KR100560992B1 - Method for preparing the polyurethane containing silicon for shape memory of fibers - Google Patents

Abstract

The present invention provides a method for producing a silicone-containing polyurethane for fiber shape material and a silicone-containing polyurethane for fiber shape material prepared according to the present invention by immersing in a cellulose-based fiber and photocrosslinked by ultraviolet light to produce a shape memory fiber. The method for preparing a silicone-containing polyurethane for a fibrous memory material comprises (A) reacting at least one polyisocyanate selected from Formula 1 below with a silanol selected from Formula 2 in the presence of a catalyst To prepare a prepolymer; (B) dissolving the prepolymer prepared in the above step in an organic solvent and then reacting by adding a chain extender; (C) after completion of the reaction, characterized in that it is subjected to a post-treatment step of drying, precipitation in deionized water, filtration and drying.

[Formula 1]

[Formula 2]

[Wherein R ¹ is selected from alkyl, cycloalkyl, or aromatic group, R ² is selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl group, n is an integer ranging from 1 to 30.]

When the silicon-containing polyurethane for fiber shape memory material according to the present invention is used, it is easy to process the fiber, and in particular, there is little deformation at a set temperature, so that the shape is maintained. There are possible advantages.

Silanol, polyisocyanate, shape memory, heat resistant polyurethane, light irradiation crosslink, wrinkle prevention

Description

Method for preparing the polyurethane-containing polyurethane for shape memory material {Method for preparing the polyurethane containing silicon for shape memory of fibers}             

1: Yield comparison according to the amount of silicone-containing polyurethane and silanol added according to the present invention.

Cellulose fibers are often used as a material of clothing because they have good comfort, excellent durability, low price and good dyeability. However, this has a big disadvantage that wrinkles are well generated and the recovery is very low after washing or during wearing. Factors affecting the wrinkles of clothes include structural variables such as fiber type, molecular form and arrangement method, number and number of twists, fabric density and thickness, and external environment such as temperature, humidity, external force and time.

Preventing wrinkles caused by these factors include chemical processing methods such as resin processing such as acid, alkali treatment or preshrinkage, aging, annealing, etc. There is a restructuring method.

Among the treatment methods described above, acid or alkali treatments are largely damaged by fabrics, and thus, physical treatments using a combination of a chemical treatment method using an anti-wrinkle processed resin and a fiber with less wrinkles such as polyester are used.

On the other hand, the physical properties of the fiber, such as strength, elasticity, moisture absorption rate, depend on the shape of the molecule from which the fiber is made and the method of molecular arrangement in the fiber.

Deformation at the molecular level depends on the molecular arrangement in the fiber, especially irregular amorphous regions are easily deformed, and the extent to which the fiber is bent and stretched is dependent on the molecules constituting the amorphous region according to external forces. Therefore, in order to prevent wrinkles of cellulose fibers, it is necessary to control the amorphous region. Molecular structure of the cellulose fiber may be a cause of wrinkle of the cellulose fiber. The cellulose molecules are hydrogen bonds, and the OH group in the cellulose undergoes new hydrogen bonding due to molecular slippage caused by external force, resulting in poor morphological stability. . Another reason is that the lower the crystallinity of the fiber, the finer the gap is enlarged by the absorption of water, the volume is increased, and the degree of shrinkage due to the tension during drying is increased, thereby decreasing the shape stability and the occurrence of wrinkles. Therefore, in order to solve this problem, the shrinkage and spindle function of the fiber should be increased by crosslinking the amorphous region through surface modification of the cellulose fiber using a resin or the like.

Currently, resins commonly used as anti-shrinkage and additives can be broadly divided into urea-formaldehyde-based, melamine-formaldehyde-based, cyclic urea-type and polycarboxylic acid-based resins. The double cyclic element type resin has excellent disadvantages of fusitivity, shrinkage resistance and durability, but has poor chlorine resistance and difficult processing.

In addition, methylol-based cyclic urea-type resin has the advantage of excellent spindle property, but formaldehyde gas that is harmful to the human body is released during the reaction with cellulose fiber, and recently, dimethyldihydroxyimidazolinone (dimethyldihydroxyimidazolinone) Non-formalin-based resins such as dihydroxy imidazolinone and DMDHI) are used. However, they are more expensive than formalin-based resins, and deteriorate fusibilization performance.

In response to these demands, polycarboxylic acid-based additive resins have recently been developed, which have a crosslinking effect on textile fabrics, improve morphological stability and spindle resistance, hydrophilicity to basic dyes or cationic processing agents, and adsorb heavy metal cations. It has the advantage of giving antifungal properties, but it has the disadvantages such as yellowing.

 Therefore, the development of a new resin without wrinkles and yellowing phenomenon is urgently required. In recent years, polymer resin additives have been used in accordance with such demands.

As known in Korean Laid-Open Patent Publication No. 1998-2415, the currently used resin additive is often a polymer material forming a film on a fiber, and polyvinyl, polyacryl, polyethylene, polyurethane, and silicone polymers are used. do.

Polyurethane-based materials are often used for top coating because they are mixed with resin crosslinking agents during processing to give a very flexible touch and resilience to treated fibers and to provide excellent mechanical resistance. In addition, silicone-based materials have a unique smoothness, flexibility, significantly improved tear strength, frictional resistance, and sealing properties. It improves shape stability.

However, there is a problem that the ratio is difficult to control due to the difference in reactivity when using the urethane and silicone as an additive when processing the resin of the fiber. Therefore, there is a demand for the development of a new fiber shape memory material to satisfy the performance of uniform silicone and urethane in the fiber.

Therefore, the object of the present invention is to overcome the above problems, while maintaining the excellent properties of the silicone compound and the urethane-based fiber treatment agent, there is no problem that the ratio adjustment is difficult due to the difference in the reactivity of the urethane and silicone compound during the resin processing of the fiber, It is easy to process, and in particular, it has the durability to maintain shape because there is little deformation at set temperature, so it is possible to manufacture new shape memory material that can replace existing expensive shape memory treatment agent at low price and fabric shape memory material It is to provide a method for producing a shape memory fiber using.

The present invention provides a method for producing a silicone-containing polyurethane for fiber shape material and a silicone-containing polyurethane for fiber shape material prepared according to the present invention by immersing in a cellulose fiber to optical cross-linking reaction by ultraviolet light to produce a shape memory fiber. It is about how to.

The method for preparing a silicone-containing polyurethane for a fibrous memory material according to the present invention comprises (A) reacting at least one polyisocyanate selected from formula (1) below with a silanol selected from formula (2) in the presence of a catalyst to prepolymer Preparing a; (B) dissolving the prepolymer prepared in the above step in an organic solvent and then reacting by adding a chain extender; (C) after the reaction is completed, characterized in that the drying, precipitation in deionized water, filtration and drying step.

[Formula 1]

[Formula 2]

[Wherein R ¹ is selected from alkyl, cycloalkyl, or aromatic group, R ² is selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl group, n is an integer ranging from 1 to 30.]

The method for producing a silicone-containing polyurethane for a fibrous memory material according to the present invention comprises a silanol and a polyisocyanate compound.

(A) reaction to prepare a prepolymer

(B) reacting the prepolymer prepared in the step.

The polyisocyanate compound used in the step (A) includes at least one compound selected from the following formula (1).

[Formula 1]

[R ¹ of the above formula is selected from alkyl, cycloalkyl, or aromatic group.]

Polyisocyanates of formula (1) can be used to form the composition, either aliphatic, cycloaliphatic or aromatic, and specific examples of polyisocyanates include 2,4 'and 4,4'-diphenylmethane diisocyanate (MDI), 2 , 4 'and 2,6'-toluene diisocyanate (TDI), paraphenylene diisocyanate, naphthylene diisocyanate, dianisidine diisocyanate, xylene diisocyanate (XDI), lysine diisocyanate, tetramethyl- Meta-xylene diisocyanate (MTMSDI), dimethyl diisocyanate (DDI), 2,4 'and 4,4'-diphenylmethane diisocyanate (MDI), 2,4' and 2,6 ' Toluene diisocyanate (TDI) is preferred.

The silanol uses at least one selected from the group of compounds represented by the following formula (2).

[Formula 2]

[Wherein R ² is selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl group, n is an integer ranging from 1 to 30.]

Among the compounds of the formula (2), specifically, R ² is methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, phenyl, preferably silanol which is methyl and phenyl group. The silanol used in the present invention preferably has an average molecular weight of 1000 to 1500.

The proportion of silanol and polyisocyanate to react is preferably 10 to 50% by weight of polyisocyanate relative to silanol.

The catalyst used in the step (A) of preparing the prepolymer may be a conventional catalyst such as an amine catalyst or a metal catalyst used in preparing a prepolymer by a conventional diol and polyisocyanate reaction, but in the case of the present invention, a stationary octoate ( stannous octoate) is preferred, and the addition amount is preferably 0.01 to 0.1% by weight based on the total reaction solution of the reaction system.

The solvent used in the preparation of the prepolymer may be an organic solvent capable of dissolving the prepolymer, but acetone, DMF, THF, and acetonitrile are preferable, and the amount used is preferably used in an amount of 2 to 5 parts by weight based on the total monomers. .

Specific reaction conditions for preparing the prepolymer include adding a silanol and an organic solvent having a predetermined composition ratio under a nitrogen atmosphere, adding a polyisocyanate compound while maintaining a reactor temperature of 50 to 70 ° C., and then reacting the reaction mixture after mixing the reaction mixture for a certain time. The catalyst is added and the reaction proceeds for 1 to 5 hours. In this case, it is preferable to use a DBA inverse titration method to identify the end point of the prepolymerization reaction.

The prepolymer prepared in step (A) is dissolved in a conventional organic solvent, and then a chain extender is added to polymerize the prepolymer. The organic solvent may be a conventional organic solvent used in the production of polyurethane, and DMF and acetonitrile are preferable. The chain extender used in the reaction may be a chain extender of a conventional polyurethane prepolymer, but 1,4-butanediol is preferred, and the amount of the chain extender is 0.5 to 7 wt% based on silanol, and 1 to 3 wt% Is preferable, and the temperature at the time of reaction has preferable 65-70 degreeC.

The post-treatment step after the reaction goes through a conventional polymer post-treatment step. Specifically, the reaction product is dried in vacuo to remove the solvent, precipitated in excess of deionized water and filtered, and then dried in a vacuum oven at 60 ℃ to obtain a silicone-containing polyurethane for the fibrous memory material.

When the silicon-containing polyurethane for thermally stable fiber shape memory material prepared according to the above method is immersed in cellulose fiber, and then photocrosslinked by ultraviolet light, it is processed into shape memory fiber.

Any solvent that can dissolve the polyurethane to some extent may be used as the solvent used for immersing the silicon-containing polyurethane for fiber shape material into the cellulose fiber, but an aqueous solution containing a surfactant in consideration of the safety of the fiber may be used. desirable.

Although the shape memory characteristics of the fiber can be known through the crosslinking reaction by the ultraviolet ray in the fiber immersion state, the fiber is immersed in the silicon-containing polyurethane solution for the fiber shape memory material similarly to the conventional fiber processing method. It is possible to reduce the consumption of the silicone-containing polyurethane solution by carrying out the photocrosslinking reaction by transferring to the ultraviolet irradiation zone separated from the immersion zone. The immersion and photocrosslinking reactions above can be easily carried out by those skilled in the art.

In order to confirm the degree of reaction and the termination of the reaction according to each reaction step and the structure of the synthesized polyurethane containing silicon, the structure of the material can be confirmed by infrared spectroscopy, and in order to quantitatively analyze the content of silicon in the reaction material, solid nuclear magnetic Resonance analysis is performed, and the physical properties of the manufactured material can be confirmed by measuring the molecular weight distribution of the material using a MALDI-TOF MS spectrometer, and measuring the amount of Si by the EDX method.

In addition, the thermal properties of the material are analyzed using differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA).

The present invention can be easily understood and practiced by those skilled in the art without a separate embodiment, but as an example for illustrating the present invention described through the following examples, the present invention is as follows. Of course, it is not limited to only.

Example 1

Preparation of Silicone-containing Polyurethane for Fiber Shape Memory Material

(A) Preparation of Prepolymer

 Into a nitrogen-filled 500 ml four-necked flask, 40 g of silanol and 200 ml of acetone mixed solution having a constant composition ratio of Dow Corning Co., Ltd., having a constant molecular weight of 1200, an OH content of 10 to 10.7, and an average viscosity of 75 cps, were added. 18 g of MDI with 31% by weight of NCO was added while maintaining at 60 ° C. After 10 minutes, 0.03% by weight of stationary octoate was added to the entire reaction solution as a catalyst, and prepolymerization was performed for 2 hours to prepare a prepolymer. At this time, DBA inverse titration was used to confirm the end point of the reaction.

Was born the NH stretching peak appeared at 3500 cm ^-1, 1660 - - 3300 Al reaction after the reaction can be that the IR spectrum analysis results MDI and silanol woke aromatic hydrocarbons characteristic peaks appear at 1300 cm ^-1, 2220 cm ^-1 The isocyanate peaks appearing on disappeared.

(B) Polymerization of Prepolymer

 After dissolving the prepolymer prepared in step (A) in a solvent, 0.5 g of 1,4-butanediol was added based on the reaction silanol and the reaction system was heated to 70 ° C. for 1.5 hours, followed by vacuum drying to remove the solvent. The precipitate was precipitated in an excess of deionized water, filtered and dried in a vacuum oven at 60 ° C. to obtain a silicone-containing polyurethane for a fibrous memory material.

After the reaction, IR spectrum analysis showed that the peak of phosphorus 3300 cm ^-1 , which shows the characteristic peak of isocyanate group, disappeared completely.

Example 2

The reaction was carried out under the same conditions as in Example 1 except that 45 g of silanol and 18 g of MDI were used.

Example 3

The reaction was carried out under the same conditions as in Example 1 except that 60 g of silanol and 18 g of MDI were used.

Example 4

The reaction was carried out under the same conditions as in Example 1 except that 75 g of silanol and 18 g of MDI were used.

Table 1. Manufacturing conditions of silicone-containing polyurethanes for fiber shape memory materials

The yield of the silicon-containing polyurethane for the fibrous memory material prepared according to the reaction conditions of Table 1 may be obtained up to 80% to 98% as the amount of silanol added as shown in FIG.

Example 5

Processing into shape memory fiber

The crosslinking reaction of the silicone-containing polyurethane for fiber-like memory material prepared in Examples 1 to 4 by ultraviolet irradiation was deposited on a cellulose cloth of a certain size, and the intensity of ultraviolet light was controlled in the photoreaction device. Irradiation time was changed while photocrosslinking.

In the crosslinking property of the optical crosslink in Example 5, the amount of crosslinking had an optimum wrinkle preventing effect at 30%, and more crosslinking showed a tendency to stiffen the fiber. The shape memory fiber crosslinked by the silicon-containing polyurethane for the fiber-shaped memory material prepared according to the present invention is easily processed compared to the processing by the conventional silicone-polyurethane composition, and also exhibited excellent anti-wrinkle effect.

The silicone-containing polyurethane for fiber shape memory material according to the present invention does not impair the basic properties of cellulose compared to the conventional method of manufacturing the shape memory fiber, and it is possible to prevent wrinkles of fibers and shrinkage and wrinkles of industrial materials by an inexpensive and simple method. There is a possible advantage, in particular, there is little deformation at a set temperature, there is a durable durability to maintain the shape, there is an advantage that can replace the existing expensive shape memory treatment agent at a low price. In addition, the material used does not emit harmful gases and substances to the human body, and the manufacturing method is relatively simple, so that it can be used not only for household goods but also for industrial materials, and in particular, by increasing the light irradiation device, continuous processing is possible when processing industrial materials. There is an advantage.

Claims (8)

(A) preparing a prepolymer by reacting at least one polyisocyanate selected from Formula 1 with at least one silanol selected from Formula 2 in the presence of at least one catalyst selected from amine catalysts and metal catalysts; (B) dissolving the prepolymer in an organic solvent and then reacting by adding a chain extender; (C) vacuum drying, precipitation in deionized water, filtration and drying steps after the reaction is completed; Method for producing a silicon-containing polyurethane for a fibrous memory material, characterized in that having a. [Formula 1]

[Formula 2]

[Wherein R ¹ is selected from alkyl, cycloalkyl, or aromatic group, R ² is selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl group, n is an integer ranging from 1 to 30.] The method of claim 1, The ratio of the silanol and polyisocyanate used in step (A) is 10 to 50% by weight of polyisocyanate relative to silanol. The method of claim 2, The amount of the chain extender added in step (B) is 0.5 to 7% by weight based on the silanol in the step (A) method for producing a silicone-containing polyurethane for fiber-like memory material, characterized in that used. The method of claim 3, wherein the at least one polyisocyanate selected from Formula 1 is 2,4'- or 4,4'-diphenylmethane dipolyisocyanate. . The method of claim 4, wherein R ² is a methyl, ethyl, propyl, or phenyl group, the method for producing a silicone-containing polyurethane for a fibrous memory material. The method of claim 5, A method for producing a silicone-containing polyurethane for a fibrous memory material, characterized in that the average molecular weight of the silanol to be used is 1000 to 1500. The method of producing a silicone-containing polyurethane for a fibrous memory material according to claim 6, wherein the chain extender used in step (B) is 1,4-butanediol. A method of manufacturing a shape memory fiber, wherein the silicone-containing polyurethane for fiber shape material prepared according to the method of claim 1 is immersed in a cellulose fiber and then photocrosslinked by ultraviolet light.

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