Polystyrene-maleic anhydride-polyethylene glycol derivative as well as preparation method and application thereof

Abstract

The invention discloses a polystyrene-maleic anhydride-polyethylene glycol derivative as well as a preparation method and application thereof. The preparation method of the derivative comprises the following steps: synthesizing a styrene-maleic anhydride copolymer by taking maleic anhydride, a solvent, a chain transfer agent, an initiator and styrene as raw materials; adding the dried styrene-maleic anhydride copolymer and methoxy polyethylene glycol amine with the molecular weight of 1000 Da into anhydrous dioxane, and reacting for 5-7 hours at the temperature of 55-65 DEG C; cooling to room temperature after the reaction is finished, adding absolute ether into the reaction liquid, centrifuging the obtained mixed liquid, and performing vacuum drying on the obtained viscous solid precipitate to obtain the polystyrene-maleic anhydride-polyethylene glycol derivative. The invention provides the application of the polystyrene-maleic anhydride-polyethylene glycol derivative in preparation of a fabric finishing agent, the washing resistance can be remarkably improved, and meanwhile, the polystyrene-maleic anhydride-polyethylene glycol derivative has the advantage of wide fabric applicability.

Description

Technical Field

[0001] This invention relates to a polystyrene-maleic anhydride-polyethylene glycol derivative, its preparation method, and its application in the preparation of fabric finishing agents. Background Technology

[0002] Fabric finishing agents can alter the chemical and physical properties of fabric fiber surfaces, transforming them from a hydrophobic (or poorly wetted) state to a hydrophilic (easily wetted) state. This improves the fabric's moisture absorption and wicking properties, imparts antistatic properties, enhances stain resistance and wrinkle resistance, and facilitates subsequent processing. For example, polyester, with its high strength, wrinkle resistance, quick-drying properties, and good shape retention, has become the world's largest-produced and most widely used synthetic fiber. However, due to the lack of hydrophilic groups in its molecular chain, polyester has poor moisture absorption, high surface resistance, and is prone to static electricity. Therefore, there is an urgent need to improve the wearing comfort of clothing through fabric finishing agents. Consequently, hydrophilic fabric finishing agents are widely used in polyester and other synthetic fiber fabrics.

[0003] Common traditional hydrophilic fabric finishing agents mainly include anionic surfactants, polymeric surfactants, polyacrylic acid and its salts. These typically provide hydrophilicity and easy stain removal by adsorbing onto the fiber surface to form a film. However, these plant-based fabric finishing agents also have significant drawbacks: due to the weak bonding between the finishing agent molecules and the fiber surface, they are easily detached under vibration, contact, mechanical friction, and washing, resulting in poor wash resistance of the fabric; secondly, the film formed by these finishing agents on the fiber surface has high hardness, leading to a stiff, rough feel and poor elasticity and comfort of the fabric; and harmful byproducts and impurities are often generated during the synthesis of these finishing agents, which can have adverse effects on aquatic organisms and the environment. Therefore, solving the above-mentioned problems in this field and developing a fabric finishing agent with excellent wash resistance and wide applicability has broad market prospects and practical significance. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a polystyrene-maleic anhydride-polyethylene glycol derivative, a method for preparing the derivative, and its application in the preparation of fabric finishing agents.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a method for preparing a polystyrene-maleic anhydride-polyethylene glycol derivative, specifically comprising the following preparation steps:

[0007] (1) Take maleic anhydride, solvent, chain transfer agent and initiator, dissolve them and add them to the reaction flask, and bubble nitrogen gas to remove oxygen;

[0008] (2) Raise the temperature of the reaction flask to 75-85 ℃, add styrene to the constant pressure dropping funnel, adjust the constant pressure dropping funnel to slowly add styrene at 1-2 drops / second, and continue the reaction for 5-7 hours after the addition is completed;

[0009] (3) After the reaction is completed, the temperature is lowered to room temperature, n-hexane is added to the reaction solution, the resulting mixture is centrifuged, and the resulting solid precipitate is dried under vacuum to obtain styrene-maleic anhydride copolymer.

[0010] (4) Take the dried styrene-maleic anhydride copolymer and methoxy polyethylene glycolamine with a molecular weight of 1000 Da and add them to anhydrous dioxane, and react at 55-65 °C for 5-7 h.

[0011] (5) After the reaction is completed, the temperature is cooled to room temperature, anhydrous diethyl ether is added to the reaction solution, the resulting mixture is centrifuged, and the resulting viscous solid precipitate is dried under vacuum to obtain the polystyrene-maleic anhydride-polyethylene glycol derivative.

[0012] The mass ratio of maleic anhydride to chain transfer agent, initiator, and styrene is 20:1-3:1-3:40; the volume of solvent used is 5-10 mL / g based on the mass of maleic anhydride.

[0013] The mass ratio of the styrene-maleic anhydride copolymer to methoxy polyethylene glycol amine is 1:3; the volume of the anhydrous dioxane used is 5-10 mL / g based on the mass of the styrene-maleic anhydride copolymer.

[0014] Preferably, the solvent in step (1) is one of p-xylene, o-xylene, or m-xylene.

[0015] Preferably, the chain transfer agent in step (1) is either trichlorobromomethane or 2,4-diphenyl-4-methyl-1-pentene.

[0016] Preferably, the initiator in step (1) is either benzoyl peroxide or azobisisobutyronitrile.

[0017] Preferably, the mass ratio of maleic anhydride to chain transfer agent, initiator, and styrene is 20:3:3:40.

[0018] Preferably, the volume of the solvent used in step (1) is 8-10 mL / g based on the mass of maleic anhydride.

[0019] Preferably, in step (1), the reaction temperature is 80°C, styrene is added slowly at 1 drop / second, and the reaction continues for 6 hours after the addition is completed.

[0020] Preferably, in step (2), the reaction temperature is 60°C and the reaction time is 6 hours.

[0021] Preferably, in step (4), the volume of the anhydrous dioxane used is 6-8 mL / g based on the mass of the styrene-maleic anhydride copolymer.

[0022] In a second aspect, the present invention provides a polystyrene-maleic anhydride-polyethylene glycol derivative prepared according to the preparation method described in the first aspect.

[0023] The number-average molecular weight M of the polystyrene-maleic anhydride-polyethylene glycol derivative described in this invention n Between 7500 and 22500 Da, the weight-average molecular weight M w Between 17700 and 56500 Da.

[0024] Thirdly, the present invention provides the application of the aforementioned polystyrene-maleic anhydride-polyethylene glycol derivative in the preparation of fabric finishing agents.

[0025] Compared with the prior art, the beneficial technical effects of the present invention are as follows: In addition to hydrophilic polyethylene glycol groups, the polystyrene-maleic anhydride-polyethylene glycol derivative of the present invention also contains highly active maleic anhydride groups, which can react with hydroxyl groups on polyester molecular chains, hydroxyl groups on vinylon molecular chains, amino groups on nylon molecular chains, and amine groups on spandex molecular chains, thereby forming stable and strong covalent bonds with the surface of polyester, vinylon, nylon, spandex and other fabrics. This significantly improves the wash resistance of fabric finishing agents based on polystyrene-maleic anhydride derivatives, and also has the advantage of wide applicability to fabrics. Attached Figure Description

[0026] Figure 1 This is the GPC spectrum of the styrene-maleic anhydride copolymer obtained in Example 1.

[0027] Figure 2 This is the GPC spectrum of the styrene-maleic anhydride-polyethylene glycol derivative obtained in Example 1. Detailed Implementation

[0028] The technical solution of the present invention will be further described in detail below through specific embodiments. The described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Unless otherwise specified in the embodiments of this invention, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained through conventional technical means or commercially available.

[0030] In this embodiment of the invention, the preparation steps of the polystyrene-maleic anhydride-polyethylene glycol derivative are as follows:

[0031] (1) Take maleic anhydride, solvent, chain transfer agent and initiator, dissolve them and add them to the reaction flask, and bubble nitrogen gas to remove oxygen;

[0032] (2) Raise the temperature of the reaction flask to 75-85 ℃, add styrene to the constant pressure dropping funnel, adjust the constant pressure dropping funnel to slowly add styrene at 1-2 drops / second, and continue the reaction for 5-7 hours after the addition is completed;

[0033] (3) After the reaction is completed, the temperature is lowered to room temperature, n-hexane is added to the reaction solution, the resulting mixture is centrifuged, and the resulting solid precipitate is dried under vacuum to obtain styrene-maleic anhydride copolymer.

[0034] (4) Take the dried styrene-maleic anhydride copolymer and methoxy polyethylene glycolamine with a molecular weight of 1000 Da and add them to anhydrous dioxane, and react at 55-65 °C for 5-7 h.

[0035] (5) After the reaction is completed, the temperature is cooled to room temperature, anhydrous diethyl ether is added to the reaction solution, the resulting mixture is centrifuged, and the resulting viscous solid precipitate is dried under vacuum to obtain the polystyrene-maleic anhydride-polyethylene glycol derivative.

[0036] The mass ratio of maleic anhydride to chain transfer agent, initiator, and styrene is 20:1-3:1-3:40; the volume of solvent used is 5-10 mL / g based on the mass of maleic anhydride.

[0037] The mass ratio of the styrene-maleic anhydride copolymer to methoxy polyethylene glycol amine is 1:3; the volume of the anhydrous dioxane used is 5-10 mL / g based on the mass of the styrene-maleic anhydride copolymer.

[0038] Preferably, the solvent in step (1) is one of p-xylene, o-xylene, or m-xylene.

[0039] Preferably, the chain transfer agent in step (1) is either trichlorobromomethane or 2,4-diphenyl-4-methyl-1-pentene.

[0040] Preferably, the initiator in step (1) is either benzoyl peroxide or azobisisobutyronitrile.

[0041] The testing and characterization methods for the polymers prepared in the embodiments of the present invention are as follows:

[0042] 1) Determination of the yield (Yield x) of the product from the first step of the polymerization reaction:

[0043] Yield x(%) = 98.1*m2 / 306.4*m1 100%

[0044] In the above formula, m1 is the mass of maleic anhydride monomer added before the polymerization reaction, and m2 is the mass of styrene-maleic anhydride copolymer obtained after drying after the reaction.

[0045] 2) Determination of the yield (Yield y) of the grafting reaction product in the second step:

[0046] Yield y(%) = m5 / (m3+ m4) 100%

[0047] In the above formula, m3 is the mass of the styrene-maleic anhydride copolymer added during the reaction with methoxy polyethylene glycolamine, m4 is the mass of the added methoxy polyethylene glycolamine, and m5 is the mass of the polystyrene-maleic anhydride-polyethylene glycol derivative obtained by centrifugation and drying after the reaction.

[0048] 3) Determination of molecular weight of styrene-maleic anhydride copolymers and their derivatives

[0049] The dried polymer powder was dissolved in tetrahydrofuran (THF) to prepare the sample, which was then analyzed using a SHIMADZU LC-16 gel permeation chromatography system. The column oven temperature was 35 °C, the mobile phase was THF, and the flow rate was 0.3 mL / min. GPC calibration curves were generated using a series of PMMA standard polymers, and the molecular weights of styrene-maleic anhydride copolymers and their derivatives were calculated.

[0050] Example 1

[0051] The specific preparation steps and testing methods for the styrene-maleic anhydride-polyethylene glycol derivative copolymer are as described above. The composition of the raw materials and the synthesis conditions for the first-step polymerization reaction are as follows: styrene, 133.0 mL; maleic anhydride, 60.0 g; xylene solvent, 525 mL; benzoyl peroxide initiator, 9.0 g; 2,4-diphenyl-4-methyl-1-pentene chain transfer agent, 9.0 mL; n-hexane, 455 mL; reaction temperature, 80 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride copolymer obtained from the polymerization reaction is 153.1 g; the GPC spectrum of the obtained styrene-maleic anhydride copolymer is shown below. Figure 1 As shown, the number-average molecular weight M n =2794 Da, weight-average molecular weight M w =6324 Da. The calculated yield of the first-step polymerization reaction is 81.7%.

[0052] The composition and synthesis conditions of the raw materials for the second-step grafting reaction are as follows: styrene-maleic anhydride copolymer: 15.0 g; methoxy polyethylene glycol amine: 45.0 g; anhydrous dioxane: 110 mL; anhydrous diethyl ether: 105 mL; reaction temperature: 60 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride-polyethylene glycol derivative obtained from the grafting reaction is 49.4 g; the GPC spectrum of the obtained styrene-maleic anhydride-polyethylene glycol derivative is shown below. Figure 2 As shown, the number-average molecular weight M n =7586 Da, weight-average molecular weight M w =18046 Da. The calculated yield of the second grafting reaction is 82.3%.

[0053] Example 2

[0054] The specific preparation steps and testing methods for the styrene-maleic anhydride-polyethylene glycol derivative copolymer are as described above. The composition of the raw materials and the synthesis conditions for the first-step polymerization reaction are as follows: styrene, 133.0 mL; maleic anhydride, 60.0 g; xylene solvent, 525 mL; azobisisobutyronitrile initiator: 6.0 g; trichlorobromomethane chain transfer agent, 4.5 mL; n-hexane, 455 mL; reaction temperature, 80 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride copolymer obtained from the polymerization reaction is 155.2 g, and the number average molecular weight M of the copolymer is... n =4153 Da, weight-average molecular weight M w =10247 Da, first step polymerization yield: 82.8%.

[0055] The composition and synthesis conditions of the raw materials for the second-step grafting reaction are as follows: styrene-maleic anhydride copolymer: 10.0 g; methoxy polyethylene glycol amine: 30.0 g; anhydrous dioxane: 73 mL; anhydrous diethyl ether: 70 mL; reaction temperature: 60℃; reaction time: 6 h. The mass of the styrene-maleic anhydride-polyethylene glycol derivative obtained from the grafting reaction is 33.6 g, and the number-average molecular weight M of the derivative is... n =13120 Da, weight-average molecular weight M w =32669 Da, second-step grafting reaction yield: 84.0%.

[0056] Example 3

[0057] The specific preparation steps and testing methods for the styrene-maleic anhydride-polyethylene glycol derivative copolymer are as described above. The composition of the raw materials and the synthesis conditions for the first-step polymerization reaction are as follows: styrene, 133.0 mL; maleic anhydride, 60.0 g; solvent – ​​o-xylene, 510 mL; initiator – benzoyl peroxide, 3.0 g; chain transfer agent – ​​2,4-diphenyl-4-methyl-1-pentene, 3.0 mL; n-hexane, 455 mL; reaction temperature – 80 ℃; reaction time – 6 h. The mass of the styrene-maleic anhydride copolymer obtained from the polymerization reaction is 163.2 g, and the number average molecular weight M of the copolymer is… n =6654 Da, weight-average molecular weight M w =16021 Da, first step polymerization yield: 87.1%.

[0058] The composition and synthesis conditions of the raw materials for the second-step grafting reaction are as follows: styrene-maleic anhydride copolymer: 20.0 g; methoxy polyethylene glycol amine: 60.0 g; anhydrous dioxane: 145 mL; anhydrous diethyl ether: 140 mL; reaction temperature: 60 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride-polyethylene glycol derivative obtained from the grafting reaction is 68.5 g, and the number average molecular weight M of the derivative is... n =22490 Da, weight-average molecular weight M w =56450 Da, second-step grafting reaction yield: 85.6%.

[0059] Example 4

[0060] The specific preparation steps and testing methods for the styrene-maleic anhydride-polyethylene glycol derivative copolymer are as described above. The composition of the raw materials and the synthesis conditions for the first-step polymerization reaction are as follows: styrene, 133.0 mL; maleic anhydride, 60.0 g; xylene solvent, 525 mL; azobisisobutyronitrile initiator: 9.0 g; trichlorobromomethane chain transfer agent, 4.5 mL; n-hexane, 455 mL; reaction temperature, 80 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride copolymer obtained from the polymerization reaction is 147.8 g, and the number average molecular weight M of the copolymer is... n =2625 Da, weight-average molecular weight M w =6064 Da, first-step polymerization yield: 78.9%.

[0061] The composition and synthesis conditions of the raw materials for the second-step grafting reaction are as follows: styrene-maleic anhydride copolymer: 10.0 g; methoxy polyethylene glycol amine: 30.0 g; anhydrous dioxane: 73 mL; anhydrous diethyl ether: 70 mL; reaction temperature: 60℃; reaction time: 6 h. The mass of the styrene-maleic anhydride-polyethylene glycol derivative obtained from the grafting reaction is 32.3 g, and the number average molecular weight M of the derivative is... n =7730 Da, weight-average molecular weight M w =17769 Da, second-step grafting reaction yield: 80.7%.

[0062] Example 5

[0063] The specific preparation steps and testing methods for the styrene-maleic anhydride-polyethylene glycol derivative copolymer are as described above. The composition of the raw materials and the synthesis conditions for the first-step polymerization reaction are as follows: styrene, 133.0 mL; maleic anhydride, 60.0 g; xylene solvent, 525 mL; perazobisisobutyronitrile initiator: 4.0 g; chain transfer agent -2,4-diphenyl-4-methyl-1-pentene, 5.0 mL; n-hexane, 455 mL; reaction temperature, 80 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride copolymer obtained from the polymerization reaction was 155.8 g, and the number average molecular weight M of the copolymer was... n =5154 Da, weight-average molecular weight M w =12326Da, first-step polymerization yield: 83.1%.

[0064] The composition and synthesis conditions of the raw materials for the second-step grafting reaction are as follows: styrene-maleic anhydride copolymer: 20.0 g; methoxy polyethylene glycol amine: 60.0 g; anhydrous dioxane: 145 mL; anhydrous diethyl ether: 140 mL; reaction temperature: 60 ℃; reaction time: 6 h. The mass of the styrene-maleic anhydride-polyethylene glycol derivative obtained from the grafting reaction is 66.3 g, and the number average molecular weight M of the derivative is... n =15040 Da, weight-average molecular weight M w =37103 Da, second-step grafting reaction yield: 82.9%.

Claims

1. A method for preparing a polystyrene-maleic anhydride-polyethylene glycol derivative, characterized in that: The preparation method includes the following preparation steps: (1) Take maleic anhydride, solvent, chain transfer agent and initiator, dissolve them and add them to the reaction flask, and bubble nitrogen gas to remove oxygen; (2) Raise the temperature of the reaction flask to 75-85 ℃, add styrene to the constant pressure dropping funnel, adjust the constant pressure dropping funnel to slowly add styrene at 1-2 drops / second, and continue the reaction for 5-7 hours after the addition is completed; (3) After the reaction is completed, the temperature is lowered to room temperature, n-hexane is added to the reaction solution, the resulting mixture is centrifuged, and the resulting solid precipitate is dried under vacuum to obtain styrene-maleic anhydride copolymer. (4) Take the dried styrene-maleic anhydride copolymer and methoxy polyethylene glycolamine with a molecular weight of 1000 Da and add them to anhydrous dioxane, and react at 55-65 °C for 5-7 h. (5) After the reaction is completed, the temperature is cooled to room temperature, anhydrous diethyl ether is added to the reaction solution, the resulting mixture is centrifuged, and the resulting viscous solid precipitate is dried under vacuum to obtain the polystyrene-maleic anhydride-polyethylene glycol derivative. The mass ratio of maleic anhydride to chain transfer agent, initiator, and styrene is 20:1-3:1-3:40; the volume of solvent used is 5-10 mL / g based on the mass of maleic anhydride. The mass ratio of the styrene-maleic anhydride copolymer to methoxy polyethylene glycol amine is 1:3; the volume of the anhydrous dioxane used is 5-10 mL / g based on the mass of the styrene-maleic anhydride copolymer.

2. The preparation method according to claim 1, characterized in that: The solvent in step (1) is one of p-xylene, o-xylene, or m-xylene.

3. The preparation method according to claim 1, characterized in that: The chain transfer agent in step (1) is either trichlorobromomethane or 2,4-diphenyl-4-methyl-1-pentene.

4. The preparation method according to claim 1, characterized in that: The initiator in step (1) is either benzoyl peroxide or azobisisobutyronitrile.

5. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of maleic anhydride to chain transfer agent, initiator, and styrene is 20:3:3:

40.

6. The preparation method according to claim 1, characterized in that: In step (1), the reaction temperature is 80℃, and styrene is slowly added at a rate of 1 drop / second. After the addition is complete, the reaction continues for 6 hours.

7. The preparation method according to claim 1, characterized in that: In step (2), the reaction temperature is 60℃ and the reaction time is 6h.

8. A polystyrene-maleic anhydride-polyethylene glycol derivative prepared by the preparation method according to any one of claims 1-7.

9. The polystyrene-maleic anhydride-polyethylene glycol derivative as described in claim 8, characterized in that: The number-average molecular weight M of the polystyrene-maleic anhydride-polyethylene glycol derivative n Between 7500 and 22500 Da, the weight-average molecular weight M w Between 17700 and 56500 Da.

10. The use of the polystyrene-maleic anhydride-polyethylene glycol derivative as described in claim 8 or 9 in the preparation of fabric finishing agents.

Images