafted modified nano zinc oxide was added, and other conditions remained unchanged.

[0093] Comparative Example 4

[0094] Compared with Example 4, in the process of preparing the organic-inorganic hybrid antistatic agent in Comparative Example 4, the intermediate product B was not added, and other conditions remained unchanged.

[0095] Comparative Example 5

[0096] Compared with Example 4, in Comparative Example 5, during the preparation of the organic-inorganic hybrid antistatic agent, no composite modified quaternary ammonium salt compound was added, and other conditions remained unchanged.

[0097] In the above embodiments and comparative examples, sucrose with a particle size of 200 mesh and a purity of 99% was obtained from Langfang Huinuo Fine Chemical Co., Ltd.; Span 80, with an appearance of a yellow oily liquid and an HLB value of 4.3, was obtained from Shandong Haochen New Materials Technology Co., Ltd.; Tween 80, with an appearance of an amber viscous oil, a specific gravity of 1.06-1.09, and an HLB value of 15, was obtained from Taizhou Jiayin Chemical Co., Ltd.; kerosene with a density of 0.79 (g / mL) and an active ingredient content of 99.98% was obtained from Handan Qianxiong Oil Technology Co., Ltd.; allyl polyoxyethylene ether with an active ingredient content of 99%, model APEG-400, a molecular weight of 400, and a hydroxyl value (mg KOH / g) of 127-155, was obtained from Hai'an Petrochemical Plant in Jiangsu Province; octylphenol polyoxyethylene ether with an active substance content of 99%, model NP-40, and an appearance of white flakes was obtained from Tianjin Daixu Chemical Trading Co., Ltd.; and nanocarbon black with an average particle size of 25 nm was obtained from Tianjin Baochi Chemical Technology Co., Ltd.

[0098] Experimental example

[0099] The composite antistatic additives prepared in Examples 2-4 of the present invention and Comparative Examples 1-5 were mixed with PA6 chips at a mass ratio of 3:100, melt-extruded and metered and homogenized into the spinning manifold through a screw extruder, and then metered and extruded by a metering pump, cooled and solidified with side air, oiled and bundled, pre-networked, stretched by a cold roller, stretched and heat-set by a hot roller, a sub-networked device, and wound to form nylon filament samples, which were respectively recorded as Sample 2, Sample 3, Sample 4 and Comparative Sample 1, Comparative Sample 2, Comparative Sample 3, Comparative Sample 4, and Comparative Sample 5.

[0100] Perform performance tests on each group of samples.

[0101] 1. Antistatic performance test: Test in accordance with GB / T 1410-2006 "Test method for volume resistivity and surface resistivity of solid insulating materials".

[0102] 2. Antibacterial performance test: Escherichia coli and Staphylococcus aureus were used as test bacteria. The test procedure was based on GB / T20944.3-2008. First, the viable bacterial concentration in the flask at the "0" contact time was measured, recorded as W0. Then, the colony count was measured after the oscillation contact time was 18 hours, recorded as Wt. The results are shown in Table 1. The antibacterial rate Y was calculated as follows: Y = (W t Then, the antibacterial rate of each group of samples after washing 50 times was tested using the same method.

[0103] 3. UV Resistance Test: The UV resistance is characterized by the average value of the UV Protection Factor (UPF). Referring to the standard GB / T18830-2009, each group of samples is first made into garters using a small hosiery machine. The garters are then placed on the sample platform of a UV transmittance tester. Ten points are evenly selected for testing. The test UV wavelength is 250-450nm, and the transmittance is 0-100%. The UPF is then calculated using the following formula.

[0104]

[0105] Where: T λ is the spectral transmittance of the sample at wavelength λ, S λ is the relative erythema dose spectral effect, E λ is the solar spectrum radiance, and △λ is the wavelength interval.

[0106] The test results are shown in Table 1:

[0107] Table 1

[0108]

[0109]

[0110] From the test results in Table 1, it can be seen that samples 2-4 of the present invention have excellent antistatic, antibacterial, anti-ultraviolet effects and water-washing resistance. From the comparison of comparative samples 1-3 and sample 4, it can be seen that ionic liquids, nano zinc oxide, and allyl polyoxyethylene ether have different degrees of influence on the antistatic effect of organic-inorganic hybrid antistatic agents. Due to the presence of nano zinc oxide in the grafted modified nano zinc oxide, it is given anti-ultraviolet and antibacterial properties, thereby affecting the anti-ultraviolet and antibacterial properties of each group of samples; from the comparison of comparative sample 4 and sample 4, it can be seen that the intermediate product B has good ultraviolet absorption properties due to the presence of π bonds (CN and CS), and can form NH under acidic conditions. + The electron-rich sulfur element is easy to bind to the cell wall and exhibits a bactericidal effect by reducing bacterial activity, thereby affecting the anti-ultraviolet and antibacterial properties of each group of samples. In addition, the intermediate product A has a significant effect on the wash resistance of the nylon filament sample due to its adhesion and the formation of covalent bonds with the nylon filament. From the comparison of comparative sample 5 and sample 4, it can be seen that the composite modified quaternary ammonium salt compound contains two quaternary ammonium salt groups and an anti-ultraviolet magnolol structure, so it has antistatic, antibacterial and anti-ultraviolet effects, and it also contains an amide group. The amide group can form hydrogen bonds with C=O and NH in the polyamide structure in nylon, thereby improving the compatibility between the organic-inorganic hybrid antistatic agent and the nylon filament, so that the organic-inorganic hybrid antistatic agent can exert better efficacy.

[0111] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a composite antistatic additive, characterized in that: The following steps are involved: Step (1), using zinc nitrate as a metal precursor and sucrose as a porogen to prepare mesoporous nano zinc oxide; the mesoporous nano zinc oxide is modified with 3-glycidyloxypropyltrimethoxysilane and then loaded with 1-allyl-3-ethylimidazolium chloride to obtain loaded modified nano zinc oxide; Step (2), after allyl polyoxyethylene ether is modified with maleic anhydride, it is grafted onto the loaded modified nano zinc oxide to obtain grafted modified nano zinc oxide; Step (3), glucose and thiourea react to obtain intermediate product A; intermediate product A reacts with thionyl chloride and then reacts with 4-penten-1-amine to obtain intermediate product B; Graft-modified nano zinc oxide, intermediate product B, and composite modified quaternary ammonium salt compound are copolymerized to obtain an organic-inorganic hybrid antistatic agent; The organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether and nano carbon black are mixed to obtain a composite antistatic auxiliary agent; The preparation method of the composite modified quaternary ammonium salt compound comprises the following steps: Step S1: 1,3-bis(dimethylamino)-2-propanol reacts with oxalyl chloride to obtain an intermediate product C; and the intermediate product C reacts with chloropropane to obtain a quaternary ammonium salt compound; Step S2: After the quaternary ammonium salt compound is grafted with mercaptoethylamine, it reacts with magnolol to obtain a composite modified quaternary ammonium salt compound.

2. The method for preparing the composite antistatic auxiliary agent according to claim 1, wherein In the step (1), the preparation method of the mesoporous nano zinc oxide is as follows: zinc nitrate hexahydrate, sucrose, ammonium chloride, ethanol, deionized water, and 25% ammonia water are mixed in a mass ratio of (8.9-17.8): (10.3-20.6): (1.6-3.2): (8-16): (10-20): (9.1-18.2), and stirred until uniform to obtain an aqueous phase; Span 80, Tween 80, and kerosene are mixed in a mass ratio of (3.5-7): (1.9-3.8): (39.5-79), The method comprises the steps of: stirring until uniform to obtain an oil phase; adding the aqueous phase dropwise to the oil phase at a rate of 1-1.5 mL / min at room temperature, stirring to obtain a transparent water-in-oil microemulsion, stirring at 79-81° C. and 0.01 MPa for 4.5-5.5 hours, naturally cooling to room temperature, centrifuging, adding the obtained precipitate to cyclohexane, and maintaining the mixture at 89-91° C. for 70-75 hours to obtain a sucrose / ZnO composite material; and extracting the sucrose / ZnO composite material with ethanol Soxhlet for 20-30 hours to obtain mesoporous nano-zinc oxide with an average particle size of 150 nm.

3. The preparation method of the composite antistatic auxiliary agent according to claim 1, characterized in that, In the step (1), the preparation method of the loaded modified nano zinc oxide is as follows: 3-glycidyloxypropyltrimethoxysilane and mesoporous nano zinc oxide are dispersed in ethanol, and then refluxed for 4-6 hours at a temperature of 75-80°C and a pH value of 4-5, centrifuged, washed, and dried to obtain surface-modified nano zinc oxide; wherein the mass ratio of 3-glycidyloxypropyltrimethoxysilane, mesoporous nano zinc oxide, and ethanol is (1-3):(10-15):(100-120); 1-allyl-3-ethylimidazolium chloride is added to ethanol, ultrasonically treated for 20-40 minutes, and then surface-modified nano-zinc oxide is added. The mixture is stirred at room temperature for 8-12 hours, filtered, washed, and dried to obtain loaded modified nano-zinc oxide; wherein the mass ratio of 1-allyl-3-ethylimidazolium chloride, ethanol, and surface-modified nano-zinc oxide is 5:60:3 or 10:80:5 or 7.5:70:

4.

4. The method for preparing the composite antistatic auxiliary agent according to claim 1, wherein In the step (2), the preparation method of the grafted modified nano zinc oxide is: Add allyl polyoxyethylene ether to chloroform, then add maleic anhydride and 4-dimethylaminopyridine, and react at room temperature for 60-80 hours. After the reaction is completed, evaporate the solvent to obtain modified allyl polyoxyethylene ether; wherein the mass ratio of allyl polyoxyethylene ether, chloroform, maleic anhydride, and 4-dimethylaminopyridine is (10-12):(80-100):(2.5-3):(0.05-0.1); Modified allyl polyoxyethylene ether and tetrabutylammonium bromide are added to deionized water and stirred until uniform to obtain a mixed solution A; the loaded modified nano zinc oxide is added to deionized water, ultrasonically dispersed for 20-40 minutes, and then the mixed solution A is added dropwise at a rate of 1-1.5 mL / min. After the addition is completed, the temperature is raised to reflux and stirred for reaction for 2-3 hours. After the reaction is completed, the mixture is centrifuged, washed, and dried to obtain grafted modified nano zinc oxide; wherein the mass ratio of modified allyl polyoxyethylene ether, tetrabutylammonium bromide, and loaded modified nano zinc oxide is (8-12):(0.2-0.5):(4-6).

5. The method for preparing the composite antistatic auxiliary agent according to claim 1, wherein In step (3), the preparation method of the intermediate product B is as follows: glucose, thiourea, and deionized water are mixed to obtain a reaction solution, wherein the concentration of glucose in the reaction solution is 50 g / L, and the mass ratio of glucose to thiourea is 1:(0.8-1.7); the pH of the reaction solution is adjusted to 12-12.5 by using a 3 mol / L sodium hydroxide aqueous solution, the reaction is carried out at 88-92° C. for 100-150 min, and the reaction is performed by distillation, washing, and drying to obtain the intermediate product A; Add the intermediate product A and thionyl chloride to N,N-dimethylformamide, heat to 55-65°C and react for 20-28 hours, then raise the temperature to 85-92°C, add 4-penten-1-amine, continue to react at 85-92°C for 20-28 hours, and rotary evaporate to obtain the intermediate product B; wherein, the mass ratio of the intermediate product A, thionyl chloride, N,N-dimethylformamide, and 4-penten-1-amine is (2-5):(6-10):(120-150):(3-5).

6. The method for preparing the composite antistatic auxiliary agent according to claim 1, characterized in that: In the step (3), the preparation method of the organic-inorganic hybrid antistatic agent is as follows: adding the grafted modified nano zinc oxide, the intermediate product B, and the composite modified quaternary ammonium salt compound to N,N-dimethylformamide, stirring for 40-60 minutes, then adding azobisisobutyronitrile, heating to 75-80°C, continuing to stir for 5-6 hours, filtering, washing, and drying to obtain the organic-inorganic hybrid antistatic agent; wherein the mass ratio of the grafted modified nano zinc oxide, the intermediate product B, the composite modified quaternary ammonium salt compound, N,N-dimethylformamide, and azobisisobutyronitrile is (2-5):(1.5-3.5):(6-10):(120-150):(0.08-0.12).

7. The method for preparing the composite antistatic auxiliary agent according to claim 1, wherein In the step (3), the mass ratio of the organic-inorganic hybrid antistatic agent, octylphenol polyoxyethylene ether, and nano carbon black is (4-6):(2-4):(1-2).

8. The method for preparing the composite antistatic auxiliary agent according to claim 1, characterized in that: In step (3), the method for preparing the composite modified quaternary ammonium salt compound comprises the following steps: Step S1, adding 1,3-bis(dimethylamino)-2-propanol to N,N-dimethylformamide, and adding dropwise a 9.5% mass fraction of oxalyl chloride / N,N-dimethylformamide mixture at a rate of 0.8-1.2 mL / min under stirring in an ice-water bath, stirring for 1.5-2.5 hours, and then continuing the reaction at room temperature for 3.5-4.5 hours. After the reaction is completed, rotary evaporation is performed to obtain an intermediate product C; wherein the mass ratio of 1,3-bis(dimethylamino)-2-propanol, N,N-dimethylformamide, and oxalyl chloride / N,N-dimethylformamide mixture is (1.5-3):(50-80):(20-35); Under stirring conditions, the intermediate product C and acetone are mixed, and then chloropropane is added dropwise at a rate of 0.8-1.2 mL / min. After the addition is completed, the mixture is stirred and reacted at 38-42° C. for 20-28 hours. After the reaction is completed, the mixture is evaporated to obtain a quaternary ammonium salt compound; wherein the mass ratio of the intermediate product C, acetone, and chloropropane is (2.4-3.6):(50-80):(1.8-4.2); Step S2, adding a quaternary ammonium salt compound to tetrahydrofuran, stirring for 20-40 min, and adding dropwise a 6.3% mass fraction of mercaptoethylamine / methanol mixture at a rate of 1-2 mL / min in a nitrogen atmosphere. After the dropwise addition, the reaction was stirred at room temperature for 10-14 h, and evaporated to obtain a grafted modified quaternary ammonium salt compound; wherein the mass ratio of the quaternary ammonium salt compound, tetrahydrofuran, and mercaptoethylamine / methanol mixture is (3.2-6.4):(30-50):(12.7-21.1); Magnolol is added to ethanol, ultrasonically treated for 20-40 minutes, heated to 60-70°C, and then a grafted modified quaternary ammonium salt compound and an azobisisobutyronitrile / ethanol mixed solution with a mass fraction of 0.5% of azobisisobutyronitrile are added, and the mixture is stirred for 3-5 hours. After the reaction is completed, the mixture is filtered, washed, and dried to obtain a composite modified quaternary ammonium salt compound, wherein the mass ratio of magnolol, ethanol, grafted modified quaternary ammonium salt compound, and azobisisobutyronitrile / ethanol mixed solution is (2.7-5.4):(50-80):(3.6-7.2):(15-20).

9. A composite antistatic additive prepared by the method for preparing a composite antistatic additive according to any one of claims 1 to 8.

10. Use of the composite antistatic additive according to claim 9 in spinning nylon filaments.

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