A durable antistatic finishing agent copolymer for polyester fabric and its preparation method

Abstract

The present invention relates to a durable antistatic finish copolymer for polyester fabrics and its preparation method. The finish copolymer comprises the following copolymer units: 1) 20-40% by weight of an unsaturated terephthalate ester copolymer containing two double bonds; 2) 40-65% by weight of polyethylene glycol methyl ether methacrylate copolymer units; and 3) 5-25% by weight of an unsaturated phosphate copolymer unit. The durable antistatic finish of the present invention exhibits excellent stability, and polyester fabrics treated with the finish exhibit excellent antistatic properties and washability.

Description

Technical Field

[0001] The invention relates to the field of textile auxiliaries, in particular to a durable antistatic finishing agent for polyester fabrics and a preparation method thereof. Background Art

[0002] Static electricity is a common phenomenon. In spinning and weaving, static electricity can cause high-speed yarns to become tangled and entangled, affecting the machine's normal operation. During dyeing and finishing, static electricity can cause fabric to cling to the machine body or drop rack during fabric drying, causing it to curl backward. During fabric processing, fabrics can attract dust and become contaminated. When consumers wear clothing, static electricity can cause clothing to cling to the body, causing discomfort.

[0003] Polyester is the world's largest and most widely used synthetic fiber, accounting for over 60% of global synthetic fiber production. To meet clothing needs, a variety of fabric types have been developed, including polyester knits, polyester coral fleece, polyester-spandex blends, and micro-fine polyester fabrics.

[0004] Polyester fabrics lack hydrophilic groups, have poor hygroscopicity, and have high surface resistance. During wear, friction causes charge to accumulate on the fabric surface, generating static electricity that seriously affects wearing comfort. Furthermore, static electricity can easily stain clothing with dust, hairiness, and other substances. To improve the wearing comfort of polyester fabrics, antistatic finishing is required.

[0005] Most common antistatic agents on the market today, such as fatty amine polyoxyethylene ethers and fatty acid phosphates, are non-durable. These non-durable antistatic agents only address the impact of static electricity during the production process. Even after the garment is finished, static electricity can still affect consumer comfort. Conventional durable antistatic finishes are mostly polyester-polyether block copolymers, typically synthesized by esterification of terephthalic acid with polyethylene glycol or transesterification of methyl terephthalate with polyethylene glycol, followed by polycondensation. These finishes offer limited antistatic effectiveness, poor fabric compatibility, and insufficient washability.

[0006] Therefore, inventing a durable antistatic finishing agent with excellent washability and wide applicability to fabrics has broad market prospects and practical significance. Summary of the Invention

[0007] One aspect of the present invention is to provide a polyester fabric durable antistatic finishing agent copolymer, comprising the following copolymerization units:

[0008] 1) 20-40 wt% of copolymerized units of unsaturated terephthalate containing two double bonds;

[0009] 2) 40-65 wt% polyethylene glycol methyl ether methacrylate copolymer units;

[0010] 3) 5-25 wt% unsaturated phosphate copolymer units.

[0011] Another aspect of the present invention is to provide a method for preparing the above-mentioned polyester fabric durable antistatic finishing agent copolymer, which comprises the following steps:

[0012] i) preparing a pre-emulsion A by combining an unsaturated terephthalate comonomer and a polyethylene glycol methyl ether methacrylate comonomer in the presence of a cationic emulsifier and a nonionic emulsifier;

[0013] ii) preparing a pre-emulsion B by copolymerizing an unsaturated phosphate comonomer in the presence of a cationic emulsifier and a nonionic emulsifier;

[0014] iii) polymerizing pre-emulsion A in the presence of a free radical initiator, and then adding pre-emulsion B and the remaining portion of the initiator to carry out polymerization. The polymerization temperature is 70-90°C.

[0015] Compared to previously disclosed antistatic finishes and their preparation methods, the durable antistatic finish for polyester fabrics of the present invention exhibits superior effects in the following aspects: 1) The incorporation of phosphate ester and polyethylene glycol methyl ether methacrylate comonomers imparts excellent antistatic properties to the polymer; 2) The incorporation of unsaturated terephthalate ester copolymer units containing two double bonds allows for both linear and network copolymerization with other copolymer units, significantly increasing the crosslink density with polyester fabric and improving washability; 3) The polymer structure of the present invention is similar to that of polyester and can penetrate the softened surface of polyester fibers at high temperatures, forming a eutectic dissolution with the polyester, allowing the finish to adhere to the polyester fibers and achieve durability. The preparation process of the present invention is easy to control, and the resulting durable antistatic finish exhibits excellent washability. DETAILED DESCRIPTION

[0016] In a preferred embodiment, the polyester fabric durable antistatic finishing agent copolymer of the present invention comprises the following copolymerized units:

[0017] 1) 25-35 wt% of copolymerized units of unsaturated terephthalate containing two double bonds;

[0018] 2) 45-60 wt% polyethylene glycol methyl ether methacrylate copolymer units;

[0019] 3) 10-20 wt% unsaturated phosphate copolymer units.

[0020] In a more preferred embodiment, the unsaturated terephthalic acid ester containing two double bonds is selected from, but not limited to, one or both of diallyl terephthalate and bis[4-(vinyloxy)butyl] terephthalate.

[0021] In a more preferred embodiment, the number average molecular weight of the polyethylene glycol methyl ether methacrylate is 600-5000.

[0022] In a more preferred embodiment, the unsaturated phosphate is selected from one or more of allyl dimethyl phosphate, allyl diethyl phosphate, isopropenyl dimethyl phosphate, polyethylene glycol methacrylate phosphate, and di[2-(methacryloyloxy)ethyl]phosphate.

[0023] In a more preferred embodiment, the preparation method of the polyester fabric durable antistatic finishing agent copolymer of the present invention comprises the following steps:

[0024] i) preparing a pre-emulsion A by combining an unsaturated terephthalate comonomer and a polyethylene glycol methyl ether methacrylate comonomer in the presence of a cationic emulsifier and a nonionic emulsifier;

[0025] ii) preparing a pre-emulsion B by copolymerizing an unsaturated phosphate comonomer in the presence of a cationic emulsifier and a nonionic emulsifier;

[0026] iii) polymerizing pre-emulsion A in the presence of a free radical initiator, and then adding pre-emulsion B and the remaining portion of the initiator to carry out polymerization.

[0027] In a more preferred embodiment, the nonionic emulsifier used in the method of the present invention is selected from one or more of fatty alcohol polyoxyethylene ether with an EO number of 15 to 40, Agricultural Ru No. 100, Agricultural Ru No. 300, and Agricultural Ru No. 600; the cationic emulsifier is selected from one or more of C12-C18 alkyl trimethyl ammonium chloride and C12-C18 alkyl trimethyl ammonium bromide.

[0028] In a more preferred embodiment, the free radical initiator is an azo initiator, such as azobisisobutylamidine hydrochloride.

[0029] In a more preferred embodiment, the polymerization reaction is carried out at 70-90°C, preferably at 75-85°C.

[0030] The durable antistatic finishing agent copolymer prepared by the invention has good stability. After being treated with the finishing agent, the antistatic property of the polyester fabric is significantly improved and the washing resistance is excellent.

[0031] Example

[0032] 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.

[0033] In each embodiment, all raw materials and fabrics are commercially available.

[0034] The performance measurement and application effect of each embodiment are measured and evaluated according to the following methods:

[0035] 1. Storage stability

[0036] Store at room temperature and observe after 6 months whether stratification or precipitation occurs.

[0037] 2. Fabric treatment process

[0038] The dosage of durable antistatic agent is 20g / L.

[0039] Process: Dip and roll, then dry at 170℃×90s.

[0040] 3. Determination and evaluation of the performance of durable antistatic agents

[0041] The test is carried out in accordance with "GB / T 12703.1-2021 Textiles Electrostatic Properties Test Method Part 1: Corona Charging Method", and the fabrics are polyester knitted fabric and coral fleece.

[0042] The washing method was carried out according to AATCC 135.

[0043] Example 1

[0044] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 15.6 g of diallyl terephthalate, 20.4 g of polyethylene glycol methyl ether methacrylate (Mn=4000), 0.9 g of Agricultural Milk No. 100, 0.9 g of fatty alcohol polyoxyethylene ether (EO number 15), 1.2 g of dodecyltrimethylammonium chloride, and 198 g of deionized water were added. After stirring and dissolving at 60° C., the mixture was stirred at high speed for 30 minutes to obtain pre-emulsion A.

[0045] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 9.0 g of allyl dimethyl phosphate, 0.3 g of Nongru No. 400, 0.3 g of fatty alcohol polyoxyethylene ether (EO number 15), 0.3 g of dodecyltrimethylammonium chloride, and 48.6 g of deionized water were added. After stirring and dissolving at a temperature not higher than 30° C., the mixture was stirred at high speed for 10 minutes to obtain pre-emulsion B.

[0046] Pre-emulsion A was heated to 74°C, and 3.6 g of a 1% aqueous solution of azobisisobutylamidine hydrochloride was slowly added dropwise. The temperature was maintained constant during the addition. After the addition was complete, the mixture was kept at 74°C for 1.5 hours. Pre-emulsion B and 0.9 g of a 1% aqueous solution of azobisisobutylamidine hydrochloride were then added dropwise. The temperature was maintained constant during the addition. After the addition was complete, the mixture was kept at 74°C for 3.5 hours to obtain durable antistatic finishing agent 1. The application results are shown in Tables 2 and 3.

[0047] Example 2

[0048] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 11.3 g of di[4-(ethyleneoxy)butyl] terephthalate, 27 g of polyethylene glycol methyl ether methacrylate (Mn=600), 0.96 g of Agricultural Milk No. 600, 0.96 g of fatty alcohol polyoxyethylene ether (EO number 20), 1.28 g of hexadecyltrimethylammonium bromide, and 210 g of deionized water were added. After stirring and dissolving at 60° C., the mixture was stirred at high speed for 30 minutes to obtain pre-emulsion A.

[0049] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 6.7 g of di[2-(methacryloyloxy)ethyl]phosphate, 0.25 g of Nongru No. 600, 0.25 g of fatty alcohol polyoxyethylene ether (EO number 20), 0.2 g of hexadecyltrimethylammonium bromide, and 36.6 g of deionized water were added. After stirring and dissolving at a temperature not higher than 30° C., the mixture was stirred at high speed for 10 minutes to obtain pre-emulsion B.

[0050] Pre-emulsion A was heated to 74°C, and 3.6 g of a 1% aqueous solution of azobisisobutylamidine hydrochloride was slowly added dropwise. The temperature was maintained constant during the addition. After the addition was complete, the mixture was kept at 74°C for 1.5 hours. Pre-emulsion B and 0.9 g of a 1% aqueous solution of azobisisobutylamidine hydrochloride were then added dropwise. The temperature was maintained constant during the addition. After the addition was complete, the mixture was kept at 74°C for 3 hours to produce durable antistatic finishing agent 2. The application results are shown in Tables 2 and 3.

[0051] Example 3

[0052] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 7.5 g of diallyl terephthalate, 6 g of di[4-(vinyloxy)butyl] terephthalate, 24 g of polyethylene glycol methyl ether methacrylate (Mn=2000), 0.9 g of Agricultural Milk No. 300, 0.9 g of fatty alcohol polyoxyethylene ether (EO number 40), 1.3 g of octadecyltrimethylammonium chloride, and 205 g of deionized water were added. After stirring and dissolving at 60° C., the mixture was stirred at high speed for 30 minutes to obtain pre-emulsion A.

[0053] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 7.5 g of allyl diethyl phosphate, 0.3 g of Nongru No. 300, 0.3 g of fatty alcohol polyoxyethylene ether (EO number 40), 0.2 g of octadecyltrimethylammonium chloride, and 41.6 g of deionized water were added. After stirring and dissolving at a temperature not higher than 30° C., the mixture was stirred at high speed for 10 minutes to obtain pre-emulsion B.

[0054] Pre-emulsion A was heated to 74°C, and 3.8 g of a 1% aqueous solution of azobisisobutylamidine hydrochloride was slowly added dropwise. The temperature was maintained constant during the addition. After the addition was complete, the mixture was kept at 74°C for 1.5 hours. Pre-emulsion B and 0.7 g of a 1% aqueous solution of azobisisobutylamidine hydrochloride were then added dropwise. The temperature was maintained constant during the addition. After the addition was complete, the mixture was kept at 74°C for 4 hours to produce durable antistatic finish 3. The application results are shown in Tables 2 and 3.

[0055] Table 1 Storage stability evaluation

[0056] sample Appearance after 6 months Example 1 No stratification, no precipitation Example 2 No stratification, no precipitation Example 3 No stratification, no precipitation

[0057] Table 2 Comparison of antistatic properties and washability of polyester knitted fabrics

[0058]

[0059] Table 3 Comparison of antistatic properties and washability of coral fleece

[0060]

[0061] It can be seen from the data in Tables 1, 2 and 3 that the durable antistatic finishing agent prepared by the present invention has good stability. The polyester knitted fabric and coral fleece fabric treated by the present invention still have good antistatic effect after 20 home washes, showing good durability.

[0062] Although the present invention has been disclosed above with reference to the embodiments, it is not intended to limit the scope of protection of the present invention. Any changes and modifications made by any technician familiar with the technology without departing from the concept and scope of the present invention should fall within the scope of protection of the present invention.

Claims

1. A polyester fabric durable antistatic finishing agent copolymer comprising the following copolymer units: 1) 20-40 wt% of copolymerized units of unsaturated terephthalate containing two double bonds; 2) 40-65 wt% polyethylene glycol methyl ether methacrylate copolymer units; 3) 5-25 wt% unsaturated phosphate copolymer units.

2. The polyester fabric durable antistatic finishing agent copolymer according to claim 1, characterized in that: It includes the following copolymerization units: 1) 25-35 wt% of copolymerized units of unsaturated terephthalate containing two double bonds; 2) 45-60 wt% polyethylene glycol methyl ether methacrylate copolymer units; 3) 10-20 wt% unsaturated phosphate copolymer units.

3. The polyester fabric durable antistatic finishing agent copolymer according to claim 1 or 2, characterized in that: The unsaturated terephthalic acid ester containing two double bonds is selected from one or both of diallyl terephthalate and bis[4-(vinyloxy)butyl] terephthalate.

4. The polyester fabric durable antistatic finishing agent copolymer according to claim 1 or 2, characterized in that: The number average molecular weight of the polyethylene glycol methyl ether methacrylate is 600-5000.

5. The polyester fabric durable antistatic finishing agent copolymer according to claim 1 or 2, characterized in that: The unsaturated phosphate is selected from one or more of allyl dimethyl phosphate, allyl diethyl phosphate, isopropenyl dimethyl phosphate, polyethylene glycol methacrylate phosphate, and di[2-(methacryloyloxy)ethyl]phosphate.

6. A method for preparing the polyester fabric durable antistatic finishing agent copolymer according to any one of claims 1 to 5, comprising the following steps: i) preparing a pre-emulsion A by combining an unsaturated terephthalate comonomer and a polyethylene glycol methyl ether methacrylate comonomer in the presence of a cationic emulsifier and a nonionic emulsifier; ii) preparing a pre-emulsion B by copolymerizing an unsaturated phosphate comonomer in the presence of a cationic emulsifier and a nonionic emulsifier; iii) polymerizing pre-emulsion A in the presence of a free radical initiator, and then adding pre-emulsion B and the remaining portion of the initiator to polymerize.

7. The preparation method according to claim 6, wherein The nonionic emulsifier is selected from one or more of fatty alcohol polyoxyethylene ether with an EO number of 15 to 40, Agricultural Ru No. 100, Agricultural Ru No. 300, and Agricultural Ru No. 600; the cationic emulsifier is selected from one or more of C12-C18 alkyl trimethyl ammonium chloride and C12-C18 alkyl trimethyl ammonium bromide.

8. The preparation method according to claim 6 or 7, characterized in that The free radical initiator is an azo initiator.

9. The preparation method according to claim 8, wherein The free radical initiator is azobisisobutylamidine hydrochloride.

10. The preparation method according to claim 6 or 7, characterized in that: The polymerization reaction is carried out at 70-90°C.

Images