CN114634601A - Polymer permanent antistatic agent and preparation method and application thereof - Google Patents

Abstract

The invention relates to the field of antistatic agents, in particular to a high-molecular permanent antistatic agent, a preparation method thereof and application thereof in PET and polyester fibers. According to the invention, through the optimized selection of the structural design of the nonionic, anionic and cationic antistatic agent monomers, the nonionic, anionic and cationic high molecular polymer antistatic agent is synthesized by utilizing a copolymerization reaction mechanism, and is firstly applied to PET sample strips and polyester fibers, the antistatic property of the antistatic agent achieves the due antistatic effect, a new antistatic selection is provided for the polyester fibers and PET high molecular materials, the long-term antistatic property of the antistatic agent is maintained, the phenomena that the antistatic agent is not easy to wash away and wipe away are avoided, and the requirement on the permanent antistatic function is met. In addition, compared with the product of the permanent antistatic agent polyether ester amide widely applied in the market, the product of the patent does not generate the phenomenon of easy yellowing of processing caused by the structure of the polyether ester amide.

Description

A kind of polymer permanent antistatic agent and its preparation method and application

technical field

The invention relates to the field of antistatic agents, in particular to a macromolecular permanent antistatic agent and a preparation method thereof and application in PET and polyester fibers thereof.

Background technique

Studies have shown that electrostatic discharges in polymer materials such as plastics, rubber, adhesives, fibers, fabrics, and coatings often affect operations, and even generate sparks to cause dangerous accidents such as fire or explosion. The application of antistatic additives during processing can reduce the surface resistivity of the material to 10 ¹¹ Ω/sq and below, the volume resistivity to 10 ¹¹ Ω·cm and below, the surface electrostatic voltage to 0.47KV, and the electrostatic half-life to 0.2s to effectively solve the electrostatic problem of polymer materials.

Small-molecule antistatic additives are usually used in PET and polyester fibers. Because of their good water solubility or strong migration ability, they are easily lost in the process of washing and wiping, causing the antistatic properties of the fiber matrix to decline. Mesoporous materials such as SiO ₂ , Fe ₃ O ₄ , and mesoporous carbon are used as carriers of small-molecule antistatic additives to control the release and migration rate of antistatic additives in the matrix material to improve their antistatic durability. There are still problems such as poor compatibility with polymer materials, and negative impact on the environment after being easily detached from the matrix material. Polymer antistatic additives are also known as permanent antistatic additives. They have certain hydrophilic properties, are well matched with polymer materials, are easy to process, and are not easily lost during long-term use or even repeated contact with water for washing. The polymer antistatic additive has no problems of melting, dissolution and color change, and is not affected by washing and friction during the application of polymer materials. It has a lasting antistatic effect, no induction period, and is environmentally friendly. Friendly and other advantages, it is deeply loved by the market. Therefore, the development of polymer permanent antistatic additives has become the research focus of domestic and foreign scholars. Hydrophilic polymer antistatic agents are divided into non-ionic, anionic, cationic and composite modified types. The permanent antistatic agent widely used in the market is non-ionic polyetheresteramide permanent antistatic agent, and its main suppliers are Arkema, Sanyo Chemical, BASF and so on. The application of ionic permanent antistatic agents in resin products has not been promoted, especially in processing-sensitive PET materials or in polyester fibers, the application development of permanent antistatic properties is extremely challenging.

SUMMARY OF THE INVENTION

The present invention hopes to apply anionic, cationic and nonionic permanent antistatic agents to PET splines and polyester fibers, and the specific scheme is as follows:

A polymer permanent antistatic agent, the structural formula is as follows,

When it is a non-ionic antistatic agent, the polymer structure is:

b=1,2,3,4,5; c=1,2,3,4,5; d=1,2,3; e=1,2,3,4,5,6,7,8;

x=5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20;

When it is a cationic antistatic agent, the polymer structure is:

or as:

f=1,2,3,4,5,6,7,8,9; g=1,2,3,4,5; h=1,2,3,4,5; j=1,2, 3; k=1,2,3,4,5,6,7,8;

x=5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20;

When it is an anionic antistatic agent, the polymer structure is:

f=1,2,3,4,5,6,7,8,9; g=1,2,3,4,5; h=1,2,3,4,5; j=1,2, 3; k=1,2,3,4,5,6,7,8;

x = 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

When it is a non-ionic antistatic agent, it can be obtained by polymerization of acrylonitrile, methacrylamide, glycidyl methacrylate and allyl polyoxyethylene ether as reaction monomers; when it is an anionic antistatic auxiliary, it is obtained by polymerization Acrylonitrile, methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether and sodium p-styrene sulfonate are obtained by polymerization of reaction monomers; when it is a cationic antistatic auxiliary, acrylonitrile, Methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether and alfa-methacryloyloxyethyltrimethylammonium chloride or triethylallylammonium chloride are polymerized as reactive monomers The reaction is obtained.

The equations for the above reactions are:

(1) Anionic antistatic agent polymerization reaction equation

(2) cationic antistatic agent polymerization reaction equation

(3) Nonionic antistatic agent polymerization reaction equation

A preparation method of a polymer permanent antistatic agent, the specific steps are as follows: adding a reaction monomer and a solvent into a reaction flask, replacing the air in the reaction flask with N , turning _on stirring and heating to 60-70° C., dripping AIBN to induce Then, the temperature is increased to control the reaction temperature of 70-85 °C, and the reaction time is 3-8 hours.

After the reaction, remove the solvent with a rotary evaporator, extract it with solvent extraction to remove low molecular weight substances, cool and solidify and grind it to small particles with a mortar; then place the product in a vacuum drying box for 40-60 Dry at ℃ for 8-12 hours, then cool, solidify, grind and granulate to obtain antistatic additives.

The ratio of the volume of the solvent to the total mass of the functional monomer does not exceed 20:1.

The solvent is acetonitrile or butanone or ethylene glycol dimethyl ether or ethylene glycol monomethyl ether or ethyl acetate or ethanol or isopropanol or toluene.

The mass fraction of the AIBN initiator solution is 0.3% or 0.5% or 1% or 2% or 3%.

The reaction flask is a three-necked flask with a reflux device dropping funnel.

The patent of the present invention has synthesized nonionic, anionic and cationic polymer antistatic agents through the optimization and selection of the monomer structure of nonionic, anionic and cationic antistatic agents, and used the mechanism of copolymerization to synthesize nonionic, anionic and cationic polymer antistatic agents, which are applied to PET splines and polyester fibers for the first time. Among them, its antistatic properties have achieved the due antistatic effect, providing a new antistatic choice for polyester fibers and PET polymer materials while maintaining their long-term antistatic properties, solving the phenomenon that antistatic agents are not easy to wash off and wipe off. At the same time, it meets the requirements of permanent antistatic function. In addition, compared with the widely used permanent antistatic agent polyetheresteramide products in the market, the patented product does not produce the phenomenon of easy yellowing during processing caused by the polyetheresteramide structure.

Description of drawings

Fig. 1 contains the PET sample plate of the anionic antistatic agent of the present invention;

Fig. 2 contains the dumbbell-shaped spline of the anionic antistatic agent of the present invention;

Fig. 3 Surface contact angle curve of antistatic additive content of antistatic additive/PET blend material;

Figure 4. Polyester fiber containing anionic antistatic agent and cationic antistatic agent.

Detailed ways

1. Synthesis of anionic, cationic and nonionic permanent antistatic agents

1.1 Raw materials and main equipment

The raw materials of cationic, anionic and nonionic permanent antistatic agent polymerized monomers are shown in Table 1; the main test instruments and equipment are shown in Table 2.

Table 1 Experimental raw materials

raw material Specification Supplier manufacturers Acrylonitrile Industrial grade Jinan Yuanxiang Chemical Co., Ltd. Methacrylamide Industrial grade Shengzhou Baili Chemical Co., Ltd. Glycidyl methacrylate Industrial grade Zaozhuang Weicheng Chemical Technology Allyl polyoxyethylene ether* Industrial grade Jiangsu Haian Petrochemical Plant Sodium p-styrene sulfonate Industrial grade Zhengzhou Meifu Chemical Products Co., Ltd. Methacryloxyethyltrimethylammonium chloride 70% aqueous solution Dengfeng Enteng Technology Co., Ltd. Azobisisobutyronitrile (AIBN) analytically pure Shanghai McLean Biotechnology Acetonitrile Industrial grade Shanghai Yishi Chemical Co., Ltd. Ethanol Industrial grade Shaoxing Light Industry Chemical Fiber grade PET chips - Zhejiang Tiansheng Chemical Fiber Co., Ltd. Antioxidant NS01 Industrial grade Shaoxing Ruikang Biotechnology Co., Ltd.

*The average relative molecular mass of allyl polyoxyethylene ether is 2500

Table 2 Experimental instruments

1.2 Synthesis method of permanent antistatic agent and formulation of polymerized monomers

The patented non-ionic antistatic agent uses acrylonitrile, methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether, etc. as antistatic additives to synthesize functional monomers (molar ratio is 5:5: 3:2-8); anionic antistatic additives are functional synthetic monomers based on acrylonitrile, methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether, and sodium p-styrene sulfonate (molar ratio is 5:5:3:2-8:1-9); cationic antistatic additives are acrylonitrile, methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether, Alfa-methacryloyloxyethyltrimethylammonium chloride or triethylallylammonium chloride (molar ratio of 5:5:3:2-8:1-9) is a synthetic functional monomer. Dissolve a certain optimized monomer in acetonitrile or methyl ethyl ketone or ethylene glycol dimethyl ether or ethylene glycol monomethyl ether or isopropanol or ethyl acetate or ethanol or toluene in a molar ratio, and add it to a magnetic stirring bar. In the three-necked flask, the ratio of the volume of the solvent to the total mass of the functional monomer may be 1:1 or 2:1 or 3:1 or 4:1 or 5:1, with a maximum of 20:1. Dissolve 0.3% or 0.5% or 1% or 2% or 3% of the AIBN free radical reaction initiator in a solvent first to prepare an initiator solution, and add dropwise to the reaction solution when the reaction temperature rises to 50-75°C.

1.2.1 Antistatic agent preparation polymerization reaction and experimental steps

1.2.1.1 Antistatic agent preparation polymerization

(1) Anionic antistatic agent polymerization reaction equation

(2) cationic antistatic agent polymerization reaction equation

(3) Nonionic antistatic agent polymerization reaction equation

1.2.1.2 General operation steps of antistatic agent preparation polymerization reaction

The reaction monomer and an appropriate amount of solvent (less than or equal to 1:20=w/v) weighed according to the set molar ratio were added to a three-necked flask equipped with a reflux device dropping funnel, and the air in the reaction flask was replaced with N ₂ After three times, place the three-necked flask in the DF-101S type collector thermostatic heating magnetic stirrer, turn on stirring and heat to 60-70°C, add AIBN initiator solution dropwise, and then increase the temperature to control the reaction temperature to 65-85°C, The reaction time is 3-8 hours. After the reaction, use a vacuum RE-2000B rotary evaporator to remove the solvent, extract it by solvent extraction to remove low molecular weight substances, and grind it to small particles with a mortar after cooling and solidification. Then, the product is placed in a vacuum drying oven at 40-60° C. to dry for 8-12 hours, and then cooled, solidified, ground and granulated to obtain an antistatic additive. The monomer formulations in the synthesis of different antistatic additives are shown in Table 3.

Table 3. Synthetic formulations of different antistatic additives*

*The data in the table is the molar ratio Note: In the antistatic agent number of this patent, N stands for non-ionic antistatic agent; A stands for anionic antistatic agent; C stands for cationic antistatic agent.

2. Anionic, cationic and non-ionic permanent antistatic performance mechanism

The anionic, cationic and nonionic antistatic agents involved in this patent have a polymer main chain structure of polyethylene and polyether (PEG) fragmented and aggregated structures, and their antistatic function is based on the side chains containing anionic structures (such as benzenesulfonic acid). acid salts), containing cationic side chains (trimethoxyethylammonium ion or triethylalkylammonium ion), and polar functional group side chains that can form hydrogen bonds and polyether segments comprehensively present the results. The antistatic performance of the polymer antistatic agent reported in this patent is directly related to the environmental humidity, because the side chain cations, anions and functional groups that can form hydrogen bonds and polyether segments have strong charges with water molecules in the environment Interaction or hydrogen bond interaction with water molecules, thus forming an effective charge transfer effect on the surface and interior of the polymer material, so as to achieve antistatic effect.

3. Preparation and performance test of antistatic agent in PET resin splines/templates and polyester fibers

The permanent antistatic agent reported in this patent is directly applied to PET resin, and PET strips and samples containing different antistatic agents and different antistatic agent contents are made, and the contact angle of water at room temperature and different humidity conditions are tested. The antistatic effect was evaluated in parallel with the polyetheresteramide permanent antistatic agent widely used in the market.

3.1 Preparation of antistatic agent PET blending injection molding splines and samples

Put the PET slices in the GHL-012 high-temperature aging test box, and after drying at 130 °C for 4 hours, blend with the patented antistatic additives, EAA compatibilizers, TPEE elastomers and antioxidants. The mass of the electrostatic aid is mixed in proportion. The amount of antioxidants is 2% of the total mass. Feed the mixed material into the SA1200II/370 plastic injection molding machine, and then process it through a specific mold to obtain a dumbbell-shaped spline (see Figure 2, the total length of the spline is L3=167mm, and the length of the parallel part of the narrow part is L1=80mm; The distance between the parallel wide parts is L2=109mm, the thickness is h=4mm; the width of the parallel part of the narrow part is b1=10mm, and the width of the end part is b2=20mm) and the cuboid model (see Figure 1, size: 110x110x2 mm) for performance testing. The parameters of the injection molding process are: the temperature of each zone of the screw is 263°C, 275°C, 275°C, 268°C, and 160°C, the injection pressure is 52-55MPa, and the injection speed is 45rpm. PET splines and samples containing the patented antistatic agent.

3.2 Performance test and test results of PET splines and samples containing the patented antistatic additives

3.2.1 Antistatic agent performance test

(1) Test and analysis of water contact angle

In this patent, the formulations of A-5 and C-5 antistatic agents are selected, and the performance of their PET modified samples is evaluated when the addition amount is different. Among them, the OCA50Micro automatic single fiber contact angle measuring instrument was used to test the water contact angle of the antistatic additive/PET blended material. The test droplet was 3.0 μL, and each sample was tested 5 times to obtain the average value. The test results are shown in Table 4 and FIG. 3 . The surface contact angle of pure PET is 77.5°, and the surface contact angle of the material after adding antioxidant to PET is 77.9°. When the patented cationic antistatic agent C-5 and anionic permanent antistatic agent A-5 are added, the water contact angle is obviously reduced, especially after the addition amount is 16%, the contact angle is especially reduced. The comparison sample polyetheresteramide water contact The contact angle no longer decreases when the angle reaches around 53 degrees (see Table 4).

Table 4: The water contact angle test results of antistatic additives A-5, C-5 and polyetheresteramide on the surface of PET samples with different antistatic additives

*Source and market Arkema products

(2) Antistatic performance test

According to GB/T 31838.3-2019, ZC36 high insulation resistance measuring instrument was used to test the antistatic properties of antistatic additives/PET blended injection molding materials. The sample is 110mm×110mm×2mm cuboid shape, the test voltage is 100V, each sample is tested 10 times to take the average value, and the surface resistance value obtained by the test is converted into surface resistivity according to formula (1). The test results are shown in Table 4 and Table 5.

In the formula: ρ _s is the surface resistivity, Ω; Rs is the surface resistance value, Ω; P is the effective circumference of the protected electrode in the specific electrode device, which is 15.708cm; G is the distance between the measuring electrode and the guard electrode , is 0.2cm. Before the test, the samples were placed in an LRH-300-S constant temperature and humidity incubator with a temperature of 23 °C and a relative humidity of 50% for more than 96 hours.

Table 5 Test Instruments

instrument model Manufacturer High insulation resistance measuring instrument ZC36 Shanghai Anbiao Electronics Co., Ltd. Microcomputer controlled electronic universal testing machine LD23.104 Shenzhen Lanbo Sansi Material Testing Co., Ltd.

Table 6: Surface resistance test results of PET samples with different antistatic agents when the addition amount is 8%

Note: (a) In the antistatic agent number of this patent, N represents non-ionic antistatic agent; A represents anionic antistatic agent; C represents cationic antistatic agent; (b) natural numbers 1, 2, 3, 4, 5, 6, 7, etc. represent different formulations; (c) humidity is 50%.

Table 7A-5, C-5 and polyetheresteramide antistatic additives with different additions of PET sample surface resistance test results

*Market permanent antistatic agent sourced from Arkema; 50% humidity.

3.3 Preparation of polyester fibers with anionic antistatic agent A-5 and cationic antistatic agent C-5 and test results of antistatic properties

Mix anionic antistatic additive A-5 and cationic antistatic additive C-5 with PET fiber resin, elastomer TPEE, compatibilizer EAA and antioxidant according to a certain reasonable mass ratio. The amount of TPEE added is from 2 -17%, and EAA addition amount of 0.5-10% shows good compatibility and processability of antistatic agent and PET. Melt extrusion through twin-screw extruder (type AK36), and pelletize by water-cooling post-cutting machine to obtain antistatic additive/PET blend masterbatch. When the mass fraction of the composite antioxidant accounts for 0.7-3.5%, better anti-yellowing and processing stability are exhibited. Using a twin-screw extruder (Nanjing Keya AK36), the temperature control of the ten zones of processing parameters is 85°C, 230°C, 285°C, 273°C, 273°C, 270°C, 270°C, 268°C, 266°C, 265°C ℃, the main engine speed is 300r/min. The PET used in the experiment was pre-dried in a blast drying oven at 130 °C for 4 h, and the TPEE was pre-dried in a blast drying oven at 105 °C for 3 h.

After the prepared antistatic auxiliary agent/PET blend masterbatch was completely dried, it was fed into a HAAKE MiniLab II hybrid rheometer for melt spinning. The main parameters of spinning are: spinning temperature of 270 °C, screw speed of 70 r/min, spinneret diameter of 2 mm, and winding speed of 150 m/min.

The antistatic properties of antistatic additives/PET blended fibers were tested by ZC36 high insulation resistance measuring instrument (Shanghai Anbiao Electronics Co., Ltd.). Before the test, the fibers are sorted into a sample cake with a mass of 2.5g, a thickness of about 1mm and a diameter of about 100mm, and placed in a LRH-300-S constant temperature and humidity incubator at 20 °C and a certain relative humidity. Equilibrate for 48 hours.

Figure 4 shows anionic antistatic additives/PET blend fibers from left to right, the content of anionic antistatic additives (A-5) is 20%; the middle picture is cationic antistatic additives (C-5) /PET blend fiber, the content is 20%; the right side is the cationic antistatic additive/PET blend fiber, the content is 16%. The upper row in each picture is for non-wetted fibers, and the lower row is for soaked in water and dried. Each two fiber samples with the same antistatic agent were equilibrated in a constant temperature and humidity phase for 96 hours, and then the antistatic properties of each of the same two fiber samples were tested, and the corresponding resistance test results are shown in Table 8.

Table 8 Resistance test results of antistatic additives A-5 and C-5 in PET blended fibers

Note: The polyester fiber with antistatic agent is soaked and then dried, and the data in the table is measured after equilibrating in a constant temperature and humidity chamber for 96 hours.

4 Discussion on the performance test results of the patented antistatic agent in PET resin and polyester fiber

According to the test results, the antistatic agent nonionic and ionic antistatic agent reported in this patent show a certain performance difference. When the content of different antistatic agents is 8%, the antistatic properties of non-ionic antistatic PET samples show higher surface resistance values, while ionic antistatic agents show smaller surface resistance values. Among them, the test results of various formulations of non-ionic, anionic and cationic antistatic agents shown in Table 6 have no obvious difference in antistatic performance. However, when the addition amount of the same antistatic agent (eg: A-5, C-5 and polyetheresteramide) in the PET resin is different, the contact angle of the corresponding modified material sample water changes obviously (see Table 4), the antistatic There were also significant changes in electrostatic properties (see Tables 7 and 8). When the A-5 antistatic agent content is from 4%, 8%, 12%, 16% to 20%, the contact angle of water gradually decreases, and the contact angle decreases significantly when the antistatic agent content reaches 16%. The contact angle of 16% anionic antistatic agent is 51.28, the contact angle of PET modified material containing 16% cationic antistatic agent is reduced to 45.52, and the non-ionic polyetheresteramide antistatic agent is 16% antistatic agent. , the contact angle is 54.14. When the content of antistatic agent continued to increase to 20%, the contact angle of PET sample water containing anionic antistatic agent decreased to 39.54, the contact angle of water containing cationic antistatic agent decreased to 35.66, and the nonionic antistatic agent of polyetheresteramide decreased to 35.66. The contact angle of agent water hardly changed significantly (53.34). Therefore, it can be expected that the ionic antistatic agent has advantages in hydrophilic properties and strong interaction with polar materials when the ambient humidity is high.

When the same anionic antistatic agent A-5, cationic antistatic agent C-5 and polyetheresteramide (Arkema) are added in different amounts in PET resin and polyester fiber, the antistatic properties are significantly different (see table). 7 and Table 8). In the antistatic agent PET modified material sample, no matter whether cationic antistatic agent or anionic antistatic agent is added, when the antistatic agent is added in an amount of 4-12%, it can show a certain antistatic effect, and its resistance value is 10 ¹³ to 10 ¹¹ ohm range, the resistivity is in the 10 ¹⁴ -10 ¹³ ohm range; when the antistatic agent added from 16% to 20%, the surface resistance value of the PET sample will increase from 10 ¹⁰ to 10 ⁹ ohms, showing High-efficiency antistatic effect. The antistatic effect of the market antistatic agent polyetheresteramide shows a similar level with the addition of different amounts.

When the same amount of antistatic agent is added to the polyester fiber, the higher the humidity, the higher the antistatic effect is. Both anionic antistatic agent and cationic antistatic agent show more efficient antistatic effect and low resistance value or low resistivity in polyester fiber. This is because compared with antistatic agent modified PET sample, polyester fiber has With a larger surface area, the surface conductive layer can be formed more effectively, thereby greatly reducing the resistance value or resistivity. As can be seen from Table 8, in the same humidity test results of two polyester fiber samples with the same amount of antistatic agent, it was found that the cationic antistatic agent (C-5) showed a lower performance than the anionic antistatic agent (A-5). Resistance value or resistivity results; even when only 16% of cationic antistatic agent is added, its antistatic effect can be better than that of polyester fiber with 20% of anionic antistatic agent, such as adding 16% cationic antistatic agent. Static agent, when the humidity is 35%, 45%, 55%, 75%, 85%, the resistance values are 4.75×10 ¹⁰ , 5.75×10 ⁹ , 5.70×10 ⁸ , 9.50×10 ⁷ , 1.00×10 ⁶ , respectively ; And the polyester fibers added with 20% anionic antistatic agent under the same humidity conditions are 2.23×10 ¹² , 1.58×10 ¹¹ , 8.20×10 ¹⁰ , 2.85×10 ⁹ , 6.85×10 ⁶ . Judging from the surface resistance value of adding 16% cationic antistatic agent at the same humidity above, each humidity shows more advantageous antistatic effect than polyester fiber adding 20% anionic antistatic agent, only when the humidity reaches 85%, A saturated conductive film can be formed on the surface of the fiber, so the resistance values are all in the same order of magnitude.

The patent of the present invention applies anionic, cationic and nonionic permanent antistatic agents to PET splines and polyester fibers for the first time. A new selection of antistatic functions has been introduced, while maintaining its long-term antistatic properties, solving the phenomenon that antistatic agents are not easy to be washed away and wiped away, and at the same time meet the requirements of permanent antistatic functions. In addition, compared with the widely used permanent antistatic agent polyetheresteramide products in the market, this patented product will not produce the yellowing phenomenon of processed products caused by the permanent antistatic agent of polyetheresteramide by controlling the synthesis conditions and processing parameters.

The applicant declares that the above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should Changes or substitutions that can be easily conceived within the technical scope all fall within the protection scope and disclosure scope of the present invention.

Claims (9)

1. a polymer permanent antistatic agent, is characterized in that, the structural formula is as follows, When it is a non-ionic antistatic agent, the polymer structure is:

b=1,2,3,4,5; c=1,2,3,4,5; d=1,2,3; e=1,2,3,4,5,6,7,8; x=5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20; When it is a cationic antistatic agent, the polymer structure is:

or as:

f=1,2,3,4,5,6,7,8,9; g=1,2,3,4,5; h=1,2,3,4,5; j=1,2, 3; k=1,2,3,4,5,6,7,8; x=5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20; When it is an anionic antistatic agent, the polymer structure is:

f=1,2,3,4,5,6,7,8,9; g=1,2,3,4,5; h=1,2,3,4,5; j=1,2, 3; k=1,2,3,4,5,6,7,8; x=5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20. 2. a preparation method of macromolecule permanent antistatic agent as claimed in claim 1 is characterized in that: when being nonionic antistatic agent, with acrylonitrile, methacrylamide, glycidyl methacrylate and Allyl polyoxyethylene ether is obtained by the polymerization of reactive monomers; when it is an anionic antistatic auxiliary, it is obtained with acrylonitrile, methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether and p-benzene. Sodium ethylene sulfonate is obtained by polymerization of reactive monomers; when it is a cationic antistatic auxiliary, it is obtained with acrylonitrile, methacrylamide, glycidyl methacrylate, allyl polyoxyethylene ether and alfa-methacrylic acid. Acyloxyethyltrimethylammonium chloride or triethylallylammonium chloride is obtained by polymerization of reaction monomers. 3. the preparation method of a kind of macromolecular permanent antistatic agent as claimed in claim ₂ , is characterized in that, concrete steps are as follows: reaction monomer and solvent are added in reaction flask, replace air in reaction flask with N , open Stir and heat to 60-70 ^℃ , add AIBN initiator solution dropwise, then increase the temperature to control the reaction temperature to 70-85 ℃, and the reaction time is 3-8 hours. 4. the preparation method of a kind of macromolecular permanent antistatic agent as claimed in claim 3, it is characterized in that: after reaction finishes, remove solvent with rotary evaporator, use solvent extraction mode to extract it to remove low molecular weight substances, After cooling and solidifying, grind it to small particles with a mortar; then place the product in a vacuum drying oven at 40-60°C for 8-12 hours, and then cool, solidify, grind and granulate to obtain an antistatic additive. 5 . The method for preparing a polymer permanent antistatic agent according to claim 3 , wherein the ratio of the volume of the solvent to the total mass of the functional monomer is not more than 10:1. 6 . 6. The preparation method of a polymer permanent antistatic agent as claimed in claim 3, wherein the mass fraction of the AIBN initiator solution is 0.3% or 0.5% or 1% or 2%. 7 . The method for preparing a polymer permanent antistatic agent according to claim 3 , wherein the reaction flask is a three-necked flask with a reflux device dropping funnel. 8 . 8. the preparation method of a kind of polymer permanent antistatic agent as claimed in claim 3, is characterized in that: described solvent is acetonitrile or butanone or ethylene glycol dimethyl ether or ethylene glycol monomethyl ether or ethyl acetate Ester or ethanol or isopropanol or toluene. 9. A polymer permanent antistatic agent as claimed in claim 1 is applied as a permanent antistatic agent for PET and polyester fibers.

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