Durable antistatic finishing agent copolymer for polyester fabric and preparation method of durable antistatic finishing agent copolymer

Abstract

The invention relates to a durable antistatic finishing agent copolymer for polyester fabrics and a preparation method of the durable antistatic finishing agent copolymer. The finishing agent copolymer comprises the following copolymerization units: 1) 20-40 wt% of a terephthalic acid unsaturated ester copolymerization unit containing two double bonds; 2) 40-65 wt% of a polyethylene glycol methyl ether methacrylate copolymerization unit; and 3) 5-25 wt% of an unsaturated phosphate copolymerization unit. The durable antistatic finishing agent disclosed by the invention is good in stability, and the polyester fabric treated by the finishing agent is excellent in antistatic performance and good in washability.

Description

Technical Field

[0001] The invention relates to the field of textile auxiliaries, and 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, due to static electricity, the high-speed yarn will be tangled and affect the normal operation of the machine; in the dyeing and finishing process, when the fabric is dried, static electricity often causes the fabric to adhere to the machine body or the cloth rack, causing reverse rolling; in the fabric processing process, the fabric will absorb dust and cause contamination; when consumers wear clothes, static electricity often causes the clothes to entangle with the human body, causing sticky discomfort.

[0003] Polyester is the world's largest and most widely used synthetic fiber, accounting for more than 60% of the world's synthetic fiber production. In order to meet clothing needs, a variety of fabrics have been developed on the market, including polyester knitted fabrics, polyester coral fleece, polyester-spandex blended fabrics, superfine polyester fabrics, etc.

[0004] Polyester fabric lacks hydrophilic groups, has poor hygroscopicity, and has high surface resistance. During wearing, due to friction, charges will accumulate on the surface of the fabric, generating static electricity, which seriously affects its comfort. In addition, due to static electricity, clothing is easily stained with dust, hairiness, etc. In order to improve the comfort of wearing polyester fabric, antistatic finishing is required for polyester fabric.

[0005] At present, most of the common antistatic agents on the market are non-durable, such as fatty amine polyoxyethylene ether, fatty acid phosphate, etc. These non-durable antistatic agents can only solve the impact of static electricity on the production and processing process. After the clothes are made, static electricity will still affect the wearing comfort of consumers. Conventional durable antistatic finishing agents are mostly polyester polyether block copolymers, which are usually synthesized by esterification of terephthalic acid and polyethylene glycol or ester exchange of methyl terephthalate and polyethylene glycol, and then polycondensation reaction. This type of finishing agent has a general antistatic effect, poor fabric applicability, and insufficient washing resistance.

[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 copolymer units:

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

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

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

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

[0012] i) preparing a pre-emulsion A with unsaturated terephthalate comonomer and 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 part of the initiator to polymerize. The polymerization temperature is 70-90°C.

[0015] Compared with the currently disclosed antistatic finishing agent and its preparation method, the excellent effect of the polyester fabric durable antistatic finishing agent of the present invention is manifested in the following aspects: 1) the introduction of phosphate ester and polyethylene glycol methyl ether methacrylate comonomers makes the polymer have excellent antistatic effect; 2) the introduction of unsaturated terephthalate ester copolymer units containing two double bonds can be copolymerized linearly or reticularly with other copolymer units, greatly improving the crosslinking density with polyester fabric and improving washing resistance; 3) the polymer structure of the present invention is similar to that of polyester, and can enter the softened fiber surface of polyester at high temperature, dissolve eutectic with polyester, so that the finishing agent is fixed on the polyester fiber to obtain durability. The preparation process of the present invention is easy to control, and the prepared durable antistatic finishing agent has good washing resistance. DETAILED DESCRIPTION

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

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

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

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

[0020] In a more preferred embodiment, the unsaturated terephthalic acid ester containing two double bonds is selected from, for example, but not limited to, one or both of diallyl terephthalate and di[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 ester 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 with unsaturated terephthalate comonomer and 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 part of the initiator to polymerize.

[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 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 azobisisobutyramidine 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] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it 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 within the scope limited by the appended claims of the application equally.

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

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

[0035] 1. Storage stability

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

[0037] 2. Fabric treatment process

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

[0039] Process: One dip and one rolling followed by drying 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 Test method for electrostatic properties of textiles 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, and after stirring and dissolving at 60°C, the mixture was stirred at a high speed for 30 minutes to obtain pre-emulsion A.

[0045] Into 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 agricultural milk 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 pre-emulsion B was obtained by high-speed stirring for 10 minutes.

[0046] The pre-emulsion A was heated to 74°C, and 3.6 g of 1% azobisisobutylamidine hydrochloride aqueous solution was slowly added dropwise, and the temperature was kept constant during the addition. After the addition was completed, the temperature was kept at 74°C for 1.5 hours, and then the pre-emulsion B and 0.9 g of 1% azobisisobutylamidine hydrochloride aqueous solution were added dropwise, and the temperature was kept constant during the addition. After the addition was completed, the temperature was kept for reaction for 3.5 hours to obtain a durable antistatic finishing agent 1. The application effects 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-(vinyloxy)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, and after stirring and dissolving at 60° C., the mixture was stirred at a 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, and after stirring and dissolving at a temperature not higher than 30° C., the mixture was stirred at a high speed for 10 minutes to obtain pre-emulsion B.

[0050] The pre-emulsion A was heated to 74°C, and 3.6 g of 1% azobisisobutylamidine hydrochloride aqueous solution was slowly added dropwise, and the temperature was kept constant during the addition. After the addition was completed, the temperature was kept at 74°C for 1.5 hours, and then the pre-emulsion B and 0.9 g of 1% azobisisobutylamidine hydrochloride aqueous solution were added dropwise, and the temperature was kept constant during the addition. After the addition was completed, the temperature was kept for reaction for 3 hours to obtain a durable antistatic finishing agent 2. The application effects 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, and after stirring and dissolving at 60° C., the mixture was stirred at a high speed for 30 minutes to obtain pre-emulsion A.

[0053] Into 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 agricultural milk No. 300, 0.3 g of fatty alcohol polyoxyethylene ether (EO number 40), 0.2 g of octadecyl trimethyl ammonium chloride, and 41.6 g of deionized water were added; after stirring and dissolving at a temperature not higher than 30° C., the pre-emulsion B was obtained by high-speed stirring for 10 minutes.

[0054] The pre-emulsion A was heated to 74°C, and 3.8 g of 1% azobisisobutylamidine hydrochloride aqueous solution was slowly added dropwise, and the temperature was kept constant during the addition. After the addition was completed, the temperature was kept at 74°C for 1.5 hours, and then the pre-emulsion B and 0.7 g of 1% azobisisobutylamidine hydrochloride aqueous solution were added dropwise, and the temperature was kept constant during the addition. After the addition was completed, the temperature was kept for reaction for 4 hours to obtain a durable antistatic finishing agent 3. The application effects 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 and washability of coral fleece

[0060]

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

[0062] Although the present invention has been disclosed as above by way of embodiments, it is not intended to limit the protection scope 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 protection scope 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% of polyethylene glycol methyl ether methacrylate copolymer units; 3) 5-25 wt% of 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% of polyethylene glycol methyl ether methacrylate copolymer units; 3) 10-20 wt% of 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 di[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 a polyester fabric durable antistatic finishing agent copolymer according to any one of claims 1 to 5, the method comprising the following steps: i) preparing a pre-emulsion A with unsaturated terephthalate comonomer and 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, characterized in that: The nonionic emulsifier is selected from one or more of fatty alcohol polyoxyethylene ether with EO number of 15 to 40, Agricultural Milk No. 100, Agricultural Milk No. 300, and Agricultural Milk 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, characterized in that: The free radical initiator is azobisisobutyramidine hydrochloride.

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

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