Preparation method of antibacterial mildew-proof polyester industrial yarn

Abstract

The invention relates to a preparation method of an antibacterial and mildew-proof polyester industrial yarn, polyester melt is extruded from a spinneret plate and then is sequentially subjected to cooling, oiling, drafting, heat setting and winding to obtain the polyester industrial yarn, and an antibacterial and mildew-proof finishing agent is added into an oiling agent used for oiling; the preparation method of the antibacterial and mildewproof finishing agent comprises the following steps: firstly, carrying out Michael addition reaction between 4-vinylpyridine and diethanol amine to obtain an intermediate, and then carrying out quaternization reaction on the intermediate to obtain the antibacterial and mildewproof chain extender. Then the antibacterial and mildew-proof chain extender, isocyanate and fluorine-containing polyether react to obtain an antibacterial and mildew-proof modified fluorine-containing polyurethane prepolymer, and finally the antibacterial and mildew-proof modified fluorine-containing polyurethane prepolymer and a curing agent are mixed to prepare the antibacterial and mildew-proof finishing agent. The polyester industrial yarn prepared by the method disclosed by the invention has lasting and stable antibacterial and mildew-proof performance, can effectively prevent adhesion of microorganisms, plays a role in timely shielding and killing mould, prevents a coating main body from being damaged, and shows double antibacterial and mildew-proof effects.

Description

Technical Field

[0001] The invention belongs to the technical field of spinning auxiliaries and relates to a method for preparing antibacterial and mildew-proof polyester industrial yarn. Background Art

[0002] Polyester fabrics, due to their excellent physical and functional properties, are widely used in clothing, tent fabrics, hoisting equipment, and advertising light box fabrics. As people's quality of life continues to improve, they have higher requirements for clothing performance. They require clothing to be both soft and comfortable while also possessing excellent antibacterial and mildew-resistant properties.

[0003] Chinese patent CN 113882147 A discloses a process for producing mildew-proof and stain-resistant polyester fabrics, comprising the following steps: preparing polyester fabric; preparing stain-resistant fabric: placing the polyester fabric in an organic fluorine fabric finishing agent, treating it by padding, and heating and baking to obtain stain-resistant polyester fabric; mildew-proofing: placing the stain-resistant polyester fabric in a finishing agent solution containing nano-silver ions for finishing; antibacterial treatment: padding the fabric treated in step 3 into the antibacterial finishing solution for treatment; and subsequent treatment: dehydrating the fabric treated in step 4 using a dehydration device. This process for producing mildew-proof and stain-resistant polyester fabrics achieves mildew-proof and stain-resistant effects, producing high-quality fabrics with antibacterial, mildew-proof, and stain-resistant properties, reducing bacterial growth, preventing odor, and not affecting personal life and environmental hygiene, thereby improving the fabric's usability. Although this finishing method can impart certain antibacterial and mildew-proof properties to polyester fabrics, the treatment method is a physical method, and the silver ions are easily migrated and precipitated, which poses a problem of durability of the antibacterial and mildew-proof properties.

[0004] Therefore, it is of great significance to study a preparation method of antibacterial and mildew-proof polyester industrial yarn to solve the problems existing in the prior art. Summary of the Invention

[0005] The purpose of the present invention is to solve the problems existing in the prior art and provide a method for preparing antibacterial and mildew-proof polyester industrial yarn.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing antibacterial and mildew-proof polyester industrial yarn, comprising: extruding a polyester melt from a spinneret, followed by cooling, oiling, drawing, heat setting, and winding to produce the polyester industrial yarn; and adding an antibacterial and mildew-proof finishing agent to the oil used for oiling.

[0008] The preparation method of the antibacterial and mildew-proof finishing agent comprises the following steps: firstly, a Michael addition reaction between 4-vinylpyridine and diethanolamine is used to obtain an intermediate; then, the intermediate is subjected to a quaternization reaction to obtain an antibacterial and mildew-proof chain extender; then, the antibacterial and mildew-proof chain extender is reacted with isocyanate and fluorinated polyether diol to obtain an antibacterial and mildew-proof modified fluorinated polyurethane prepolymer; and finally, the antibacterial and mildew-proof modified fluorinated polyurethane prepolymer and a curing agent are mixed to obtain the antibacterial and mildew-proof finishing agent.

[0009] The antibacterial and mildew-proof finishing agent cross-links and solidifies into modified polyurethane during heat setting; the antibacterial and mildew-proof chain extender allows quaternary ammonium salts to be suspended on the side chains of the modified polyurethane, which can disinfect bacteria and exert antibacterial and mildew-proof effects; the fluorinated polyether allows fluorine atoms to be suspended on the side chains of the modified polyurethane. Fluorinated substances have low surface energy and are hydrophobic and oleophobic, so they can significantly reduce the surface energy of the coating, prevent bacteria from adhering, and play an anti-fouling role; when fluorine atoms are not introduced, the fiber surface does not have low surface energy anti-fouling properties after finishing, and bacteria and other pollutants may be loaded on the fiber surface in large quantities, which puts pressure on the bactericidal effect of the quaternary ammonium salt. A large amount of quaternary ammonium salt groups is required to achieve a good antibacterial and mildew-proof effect. If fluorine atoms are introduced at this time, the pressure on the quaternary ammonium salt groups will be reduced, and an excellent antibacterial and mildew-proof effect can be achieved at a smaller dosage; on the contrary, if a simple fluorinated polyurethane finishing agent is prepared, the fluorine atoms themselves have no antibacterial effect, and when encountering some low-surface-energy bacterial pollutants, they are difficult to resist.

[0010] As the preferred technical solution:

[0011] The specific preparation steps of the antibacterial and mildew-proof polyester industrial yarn preparation method and the antibacterial and mildew-proof finishing agent are as follows:

[0012] (1) Synthesis of antibacterial and antifungal chain extenders:

[0013] First, diethanolamine is added to a flask and stirred, and then 4-vinylpyridine is added dropwise to the flask to carry out a Michael addition reaction with diethanolamine. During the dropwise addition process, the reaction temperature is 50-60°C and the dropwise addition time is 1-2 hours. Then, triethylamine is added to the flask to continue catalyzing the Michael addition reaction. The reaction temperature after the addition of triethylamine is controlled to be 60-65°C, that is, the reaction system will heat up after the addition of triethylamine. The temperature is controlled at 60-65°C and the reaction time is 12-16 hours. Then, residual 4-vinylpyridine and triethylamine are removed by reduced pressure distillation to obtain an intermediate. Finally, the intermediate and 4-chlorobutyric anhydride are reacted at room temperature for 12 hours to ensure that the pyridine ring has been completely quaternized. After separation and purification, an antibacterial and antifungal chain extender is obtained, wherein the mass ratio of diethanolamine to 4-vinylpyridine is 10-15:20-30, and the mass ratio of the intermediate to 4-chlorobutyric anhydride is 10:30-40.

[0014] First, add diethanolamine, then add 4-vinylpyridine dropwise. The Michael addition reaction begins during the addition process, and there will be a slight release of heat, so the temperature should be controlled at 50-60°C. The purpose of adding triethylamine is to increase the conversion rate of the monomer. Because the reaction rate decreases in the later stage, triethylamine is added as a catalyst to ensure that as much diethanolamine as possible is added to vinylpyridine in a short period of time.

[0015] In the structure of 4-chlorobutyric anhydride, due to the electron-withdrawing property of the carbonyl oxygen atom, it has an acid anhydride group with good activity and is easy to form a carbonyl carbon ion (such as Figure 1 Intermediate (structural formula as shown); Figure 2 As shown in the figure, the nitrogen atom of pyridine in the intermediate structure has a lone pair of electrons and can act as a nucleophile to attack the partially positively charged carbonyl carbon in 4-chlorobutyric anhydride. The CO bond of the anhydride breaks, and the nitrogen atom of pyridine forms a covalent bond with the carbonyl carbon to generate an N-acylpyridine intermediate (structural formula as shown in the figure). Figure 3 In addition to reacting with carbonyl carbon, the basic intermediate can also induce 4-chlorobutyric anhydride to dissociate Cl - , the reaction formula is as follows Figure 4 As shown; Finally, Cl - With N + Combined to form quaternary ammonium salt, an antibacterial and mildew-proof chain extender is obtained (the antibacterial and mildew-proof chain extender obtained after separation and purification has the structural formula Figure 5 and 6 mixture of the two substances shown);

[0016] (2) Preparation of antibacterial and mildew-proof modified polyurethane prepolymer:

[0017] The dehydrated fluorinated polyether diol is added to a reactor, and then isocyanate and organic bismuth catalyst I are added in sequence. The temperature is then raised to 80-85°C and the reaction is carried out for 1-2 hours. Thereafter, an antibacterial and mildew-proof chain extender is added to the reactor and the reaction is carried out at 80-85°C for 1-2 hours to obtain an antibacterial and mildew-proof modified polyurethane prepolymer, which is a hydroxyl-terminated antibacterial and mildew-proof modified polyurethane prepolymer. The mass ratio of the dehydrated fluorinated polyether diol, isocyanate, organic bismuth catalyst I and antibacterial and mildew-proof chain extender is 40-60:18-25:0.05-0.1:6-10.

[0018] Fluorinated polyether diols are dehydrated to avoid side reactions. The main reaction is the polyaddition reaction between hydroxyl groups and isocyanates. Diols usually contain trace amounts of water during storage. When reacting with isocyanates, the reaction between water and isocyanate is a side reaction, so water must be removed first.

[0019] The reason for adding the antibacterial and antifungal chain extender after heating to 80-85°C and reacting for 1-2 hours is to make the antibacterial and antifungal chain extender more evenly distributed in the polyurethane macromolecules.

[0020] (3) Preparation of antibacterial and antifungal finishing agents:

[0021] The antibacterial and mildew-proof modified polyurethane prepolymer, curing agent and organic bismuth catalyst II are uniformly mixed to obtain an antibacterial and mildew-proof finishing agent; wherein the mass ratio of the antibacterial and mildew-proof modified polyurethane prepolymer, curing agent and organic bismuth catalyst II is 80-100:20-30:0.05-0.1;

[0022] The antibacterial and mildew-proof finishing agent in step (3) is a solvent-free two-component antibacterial and mildew-proof finishing agent, which does not contain any added solvent and is more environmentally friendly.

[0023] In the above-mentioned method for preparing the antibacterial and mildew-proof polyester industrial yarn, the preparation process of the intermediate is carried out under nitrogen protection.

[0024] In the above-mentioned method for preparing antibacterial and mildew-proof polyester industrial yarn, the fluorinated polyether diol is a perfluoropolyether diol having a number average molecular weight of 1000-4000.

[0025] In the above-mentioned method for preparing antibacterial and mildew-proof polyester industrial yarn, the isocyanate is isophorone diisocyanate or hexamethylene diisocyanate.

[0026] In the above-mentioned method for preparing antibacterial and mildew-proof polyester industrial yarn, the curing agent is HDI trimer or IPDI trimer.

[0027] In the above-mentioned method for preparing antibacterial and mildew-proof polyester industrial yarn, the organic bismuth catalyst I and the organic bismuth catalyst II are each independently selected from at least one of bismuth neodecanoate and bismuth isooctanoate.

[0028] As described above, in the preparation method of the antibacterial and mildew-proof polyester industrial yarn, the heat setting temperature is 90~110℃ and the time is 2~3s. Although there will be temperature during stretching, the stretching speed is relatively fast, and a small part will be solidified, but the solidification is incomplete, so further heat curing is required. The heat setting process can achieve complete curing.

[0029] In the above-mentioned method for preparing antibacterial and mildew-proof polyester industrial yarn, the content of the antibacterial and mildew-proof finishing agent in the oil is 50-60wt%, and the amount of oil applied is 1-2wt%.

[0030] The above-mentioned method for preparing an antibacterial and mildew-proof polyester industrial yarn has excellent antibacterial and mildew-proof durability. After washing according to GB / T 8629-2017, the antibacterial and mildew-proof polyester industrial yarn has an inhibition rate against Escherichia coli higher than 95%; according to the stain resistance test according to GB / T 30159.1-2013, the stain level of the fabric woven with the antibacterial and mildew-proof polyester industrial yarn is level 5.

[0031] Beneficial effects:

[0032] (1) The present invention provides a method for preparing antibacterial and mildew-proof polyester industrial yarn, which synthesizes an antibacterial and mildew-proof finishing agent containing dihydroxyl groups and introduces it into the heat-curing system of the spinning finishing agent in the form of covalent and hanging side chains. After heat setting, curing and cross-linking, the oil agent can form a uniform and dense coating on the surface of the industrial yarn. On the one hand, it can effectively improve the migration resistance and distribution uniformity of the antibacterial and mildew-proof finishing agent in the coating, and the antibacterial and mildew-proof performance is long-lasting and stable; on the other hand, the antibacterial and mildew-proof groups are all suspended on the macromolecular side chains and play a synergistic role with the fluorine-containing soft segments, so that when the industrial yarn is subjected to mold, it can effectively prevent the attachment of microorganisms, play a role in timely shielding and disinfecting mold, and protect the coating body from damage, showing a dual antibacterial and mildew-proof effect;

[0033] (2) The present invention provides a method for preparing antibacterial and mildew-proof polyester industrial yarn, which cleverly utilizes the original oiling process in the manufacture of polyester industrial yarn to evenly apply the antibacterial and mildew-proof finishing agent to the surface of the industrial yarn, and further heat-sets it to form a coating. This method does not require changing the original continuous spinning process of the polyester industrial yarn, and can impart significant antibacterial and mildew-proof properties to the industrial yarn while retaining its original structure and excellent mechanical properties.

[0034] (3) The present invention provides a method for preparing antibacterial and mildew-proof polyester industrial yarn. The prepared antibacterial and mildew-proof finishing agent does not use any organic solvent, which can achieve a clean production process. The prepared polyester industrial yarn is an environmentally friendly product, which is in line with the industry development trend and meets the green and healthy needs of consumers. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Schematic diagram of the formation of carbonyl carbenium ion from the anhydride group in 4-chlorobutyric anhydride;

[0036] Figure 2 is a schematic diagram of the structure of the intermediate;

[0037] Figure 3 Schematic diagram of the structure of N-acylpyridine intermediate;

[0038] Figure 4 As an intermediate, it induces 4-chlorobutyric anhydride to dissociate Cl - The reaction formula of

[0039] Figure 5 and Figure 6 Schematic diagram of the structure of the antibacterial and antifungal chain extender. DETAILED DESCRIPTION

[0040] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0041] The test methods involved in the performance indicators of the present invention are as follows:

[0042] Antibacterial rate against Escherichia coli: tested in accordance with GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method".

[0043] Contamination level: According to GB / T 30159.1-2013, polyester knitted fabrics woven from antibacterial and mildew-proof polyester industrial yarns (weight 120~180 g / m 2 ) for stain resistance test.

[0044] Example 1

[0045] A method for preparing antibacterial and mildew-proof polyester industrial yarn, comprising the following specific steps:

[0046] (1) Synthesis of antibacterial and antifungal chain extenders:

[0047] (1.1) Under nitrogen, diethanolamine was first added to a flask and stirred. 4-vinylpyridine was then added dropwise to the flask to react with diethanolamine via a Michael addition reaction. The reaction temperature was 50°C for 1 hour. Triethylamine was then added to the flask to continue the Michael addition reaction for 12 hours. The reaction temperature after the addition of triethylamine was controlled at 60°C to obtain the intermediate.

[0048] The mass ratio of diethanolamine, 4-vinylpyridine and triethylamine is 10:20:10;

[0049] (1.2) The intermediate and 4-chlorobutyric anhydride are reacted at room temperature for 12 h, and an antibacterial and antifungal chain extender is obtained after separation and purification. The mass ratio of the intermediate to 4-chlorobutyric anhydride is 10:30.

[0050] (2) Preparation of antibacterial and mildew-proof modified polyurethane prepolymer:

[0051] Dehydrated perfluoropolyether diol (number average molecular weight of 4000) was added to a reactor, followed by isophorone diisocyanate and bismuth neodecanoate. The temperature was then raised to 85°C and the reaction was continued for 1 hour. An antibacterial and mildew-proof chain extender was then added to the reactor and the reaction was continued at 80°C for 1 hour to obtain an antibacterial and mildew-proof modified polyurethane prepolymer.

[0052] The mass ratio of the dehydrated perfluoropolyether diol, isophorone diisocyanate, bismuth neodecanoate and antibacterial and mildew-proof chain extender is 40:18:0.1:6;

[0053] (3) Preparation of antibacterial and antifungal finishing agents:

[0054] The antibacterial and mildew-proof modified polyurethane prepolymer, HDI trimer (manufacturer: Bayer, brand: N3900) and bismuth neodecanoate are uniformly mixed to obtain an antibacterial and mildew-proof finishing agent;

[0055] The mass ratio of the antibacterial and antifungal modified polyurethane prepolymer, HDI trimer and bismuth neodecanoate is 80:20:0.05;

[0056] (4) After the polyester melt is extruded from the spinneret, it is sequentially cooled, oiled, drawn, heat-set, and wound to produce polyester industrial yarn. The oil used for oiling is added with an antibacterial and antifungal finishing agent, and the content of the antibacterial and antifungal finishing agent in the oil is 50wt%;

[0057] The process parameters are as follows: spinning temperature 300 ℃, cooling temperature 18 ℃; oiling amount 1 wt%; drawing temperature 140 ℃, drawing ratio 4 times; heat setting temperature 90 ℃, time 3 s.

[0058] According to GB / T 8629-2017, after washing, the antibacterial and mildew-proof polyester industrial yarn has an antibacterial rate of 99.6% against Escherichia coli; according to the stain resistance test of GB / T 30159.1-2013, the polyester knitted fabric woven with antibacterial and mildew-proof polyester industrial yarn (weight 120g / m 2 ) is contamination level 5.

[0059] Comparative Example 1

[0060] A method for preparing antibacterial and mildew-proof polyester industrial yarn is basically the same as Example 1, except that the perfluoropolyether diol in step (2) is replaced by polytetramethylene ether diol.

[0061] After washing according to GB / T 8629-2017, the antibacterial and mildew-proof polyester industrial yarn has an inhibition rate of 18% against Escherichia coli; according to the stain resistance test of GB / T 30159.1-2013, the stain level of polyester knitted fabric woven with antibacterial and mildew-proof polyester industrial yarn is Level 1.

[0062] Comparing Comparative Example 1 with Example 1, it can be found that the antibacterial rate of Comparative Example 1 is reduced. This is because polytetramethylene ether glycol contains a large number of polar ether bonds, does not contain fluorine atoms, has no anti-fouling function, and is hydrophilic and easily contaminated by liquid pollutants.

[0063] Example 2

[0064] A method for preparing antibacterial and mildew-proof polyester industrial yarn, comprising the following specific steps:

[0065] (1) Synthesis of antibacterial and antifungal chain extenders:

[0066] (1.1) Under nitrogen, diethanolamine was first added to a flask and stirred. 4-vinylpyridine was then added dropwise to the flask to react with diethanolamine via a Michael addition reaction. The reaction temperature was 55°C for 1 hour. Triethylamine was then added to the flask to catalyze the Michael addition reaction for 12 hours. The reaction temperature after the addition of triethylamine was controlled at 60°C to obtain the intermediate.

[0067] The mass ratio of diethanolamine, 4-vinylpyridine and triethylamine is 10:20:10;

[0068] (1.2) The intermediate and 4-chlorobutyric anhydride are reacted at room temperature for 12 h, and an antibacterial and antifungal chain extender is obtained after separation and purification. The mass ratio of the intermediate to 4-chlorobutyric anhydride is 10:35.

[0069] (2) Preparation of antibacterial and mildew-proof modified polyurethane prepolymer:

[0070] Dehydrated perfluoropolyether diol (number average molecular weight of 3000) was added to a reactor, followed by isophorone diisocyanate and bismuth isooctanoate. The temperature was then raised to 80°C and the reaction was continued for 1 hour. An antibacterial and mildew-proof chain extender was then added to the reactor and the reaction was continued at 85°C for 2 hours to obtain an antibacterial and mildew-proof modified polyurethane prepolymer.

[0071] The mass ratio of the dehydrated perfluoropolyether diol, isophorone diisocyanate, bismuth isooctanoate and antibacterial and mildew-proof chain extender is 40:18:0.1:8;

[0072] (3) Preparation of antibacterial and antifungal finishing agents:

[0073] The antibacterial and mildew-proof modified polyurethane prepolymer, HDI trimer (manufacturer: Bayer, brand: N3900) and bismuth isooctanoate are uniformly mixed to obtain an antibacterial and mildew-proof finishing agent;

[0074] The mass ratio of the antibacterial and antifungal modified polyurethane prepolymer, HDI trimer and bismuth isooctanoate is 90:24:0.05;

[0075] (4) After the polyester melt is extruded from the spinneret, it is sequentially cooled, oiled, drawn, heat-set, and wound to produce polyester industrial yarn. The oil used for oiling is added with an antibacterial and antifungal finishing agent, and the content of the antibacterial and antifungal finishing agent in the oil is 50wt%;

[0076] The process parameters are as follows: spinning temperature 310 ℃, cooling temperature 24 ℃; oiling amount 2 wt%; drawing temperature 150 ℃, drawing ratio 5 times; heat setting temperature 100 ℃, time 2 s.

[0077] According to GB / T 8629-2017, after washing, the antibacterial and mildew-proof polyester industrial yarn has an antibacterial rate of 99.5% against Escherichia coli; according to the GB / T 30159.1-2013 stain resistance test, the polyester knitted fabric woven with antibacterial and mildew-proof polyester industrial yarn (weight 140g / m 2 ) is contamination level 5.

[0078] Example 3

[0079] A method for preparing antibacterial and mildew-proof polyester industrial yarn, comprising the following specific steps:

[0080] (1) Synthesis of antibacterial and antifungal chain extenders:

[0081] (1.1) Under nitrogen, diethanolamine was first added to a flask and stirred. 4-vinylpyridine was then added dropwise to the flask to react with diethanolamine via a Michael addition reaction. The reaction temperature was 60°C for 1 hour. Triethylamine was then added to the flask to catalyze the Michael addition reaction for 12 hours. The reaction temperature after the addition of triethylamine was controlled at 65°C to obtain the intermediate.

[0082] The mass ratio of diethanolamine, 4-vinylpyridine and triethylamine is 10:20:10;

[0083] (1.2) The intermediate and 4-chlorobutyric anhydride are reacted at room temperature for 12 h, and an antibacterial and antifungal chain extender is obtained after separation and purification. The mass ratio of the intermediate to 4-chlorobutyric anhydride is 10:40.

[0084] (2) Preparation of antibacterial and mildew-proof modified polyurethane prepolymer:

[0085] Dehydrated perfluoropolyether diol (number average molecular weight of 1000) was added to a reactor, followed by hexamethylene diisocyanate and bismuth isooctanoate. The temperature was then raised to 85°C and the reaction was continued for 1 hour. An antibacterial and mildew-proof chain extender was then added to the reactor and the reaction was continued at 85°C for 2 hours to obtain an antibacterial and mildew-proof modified polyurethane prepolymer.

[0086] The mass ratio of the dehydrated perfluoropolyether diol, hexamethylene diisocyanate, bismuth isooctanoate and antibacterial and mildew-proof chain extender is 60:25:0.1:10;

[0087] (3) Preparation of antibacterial and antifungal finishing agents:

[0088] The antibacterial and mildew-proof modified polyurethane prepolymer, IPDI trimer (manufacturer: Bayer, brand: BL 4265 SN) and bismuth isooctanoate are uniformly mixed to obtain an antibacterial and mildew-proof finishing agent;

[0089] The mass ratio of the antibacterial and antifungal modified polyurethane prepolymer, IPDI trimer and bismuth isooctanoate is 100:30:0.1;

[0090] (4) After the polyester melt is extruded from the spinneret, it is cooled, oiled, drawn, heat-set, and wound to produce polyester industrial yarn. The oil used for oiling is added with an antibacterial and antifungal finishing agent, and the content of the antibacterial and antifungal finishing agent in the oil is 60wt%;

[0091] The process parameters are as follows: spinning temperature 320 ℃, cooling temperature 28 ℃; oiling amount 1 wt%; drawing temperature 160 ℃, drawing ratio 6 times; heat setting temperature 110 ℃, time 2 s.

[0092] According to GB / T 8629-2017, after washing, the antibacterial and mildew-proof polyester industrial yarn has an antibacterial rate of 99.9% against Escherichia coli; according to the stain resistance test of GB / T 30159.1-2013, the polyester knitted fabric woven with antibacterial and mildew-proof polyester industrial yarn (weight 160g / m 2 ) is contamination level 5.

[0093] Example 4

[0094] A method for preparing antibacterial and mildew-proof polyester industrial yarn, comprising the following specific steps:

[0095] (1) Synthesis of antibacterial and antifungal chain extenders:

[0096] (1.1) Under nitrogen, diethanolamine was first added to a flask and stirred. 4-vinylpyridine was then added dropwise to the flask to react with diethanolamine via a Michael addition reaction. The reaction temperature was 50°C for 2 h. Triethylamine was then added to the flask to catalyze the Michael addition reaction for 12 h. The reaction temperature after the addition of triethylamine was controlled at 65°C to obtain the intermediate.

[0097] The mass ratio of diethanolamine, 4-vinylpyridine and triethylamine is 15:30:10;

[0098] (1.2) The intermediate and 4-chlorobutyric anhydride are reacted at room temperature for 12 h, and an antibacterial and antifungal chain extender is obtained after separation and purification. The mass ratio of the intermediate to 4-chlorobutyric anhydride is 10:40.

[0099] (2) Preparation of antibacterial and mildew-proof modified polyurethane prepolymer:

[0100] Dehydrated perfluoropolyether diol (number average molecular weight of 1000) was added to a reactor, followed by the addition of hexamethylene diisocyanate and a 1:1 mass ratio mixed catalyst of bismuth neodecanoate and bismuth isooctanoate. The temperature was then raised to 80°C and the reaction was carried out for 2 h. An antibacterial and mildew-proof chain extender was then added to the reactor and the reaction was carried out at 85°C for 2 h to obtain an antibacterial and mildew-proof modified polyurethane prepolymer.

[0101] The mass ratio of the dehydrated perfluoropolyether diol, hexamethylene diisocyanate, bismuth neodecanoate and bismuth isooctanoate mixed catalyst in a mass ratio of 1:1 and the antibacterial and mildew-proof chain extender is 50:20:0.05:8;

[0102] (3) Preparation of antibacterial and antifungal finishing agents:

[0103] The antibacterial and mildew-proof modified polyurethane prepolymer, IPDI trimer (manufacturer: Bayer, brand: BL 4265 SN) and a mixed catalyst of bismuth neodecanoate and bismuth isooctanoate in a mass ratio of 1:1 are uniformly mixed to obtain an antibacterial and mildew-proof finishing agent;

[0104] Among them, the mass ratio of antibacterial and antifungal modified polyurethane prepolymer, IPDI trimer and 1:1 mass ratio of bismuth neodecanoate and bismuth isooctanoate mixed catalyst is 95:27:0.08;

[0105] (4) After the polyester melt is extruded from the spinneret, it is cooled, oiled, drawn, heat-set, and wound to produce polyester industrial yarn. The oil used for oiling is added with an antibacterial and antifungal finishing agent, and the content of the antibacterial and antifungal finishing agent in the oil is 60wt%;

[0106] The process parameters are as follows: spinning temperature 320 ℃, cooling temperature 28 ℃; oiling amount 2 wt%; drawing temperature 160 ℃, drawing ratio 6 times; heat setting temperature 105 ℃, time 2.5 s.

[0107] According to GB / T 8629-2017, after washing, the antibacterial and mildew-proof polyester industrial yarn has an antibacterial rate of 99.8% against Escherichia coli; according to the stain resistance test of GB / T 30159.1-2013, the polyester knitted fabric woven with antibacterial and mildew-proof polyester industrial yarn (weight 180g / m 2 ) is contamination level 5.

Claims

1. A method for preparing antibacterial and mildew-proof polyester industrial yarn, wherein the polyester melt is extruded from a spinneret and then subjected to cooling, oiling, drawing, heat setting, and winding to obtain the polyester industrial yarn, characterized in that: Add antibacterial and anti-mildew finishing agents to the oil used for oiling; The preparation method of the antibacterial and mildew-proof finishing agent comprises the following steps: firstly, a Michael addition reaction between 4-vinylpyridine and diethanolamine is used to obtain an intermediate; then, the intermediate is subjected to a quaternization reaction to obtain an antibacterial and mildew-proof chain extender; then, the antibacterial and mildew-proof chain extender is reacted with isocyanate and fluorinated polyether diol to obtain an antibacterial and mildew-proof modified fluorinated polyurethane prepolymer; and finally, the antibacterial and mildew-proof modified fluorinated polyurethane prepolymer and a curing agent are mixed to obtain the antibacterial and mildew-proof finishing agent.

2. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 1, characterized in that: The specific preparation steps of the antibacterial and mildew-proof finishing agent are as follows: (1) Synthesis of antibacterial and antifungal chain extenders: First, diethanolamine is added to a flask and stirred. Then, 4-vinylpyridine is added dropwise to the flask to undergo a Michael addition reaction with the diethanolamine. The reaction temperature during the dropwise addition process is 50-60°C and the dropwise addition time is 1-2 hours. Then, triethylamine is added to the flask to continue catalyzing the Michael addition reaction. The reaction temperature after the addition of triethylamine is controlled to be 60-65°C and the reaction time is 12-16 hours to obtain an intermediate. Finally, the intermediate is reacted with 4-chlorobutyric anhydride at room temperature for 12 hours to obtain an antibacterial and mildew-proof chain extender. The mass ratio of diethanolamine to 4-vinylpyridine is 10-15:20-30, and the mass ratio of the intermediate to 4-chlorobutyric anhydride is 10:30-40. (2) Preparation of antibacterial and mildew-proof modified polyurethane prepolymer: The dehydrated fluorinated polyether diol is added to a reactor, and then isocyanate and organic bismuth catalyst I are added in sequence. The temperature is then raised to 80-85°C and the reaction is carried out for 1-2 hours. Thereafter, an antibacterial and mildew-proof chain extender is added to the reactor and the reaction is carried out at 80-85°C for 1-2 hours to obtain an antibacterial and mildew-proof modified polyurethane prepolymer. The mass ratio of the dehydrated fluorinated polyether diol, isocyanate, organic bismuth catalyst I, and antibacterial and mildew-proof chain extender is 40-60:18-25:0.05-0.1:6-10. (3) Preparation of antibacterial and antifungal finishing agents: The antibacterial and mildew-proof modified polyurethane prepolymer, curing agent and organic bismuth catalyst II are uniformly mixed to obtain an antibacterial and mildew-proof finishing agent; wherein the mass ratio of the antibacterial and mildew-proof modified polyurethane prepolymer, curing agent and organic bismuth catalyst II is 80-100:20-30:0.05-0.

1.

3. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 2, characterized in that: The preparation process of the intermediates was carried out under nitrogen protection.

4. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 2, characterized in that: The fluorinated polyether diol is a perfluoropolyether diol having a number average molecular weight of 1000 to 4000.

5. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 2, characterized in that: The isocyanate is isophorone diisocyanate or hexamethylene diisocyanate.

6. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 2, characterized in that: The curing agent is HDI trimer or IPDI trimer.

7. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 2, characterized in that: The organic bismuth catalyst I and the organic bismuth catalyst II are each independently selected from at least one of bismuth neodecanoate and bismuth isooctanoate.

8. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 1, characterized in that: The heat setting temperature is 90~110℃ and the time is 2~3s.

9. The method for preparing antibacterial and mildew-proof polyester industrial yarn according to claim 1, characterized in that: The content of the antibacterial and anti-mildew finishing agent in the oil is 50-60wt%, and the amount of oil applied is 1-2wt%.

10. The method for preparing the antibacterial and mildew-resistant polyester industrial yarn according to any one of claims 1 to 9, wherein after washing in accordance with GB / T 8629-2017, the antibacterial and mildew-resistant polyester industrial yarn has an inhibition rate against Escherichia coli greater than 95%; and according to the stain resistance test in accordance with GB / T 30159.1-2013, the stain grade of the fabric woven from the antibacterial and mildew-resistant polyester industrial yarn is 5.

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