Modified silicone oil for regenerated polyester staple fibers and production process of modified silicone oil

Abstract

The invention belongs to the field of synthetic polymers, and particularly relates to modified silicone oil for regenerated polyester staple fibers and a production process of the modified silicone oil. Octamethylcyclotetrasiloxane, methyl high-hydrogen-content silicone oil and hydrogen-containing double end sockets are used as raw materials, and side-end hydrogen-containing silicone oil is prepared under the action of a catalyst; glycidyl methacrylate is grafted into side-end hydrogen-containing silicone oil through a hydrosilylation reaction, side-end epoxy silicone oil is obtained, then polyethylene polyamine is adopted for carrying out ring opening treatment on an epoxy group, then modified silicone oil is obtained, the modified silicone oil contains ester groups, ether bonds and amino groups at the same time, and due to the fact that the amino groups and hydroxyl groups have high polarity, the side-end hydrogen-containing silicone oil can be used for preparing the epoxy silicone oil. According to the present invention, the siloxane can interact with the hydroxyl group, the carboxyl group and other groups in the fiber to produce the strong orientation and the strong adsorption, such that the directional arrangement of the siloxane on the fiber is substantially improved, and when the siloxane is applied to the after-finishing process of the regenerated polyester fiber fabric, the fabric can have the super soft, smooth and plump hand feeling, and further has characteristics of good moisture absorption and good durability.

Description

Technical Field

[0001] The invention belongs to the field of synthetic polymers, and in particular relates to modified silicone oil for regenerated polyester staple fibers and a production process thereof. Background Art

[0002] Recycled polyester mainly comes from recycled plastic bottles, old clothes and industrial waste. Through physical or chemical means, these wastes are processed into polyester fibers, and then woven into new fabrics. With the enhancement of environmental awareness and the popularization of the concept of sustainable development, recycled polyester fabrics are receiving more and more attention in the textile industry. Polyester fiber has the advantages of high strength, good dyeability, wear resistance, corrosion resistance and good dimensional stability, which have contributed to its becoming one of the three most important synthetic fibers today. However, since polyester is a hydrophobic fiber, polyester fabrics also have many disadvantages, such as poor hygroscopicity, easy to carry static electricity, rough feel, easy to stain, etc. Therefore, people often perform hydrophilic finishing on polyester clothing fabrics. Fiber softener is a surfactant that can reduce the static friction coefficient between fibers and make the fibers soft. After being treated with it, the fabric has a noticeably soft and plump feel. Compared with ordinary amino-modified silicone oil, hydrophilic amino-modified silicone oil introduces other hydrophilic groups (such as polyether groups and quaternary ammonium salt groups) in its structure in addition to amino groups. This unique multi-functional group modification is conducive to better self-emulsification and dispersion, higher emulsion stability, and the fabric finished with it has good hydrophilicity and excellent non-repairing and reconditioning performance. Although amino silicone oil has good washability and softness, the fabric finished with amino silicone oil has the risk of yellowing due to its poor light and heat stability and roller sticking and demulsification due to poor hydrophilicity. It also has the disadvantages of not being resistant to high temperature and hard water. Therefore, it is necessary to provide a finishing agent for recycled polyester fiber to solve the above technical defects. Summary of the invention

[0003] In order to solve the related problems in the above-mentioned background technology, the present invention provides a modified silicone oil for regenerated polyester staple fibers and a production process thereof. The modified silicone oil has both hydroxyl groups and a multi-dimensional network cross-linked structure. When applied to the finishing of regenerated polyester fiber fabrics, the softness, hydrophilicity and anti-yellowing properties of the regenerated polyester fiber fabrics can be improved.

[0004] One of the purposes of the present invention is to provide a production process of modified silicone oil for regenerated polyester staple fibers, characterized in that it comprises the following steps: S1: Using octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double head as raw materials, side-end hydrogen-containing silicone oil is prepared under the action of a catalyst; the mass ratio of octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double head is 10-12:3-4:1; the reaction temperature is 60-68°C, and the reaction time is 10-12 hours.

[0005] S2: preparing side-terminal epoxy silicone oil by using the side-terminal hydrogen-containing silicone oil and glycidyl methacrylate prepared in step S1 under the catalysis of chloroplatinic acid; the mass ratio of the side-terminal hydrogen-containing silicone oil to glycidyl methacrylate is 5-8:1; the mass ratio of chloroplatinic acid to glycidyl methacrylate is 1-5:1; S3: using polyethylene polyamine as a ring-opening reagent to perform a ring-opening treatment on the side-terminated epoxy silicone oil prepared in step S2 to obtain the modified silicone oil, wherein the molar ratio of the side-terminated epoxy silicone oil to the polyethylene polyamine is 1:1-3.

[0006] Furthermore, in step S1, the mass ratio of octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double head is 12:3:1.

[0007] Furthermore, the catalyst in step S1 is dibutyltin oxide, and the mass ratio of the hydrogen-containing double head to dibutyltin oxide is 1:1-3; the reaction temperature of step S1 is 65° C., and the reaction time is 12 hours.

[0008] Furthermore, in step S2, the mass ratio of the side-terminal hydrogen-containing silicone oil to glycidyl methacrylate is 6:1; and the mass ratio of chloroplatinic acid to glycidyl methacrylate is 3:1.

[0009] Furthermore, in step S2, the reaction temperature is 80-85° C., and the reaction time is 4-6 h.

[0010] Furthermore, in step S3, the polyethylene polyamine is any one of triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

[0011] Furthermore, in step S3, the polyethylene polyamine is tetraethylene pentamine.

[0012] Furthermore, the molar ratio of the side-terminated epoxy silicone oil to polyethylene polyamine is 1:2.

[0013] Furthermore, in step S3, isopropanol is used as the reaction solvent, the amount of isopropanol used is the sum of the weights of the side-terminated epoxy silicone oil and the polyethylene polyamine, the reaction temperature is 80-90° C., and the reaction time is 10-12 hours.

[0014] Another object of the present invention is to provide a modified silicone oil for regenerated polyester staple fibers, characterized in that it is prepared by the above-mentioned preparation method.

[0015] The present invention has the following beneficial effects: The invention uses octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double cap as raw materials, prepares side-terminal hydrogen silicone oil under the action of a catalyst, grafts glycidyl methacrylate to the side-terminal hydrogen silicone oil by means of a silylation reaction to obtain side-terminal epoxy silicone oil, and then uses polyethylene polyamine to perform ring-opening treatment on the epoxy group to obtain modified silicone oil. The modified silicone oil has an ester group, an ether bond and an amino group at the same time. Since the amino group and the hydroxyl group have strong polarity, they can interact with groups such as hydroxyl and carboxyl groups in the fiber to generate extremely strong orientation and adsorption, thereby greatly improving the directional arrangement of siloxane on the fiber. The invention is applied to the post-finishing process of regenerated polyester fiber fabrics, and can make the fabric feel super soft, smooth and plump, and have good hygroscopicity and durability.

[0016] The present invention controls the specific type and amount of polyethylene polyamine so that the side chain and the terminal active groups cooperate with the polyethylene polyamine to form a multi-dimensional network self-crosslinking structure. On the one hand, the network crosslinking structure covers the surface of the fabric, making the fabric softer and fuller, and having a better rebound effect. On the other hand, the use of polyethylene polyamine as a crosslinking can convert the primary amines in the polyethylene polyamine into swollen amines, reduce the relative content of the primary amines in the system, and further reduce the amino yellowing. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Schematic diagram of the synthesis equation of modified silicone oil in Example 2 of the present invention. DETAILED DESCRIPTION

[0018] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. The present invention can be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein. On the contrary, these embodiments are provided so that this disclosure will be thorough and complete, and the concept of the present invention will be fully conveyed to those skilled in the art, and the present invention will only be limited by the claims.

[0019] Example 1 In parts by weight, 100 parts of octamethylcyclotetrasiloxane, 30 parts of high hydrogen-containing silicone oil, and 10 parts of hydrogen-containing double-capped silicone oil are mixed evenly, 10 parts of dibutyltin oxide are added, the reaction time is 10 hours at 60°C, and when the material turns from turbid to transparent, the system temperature is lowered to 25°C, and the pH is adjusted to 6 to obtain side-terminal hydrogen-containing silicone oil.

[0020] Take 50 parts of side-terminal hydrogenated silicone oil and transfer it into a three-necked flask equipped with a stirrer and a condenser, add 10 parts of glycidyl methacrylate and 10 parts of chloroplatinic acid, react at 80°C for 4 hours, then evaporate the low-boiling point substance under a vacuum condition of 0.09 MPa to obtain side-terminal epoxy silicone oil.

[0021] Take side-terminated epoxy silicone oil and tetraethylene pentamine and mix them evenly, the molar ratio of the side-terminated epoxy silicone oil and tetraethylene pentamine is 1:1, add isopropanol as a solvent, the amount of isopropanol used is the sum of the weights of the side-terminated epoxy silicone oil and tetraethylene pentamine, react at 80°C for 12 hours, and then evaporate the isopropanol under normal pressure to obtain hydrophilic amino silicone oil.

[0022] Example 2 In parts by weight, 120 parts of octamethylcyclotetrasiloxane, 30 parts of high hydrogen-containing silicone oil, and 10 parts of hydrogen-containing double-capped silicone oil are mixed evenly, 20 parts of dibutyltin oxide are added, the reaction temperature is 65°C, and the reaction time is 12 hours. When the material turns from turbid to transparent, the system temperature is lowered to 25°C, and the pH is adjusted to 6 to obtain side-terminal hydrogen-containing silicone oil.

[0023] Take 60 parts of side-terminated hydrogenated silicone oil and transfer it into a three-necked flask equipped with a stirrer and a condenser, add 10 parts of glycidyl methacrylate and 30 parts of chloroplatinic acid, react at 85°C for 5 hours, then evaporate the low-boiling point substance under a vacuum condition of 0.09 MPa to obtain side-terminated epoxy silicone oil.

[0024] Take side-terminated epoxy silicone oil and tetraethylene pentamine and mix them evenly, the molar ratio of the side-terminated epoxy silicone oil and tetraethylene pentamine is 1:2, add isopropanol as a solvent, the amount of isopropanol is the sum of the weights of the side-terminated epoxy silicone oil and tetraethylene pentamine, react at 85°C for 10 hours, and then evaporate the isopropanol under normal pressure to obtain hydrophilic amino silicone oil.

[0025] Example 3 In parts by weight, 100 parts of octamethylcyclotetrasiloxane, 40 parts of high hydrogen-containing silicone oil, and 10 parts of hydrogen-containing double-end silicone oil are mixed evenly, 30 parts of dibutyltin oxide are added, the reaction time is 10 hours at 68°C, and when the material turns from turbid to transparent, the system temperature is lowered to 25°C, and the pH is adjusted to 6 to obtain side-terminal hydrogen-containing silicone oil.

[0026] Take 80 parts of side-terminal hydrogenated silicone oil and transfer it into a three-necked flask equipped with a stirrer and a condenser, add 10 parts of glycidyl methacrylate and 50 parts of chloroplatinic acid, react at 83°C for 6 hours, then evaporate the low-boiling point substance under a vacuum condition of 0.09 MPa to obtain side-terminal epoxy silicone oil.

[0027] Take side-terminated epoxy silicone oil and tetraethylene pentamine and mix them evenly, the molar ratio of the side-terminated epoxy silicone oil and tetraethylene pentamine is 1:3, add isopropanol as a solvent, the amount of isopropanol is the sum of the weights of the side-terminated epoxy silicone oil and tetraethylene pentamine, react at 90°C for 10 hours, and then evaporate the isopropanol under normal pressure to obtain hydrophilic amino silicone oil.

[0028] Example 4 In parts by weight, 120 parts of octamethylcyclotetrasiloxane, 40 parts of high hydrogen-containing silicone oil, and 10 parts of hydrogen-containing double-end silicone oil are mixed evenly, 10 parts of dibutyltin oxide are added, and the reaction time is 10 hours at 65°C. When the material turns from turbid to transparent, the system temperature is lowered to 25°C, and the pH is adjusted to 6 to obtain side-terminal hydrogen-containing silicone oil.

[0029] Take 80 parts of side-terminated hydrogenated silicone oil and transfer it into a three-necked flask equipped with a stirrer and a condenser, add 10 parts of glycidyl methacrylate and 30 parts of chloroplatinic acid, react at 83°C for 6 hours, then evaporate the low-boiling point substance under a vacuum condition of 0.09 MPa to obtain side-terminated epoxy silicone oil.

[0030] Take side-terminated epoxy silicone oil and tetraethylene pentamine and mix them evenly, the molar ratio of the side-terminated epoxy silicone oil and tetraethylene pentamine is 1:2, add isopropanol as a solvent, the amount of isopropanol used is the sum of the weights of the side-terminated epoxy silicone oil and tetraethylene pentamine, react at 90°C for 10 hours, and then evaporate the isopropanol under normal pressure to obtain hydrophilic amino silicone oil.

[0031] Comparative Example 1 In parts by weight, 120 parts of octamethylcyclotetrasiloxane, 30 parts of high hydrogen-containing silicone oil, and 10 parts of hydrogen-containing double-capped silicone oil are mixed evenly, 20 parts of dibutyltin oxide are added, the reaction temperature is 65°C, and the reaction time is 12 hours. When the material turns from turbid to transparent, the system temperature is lowered to 25°C, and the pH is adjusted to 6 to obtain side-terminal hydrogen-containing silicone oil.

[0032] Take 60 parts of side-terminated hydrogenated silicone oil and transfer it into a three-necked flask equipped with a stirrer and a condenser, add 10 parts of glycidyl methacrylate and 30 parts of chloroplatinic acid, react at 85°C for 5 hours, then evaporate the low-boiling point substance under a vacuum condition of 0.09 MPa to obtain side-terminated epoxy silicone oil.

[0033] Take side-terminated epoxy silicone oil and triethylenetetramine and mix them evenly, the molar ratio of the side-terminated epoxy silicone oil and triethylenetetramine is 1:2, add isopropanol as a solvent, the amount of isopropanol is the sum of the weights of the side-terminated epoxy silicone oil and triethylenetetramine, react at 85°C for 10 hours, and then evaporate the isopropanol under normal pressure to obtain hydrophilic amino silicone oil.

[0034] Comparative Example 2 In parts by weight, 120 parts of octamethylcyclotetrasiloxane, 30 parts of high hydrogen-containing silicone oil, and 10 parts of hydrogen-containing double-capped silicone oil are mixed evenly, 20 parts of dibutyltin oxide are added, the reaction temperature is 65°C, and the reaction time is 12 hours. When the material turns from turbid to transparent, the system temperature is lowered to 25°C, and the pH is adjusted to 6 to obtain side-terminal hydrogen-containing silicone oil.

[0035] Take 60 parts of side-terminated hydrogenated silicone oil and transfer it into a three-necked flask equipped with a stirrer and a condenser, add 10 parts of glycidyl methacrylate and 30 parts of chloroplatinic acid, react at 85°C for 5 hours, then evaporate the low-boiling point substance under a vacuum condition of 0.09 MPa to obtain side-terminated epoxy silicone oil.

[0036] Take side-terminated epoxy silicone oil and pentaethylene hexamine and mix them evenly, the molar ratio of the side-terminated epoxy silicone oil and pentaethylene hexamine is 1:2, add isopropanol as a solvent, the amount of isopropanol is the sum of the weights of the side-terminated epoxy silicone oil and pentaethylene hexamine, react at 85°C for 10 hours, and then evaporate the isopropanol under normal pressure to obtain hydrophilic amino silicone oil.

[0037] Performance characterization: The amino silicone oil prepared in the above examples and comparative examples was used to finish the regenerated polyester staple fibers. The softening finishing was carried out under the conditions of 20 g / L amino silicone softener, 175°C, speed 35 m / min, and overfeed 2%.

[0038] Slipperiness: Through a touch test, 10 professionals are divided into groups to rate the touch, with a grade of 1-5. The higher the grade number, the better the softness. Hydrophilicity: The hydrophilicity of a fabric is defined by measuring the time in seconds for a drop of water to be completely absorbed by the fabric. The shorter the time, the better the hydrophilicity. The WIE whiteness value is measured using a colorquest colorimeter. The larger the value, the higher the whiteness and the smaller the yellowing.

[0039] Table 1 Performance characteristics of regenerated polyester staple fibers treated with amino silicone oil in the examples and comparative examples

[0040] Table 1 shows the performance results of regenerated polyester staple fibers treated with amino silicone oils in Examples and Comparative Examples. By comparing Example 2 with Comparative Examples 1-2, it can be seen that, under the premise that other conditions are basically the same, only the specific type of polyethylene polyamine is changed, and tetraethylene pentamine is selected as the ring-opening agent to obtain better comprehensive performance than triethylenetetramine and pentaethylenehexamine. The possible reason is that the molecular chain length of tetraethylene pentamine is relatively appropriate, which is conducive to crosslinking or ring formation between it and the side-terminal epoxy silicone oil.

[0041] The invention uses octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double cap as raw materials, prepares side-terminal hydrogen silicone oil under the action of a catalyst, grafts glycidyl methacrylate to the side-terminal hydrogen silicone oil by means of a silylation reaction to obtain side-terminal epoxy silicone oil, and then uses polyethylene polyamine to perform ring-opening treatment on the epoxy group to obtain modified silicone oil. The modified silicone oil has an ester group, an ether bond and an amino group at the same time. Since the amino group and the hydroxyl group have strong polarity, they can interact with groups such as hydroxyl and carboxyl groups in the fiber to generate extremely strong orientation and adsorption, thereby greatly improving the directional arrangement of siloxane on the fiber. The invention is applied to the post-finishing process of regenerated polyester fiber fabrics, and can make the fabric feel super soft, smooth and plump, and have good hygroscopicity and durability.

[0042] The present invention controls the specific type and amount of polyethylene polyamine so that the side chain and the terminal active groups cooperate with the polyethylene polyamine to form a multi-dimensional network self-crosslinking structure. On the one hand, the network crosslinking structure covers the surface of the fabric, making the fabric softer and fuller, and having a better rebound effect. On the other hand, the use of polyethylene polyamine as a crosslinking agent can convert the primary amines in the polyethylene polyamine into secondary amines, reduce the relative content of the primary amines in the system, and further reduce the yellowing of the amino group.

[0043] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A production process of modified silicone oil for regenerated polyester staple fibers, characterized in that: The steps include: S1: using octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double head as raw materials, preparing side-terminal hydrogen-containing silicone oil under the action of catalyst; the mass ratio of octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double head is 10-12:3-4:1; the reaction temperature is 60-68°C, and the reaction time is 10-12 hours; S2: preparing side-terminal epoxy silicone oil by using the side-terminal hydrogen-containing silicone oil and glycidyl methacrylate prepared in step S1 under the catalysis of chloroplatinic acid; the mass ratio of the side-terminal hydrogen-containing silicone oil to glycidyl methacrylate is 5-8:1; the mass ratio of chloroplatinic acid to glycidyl methacrylate is 1-5:1; S3: using polyethylene polyamine as a ring-opening reagent to perform a ring-opening treatment on the side-terminated epoxy silicone oil prepared in step S2 to obtain the modified silicone oil, wherein the molar ratio of the side-terminated epoxy silicone oil to the polyethylene polyamine is 1:1-3.

2. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: In step S1, the mass ratio of octamethylcyclotetrasiloxane, methyl high hydrogen silicone oil and hydrogen-containing double head is 12:3:

1.

3. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: The catalyst in step S1 is dibutyltin oxide, and the mass ratio of the hydrogen-containing double end cap to dibutyltin oxide is 1:1-3; the reaction temperature of step S1 is 65° C., and the reaction time is 12 hours.

4. The production process of modified silicone oil for regenerated polyester staple fibers according to claim 1, characterized in that: In step S2, the mass ratio of the side-terminal hydrogen-containing silicone oil to glycidyl methacrylate is 6:1; the mass ratio of chloroplatinic acid to glycidyl methacrylate is 3:

1.

5. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: In step S2, the reaction temperature is 80-85° C. and the reaction time is 4-6 h.

6. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: In step S3, the polyethylene polyamine is any one of triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

7. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: In step S3, the polyethylene polyamine is tetraethylene pentamine.

8. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: The molar ratio of the side-terminated epoxy silicone oil to the polyethylene polyamine is 1:

2.

9. The production process of modified silicone oil for regenerated polyester staple fiber according to claim 1, characterized in that: In step S3, isopropanol is used as the reaction solvent. The amount of isopropanol used is the sum of the weights of the side-terminated epoxy silicone oil and the polyethylene polyamine. The reaction temperature is 80-90° C. and the reaction time is 10-12 hours.

10. A modified silicone oil for regenerated polyester staple fibers, characterized in that The product is prepared by the production process described in any one of claims 1 to 9.

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