CN1995530A - Synthetic fiber and its fabric hydrophilic finish method - Google Patents

Abstract

The invention discloses a method for hydrophilic finishing of synthetic fibers and their fabrics, which comprises the steps of pre-irradiation treatment of synthetic fibers and their fabrics, preparation of inverse emulsion and graft modification treatment. Pre-irradiation treatment includes low-temperature plasma treatment or ultraviolet radiation treatment; the preparation process of inverse emulsion is: prepare water and water-soluble monomer system into water phase system, surfactant and co-solvent are mixed to prepare oil phase system, Then slowly pour the water phase system into the oil phase system to form a reverse emulsion; the graft modification treatment method is: put the pre-irradiated synthetic fibers and their fabrics into the prepared reverse emulsion, and blow nitrogen to drive off the reverse emulsion. The air in the phase emulsion system carries out the grafting reaction at a temperature of 45-95°C. According to the method for hydrophilic finishing, the grafting rate of the finished product is controllable, the hydrophilic performance is good, and the technological process is simple and feasible, without environmental pollution, which is favorable for popularization and application.

Description

A kind of synthetic fiber and its fabric hydrophilic finishing method

technical field

The invention relates to a method for hydrophilic finishing of synthetic fibers and their fabrics, in particular to a hydrophilic finishing agent for synthetic fibers and their fabrics, the preparation method and application of the finishing agent, which belongs to the surface modification of polymer materials technology field.

Background technique

在20℃下的回潮率仅为0.05％，几乎不吸湿。这大大地限制了其在床上用品、服装衣料、卫生用品等民用品以及在土工布、帐篷、纤维增强胶凝材料等工程领域的应用。为了改善合成纤维的亲水性能，多年来人们在改善涤纶、丙纶亲水性能方面做了大量的研究工作。通过共聚、共混方法向纤维中引入亲水基团；制备表面具有微坑穴的纤维，利用毛细吸水原理改善吸水性；纤维的细旦化、混纤、异收缩与织造工艺相结合，利用织物的结构改善亲水性；用亲水性试剂对纤维、织物表面进行后整理、化学接枝和物理辐照等方法赋予织物一定的吸湿亲水性。Among synthetic fibers, polyester fabric has excellent properties such as high strength, good wear resistance, stable size, excellent wrinkle resistance, not easy to mildew and moth, and has become the main clothing fabric. However, polyester fiber has high crystallinity, and there are no other hydrophilic groups except the hydroxyl group on the molecular chain, so its hygroscopicity is poor, resulting in stuffy wearing and lack of comfort. stained. Polypropylene fiber has the characteristics of light specific gravity, high strength, good elasticity, corrosion resistance, no pilling, no skin irritation, excellent heat insulation and antibacterial effect, so it has received more and more attention. Similarly, the hygroscopicity of polypropylene fiber is poor, and the contact angle with water is 86

The moisture regain at 20°C is only 0.05%, and it hardly absorbs moisture. This greatly limits its application in civilian products such as bedding, clothing materials, and sanitary products, as well as in engineering fields such as geotextiles, tents, and fiber-reinforced cementitious materials. In order to improve the hydrophilic properties of synthetic fibers, people have done a lot of research work on improving the hydrophilic properties of polyester and polypropylene fibers for many years. Introduce hydrophilic groups into fibers through copolymerization and blending methods; prepare fibers with micro-pockets on the surface, and use the principle of capillary water absorption to improve water absorption; combine fine denier, fiber blending, and different shrinkage with weaving technology, use The structure of the fabric improves the hydrophilicity; after finishing the fiber and the surface of the fabric with a hydrophilic agent, chemical grafting and physical irradiation, the fabric is endowed with a certain degree of hygroscopicity and hydrophilicity.

There are many ways to improve the hygroscopicity of synthetic fiber fabrics, such as blend spinning modification, high-energy ray irradiation modification, irradiation and chemical graft modification, and fabric hydrophilic finishing. The hydrophilic polymers added by the blending method, such as water-soluble polyacrylamide, polyethylene oxide, water-soluble copolyester and polymaleic anhydride, have complicated production processes and high raw material costs. Through treatment methods such as plasma, high-energy electrons and ultraviolet rays, the surface roughness of the fiber and the polar groups on the surface of the fiber are increased, thereby improving its hygroscopic performance. However, the long-term effect of this treatment is poor and the mechanical properties of the body are reduced, which is not conducive to the application in civil and engineering fields. The surface treatment process of hydrophilic finishing agent is simple, requires less investment, and has good moisture absorption effect, but it affects the air permeability and hand feel of the fabric, and the durability of hydrophilic treatment may not be good. Irradiation and graft polymerization are used together to etch the fiber surface to a certain extent, increase the roughness of the fiber surface, and at the same time introduce active sites and groups available for polymerization, which is convenient for grafting hydrophilic polymers. , can reduce the irradiation intensity, and has no obvious effect on the strength of the fiber body. The grafted polymer greatly increases the hydrophilicity of the fiber. This treatment technology has gradually gained attention and application in the engineering field. In comparison, the chemical grafting method needs to select a suitable initiator, which may form more homopolymers, and the processing effect is not good. In the irradiation graft polymerization method, the graft polymerization reaction is usually carried out in gas phase or solution. In the gas phase, the grafting rate is low; while in the solution, although the grafting rate can be high, the solution The size of the grafted polymer is relatively large, the content of the homopolymer is high, and the free radicals undergo chain transfer. Therefore, there are defects that the graft polymerization reaction is difficult to control.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art and provide a synthetic fiber with controllable grafting rate, good hydrophilicity of the finished product and a method for post-finishing the fabric thereof.

The technical scheme of the present invention is to provide a method for the hydrophilic finishing of synthetic fibers and their fabrics, which includes the pre-irradiation treatment of synthetic fibers and their fabrics, the preparation of inverse emulsions and the grafting modification process; The pre-irradiation treatment of synthetic fibers and their fabrics includes low-temperature plasma treatment or ultraviolet radiation treatment; the preparation process of the inverse emulsion is: prepare water and water-soluble monomer system in a mass ratio of 100:20-600 Aqueous phase system, wherein the water-soluble monomer system is a mixture of monomers or monomer mixtures or acidic monomers, monomer mixtures and inorganic bases, and the molar ratio of acidic water-soluble monomers to inorganic bases is 100:40-100 ; Prepare the oil phase system by mixing the surfactant and the cosolvent, the volume ratio of the surfactant, the cosolvent and the water phase system is 1:1～30:1～30; then slowly pour the water phase system into the oil phase system , stirring to form an inverse emulsion; the graft modification treatment process is: putting the pre-irradiated synthetic fibers and their fabrics into the prepared inverse emulsion, and purging the air in the inverse emulsion system with nitrogen gas , carry out grafting treatment in nitrogen or inert gas atmosphere, the reaction temperature is 45 ~ 95 ℃, reach the set grafting rate, after taking out, wash with hydrocarbon solvent, acetone and water respectively, and dry.

The water-soluble monomer is acrylamide, methacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, One of hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate or a combination thereof.

The surfactant is one or a combination of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.

The co-solvent is one of alkanes and cycloalkanes with not less than 5 carbon atoms, aromatic hydrocarbons, fatty alcohols with not less than 3 carbon atoms, or a combination thereof.

Compared with the prior art, the present invention has the following salient features:

1. Because the present invention adopts the method that radiation treatment and polymer grafting treatment combine, especially adopted the technology that inverse emulsion is the grafting treatment liquid, graft size and emulsion particle size are suitable, and its particle diameter is smaller than fiber Therefore, it not only maintains the original good feel, air permeability and mechanical properties of synthetic fiber fabrics, but also greatly improves the hydrophilicity of the finished product.

2. Since there is no obvious chain transfer of free radicals between the emulsion particles, the grafting rate of the inverse emulsion polymer graft can be controlled by changing the grafting reaction time and other conditions; moreover, the grafted emulsion can be used multiple times , reducing the processing cost.

Detailed ways

The present invention will be further described below in conjunction with embodiment:

Embodiment one:

Take 100 parts of polypropylene fibers, wash them with acetone solvent under reflux conditions for 4 hours, take them out, and dry them in vacuum. Dissolve the photosensitizer benzophenone in a certain amount of acetone. After immersing the washed fiber in the photosensitizer solution for 10 minutes, it was taken out and dried. Use a 500W UV lamp with a radiation flux of 4W/ ^cm2 to irradiate the pre-impregnated fibers in a nitrogen environment. After irradiating for 15 minutes, take it out and store it in a vacuum or an inert atmosphere, or put it directly into the Stored in grafted emulsion.

Weigh 640 parts of xylene, 30 parts of Span 80, mix to form an oil phase; weigh 130 parts of acrylamide, 200 parts of deionized water, mix to form a water phase; slowly put the water phase into the oil phase and stir to form a uniform Inverse emulsion system.

Fill the above inverse emulsion system into a suitable reaction vessel, install a reflux condensing device and a stirring device, repeatedly remove the remaining air in the container, add the pre-irradiated fibers into the reaction container, continue to pass nitrogen protection, and raise the polymerization temperature to 85 ℃, after 4 hours of reaction, the samples were taken out, washed with toluene, acetone and deionized water, and dried. The grafting ratio of the treated fibers was measured to be 3.5%, and the wetting contact angle with glycerol was 40

Embodiment two

Take 100 parts of polypropylene fabrics, wash them with acetone solvent under reflux conditions for 4 hours, take them out, and dry them in vacuum. Dissolve the photosensitizer benzoin dimethyl ether in a certain amount of acetone. After soaking the washed polypropylene fabric in the photosensitizer solution for 5 minutes, take it out and dry it. Use a low-pressure ultraviolet lamp and control the radiation flux to 2W/cm ² , and irradiate the pre-impregnated sample in a nitrogen environment. After irradiating for 20 minutes, take it out and store it in a vacuum or an inert atmosphere, or put it directly Stored in grafted emulsion.

Weigh 600 parts of liquid paraffin, 40 parts of Tween 80, and mix to form an oil phase; weigh 100 parts of acrylic acid, 50 parts of sodium hydroxide, and 210 parts of deionized water, and mix to form a water phase; slowly pour the water phase into the oil phase And stir to form a uniform inverse emulsion system.

Fill the above inverse emulsion system into a suitable reaction vessel, install a reflux condensing device and a stirring device, repeatedly purge nitrogen to drive off the remaining air in the container, add the pre-irradiated sample into the reaction vessel, continue to pass nitrogen protection, and increase the polymerization temperature After reacting for 6 hours at 75°C, wash and dry with cyclohexane, acetone and deionized water respectively. The grafting ratio of the processed sample was measured to be 4.5%, and the wetting contact angle with glycerol was 34

Embodiment three

Take 100 parts of polyester fabric, put it into acetone and stir for 8 hours, take it out, dry it in vacuum and weigh it. The radio frequency frequency of the plasma generator is 13.65 MHz, the pressure of the atmosphere air is 100 Pa, the discharge power is 100 watts, and the discharge time is 4 minutes. After the treatment, the fabric is placed in a vacuum or inert atmosphere or stored in a grafted emulsion for future use.

Weigh 500 parts of n-heptane, 150 parts of n-hexanol, and 60 parts of Tween 60, and mix them to form an oil phase; weigh 140 parts of methacrylamide and 150 parts of deionized water, and mix them to form a water phase; phase and stir to form a homogeneous inverse emulsion system.

Fill the above inverse emulsion system into a suitable reaction vessel, install a reflux condensing device and a stirring device, repeatedly pass nitrogen to remove the remaining air in the vessel, add the sample after plasma treatment into the reaction vessel, raise the polymerization temperature to 65°C, and react After 2 hours, wash with n-heptane, acetone and deionized water, and dry. It is measured that the grafting rate of the treated sample is 14.5%, and the moisture regain is 2.5%.

Embodiment Four

Take 100 parts of polyester fiber, put it into acetone and stir for 10 hours, take it out, dry it in vacuum and weigh it. The radio frequency frequency of the plasma generator is 13.65MHz, the pressure of argon in the processing atmosphere is 40 Pa, the discharge power is 160 watts, and the discharge time is 3 minutes. After the treatment, the fiber is placed in vacuum or inert atmosphere or stored in grafted emulsion for future use.

Weigh 700 parts of cyclohexane, 30 parts of Tween 80 and 30 parts of Span 80, and mix them to form an oil phase; weigh 100 parts of methacrylic acid, 50 parts of sodium hydroxide, and 210 parts of deionized water, and mix them to form an aqueous phase; Slowly pour the phase into the oil phase and stir to form a homogeneous inverse emulsion system.

Fill the above inverse emulsion system into a suitable reaction vessel, install a reflux condensing device and a stirring device, repeatedly pass nitrogen to drive off the remaining air in the vessel, add the sample after plasma treatment into the reaction vessel, raise the polymerization temperature to 55°C, and react After 4 hours, wash with cyclohexane, acetone and deionized water, and dry. It is measured that the grafting rate of the treated sample is 10.5%, and the moisture regain is 1.7%.

Claims (4)

1. A method for the hydrophilic finishing of synthetic fibers and their fabrics, characterized in that: it comprises the pre-irradiation treatment of synthetic fibers and their fabrics, the preparation of inverse emulsions and the graft modification process; The pre-irradiation treatment of the synthetic fibers and their fabrics includes low-temperature plasma treatment or ultraviolet radiation treatment; The preparation process of the inverse emulsion is: prepare water and water-soluble monomer system in a mass ratio of 100:20-600 to form an aqueous phase system, wherein the water-soluble monomer system is a monomer or a monomer mixture or an acidic A mixture of monomers, monomer mixtures and inorganic bases, the molar ratio of acidic water-soluble monomers to inorganic bases is 100:40-100; the oil phase system is prepared by mixing surfactants and co-solvents, surfactants, co-solvents The volume ratio of the water phase system and the water phase system is 1:1~30:1~30; then slowly pour the water phase system into the oil phase system, and stir to form an inverse emulsion; The graft modification treatment process is: put the pre-irradiated synthetic fiber and its fabric into the prepared inverse emulsion, and carry out graft treatment in a nitrogen or inert gas atmosphere, and the reaction temperature is 45-45℃. After reaching the set grafting rate at 95°C, take it out and wash it with hydrocarbon solvent, acetone and water respectively, and dry it. 2. the method for a kind of synthetic fiber and its fabric hydrophilic finishing according to claim 1, is characterized in that: described water-soluble monomer is acrylamide, methacrylamide, N-isopropylacrylamide , N-isopropyl methacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, methacrylate shrink One or a combination of glycerides. 3. a kind of synthetic fiber according to claim 1 and the method for fabric hydrophilic finishing thereof are characterized in that: described surfactant is anionic surfactant, cationic surfactant, amphoteric surfactant and one or a combination of nonionic surfactants. 4. the method for a kind of synthetic fiber and its fabric hydrophilic finishing according to claim 1, is characterized in that: described solubilizer is the alkanes and naphthenes, aromatic hydrocarbons that carbon atom number is not less than 5 , one or a combination of fatty alcohols with not less than 3 carbon atoms.