Recycled colored terylene bulked filament prepared by grading opaque coloring technology

Abstract

The invention relates to a recycled colored terylene bulked filament prepared by a grading shading coloring technology, and belongs to the technical field of fiber materials. According to the invention, waste colored polyester, conventional semi-dull polyester, color master batch, zinc acetate, antimony trioxide and a self-made reinforcing agent are used as raw materials to prepare the polyester reclaimed material colored fiber prepared based on a grading shading coloring technology, the waste colored polyester is classified according to color systems, and the self-made reinforcing agent is used for chain extension, so that the colored fiber is obtained. And then adding dark color master batches for color masking, adding conventional polyester chips, mixing together, and carrying out melt spinning to obtain the recycled colored polyester bulked filament. The recycled colored polyester bulked filament is produced by directly using the waste colored polyester by using a grading shading coloring technology, the colored waste polyester does not need to be decolored, the recycled colored polyester bulked filament is green and environment-friendly, and the prepared recycled colored bulked filament has good strength and rebound resilience and can be widely applied to the field of carpet yarns.

Description

Technical Field

[0001] The invention belongs to the technical field of fiber materials, and in particular relates to recycled colored regenerated polyester bulked filaments prepared by graded color-shading coloring technology. Background Art

[0002] Polyester fiber is widely used in the field of carpet yarn due to its excellent physical and chemical properties, which also leads to an increasing amount of waste polyester. Since polyester is difficult to biodegrade, its waste is piled up in large quantities and even flows into the ocean, causing serious environmental pollution. Carpet yarn is a kind of silk thread material used to make carpets, usually made of natural fibers or synthetic fibers. The production process of carpet yarn includes raw material preparation, melt drawing, twisting and shaping, etc.

[0003] In the prior art, although colored polyester accounts for a large proportion of waste polyester, it is generally landfilled or incinerated, or downgraded to carpets, engineering fillers, asphalt and other products that do not require high color due to the high cost and difficulty of decolorization and separation and purification. Based on this, the present invention provides a recycled colored regenerated polyester bulked filament prepared based on a graded color shading coloring technology, which can directly use waste colored polyester to prepare recycled colored polyester bulked filament (BCF) without decolorization. Summary of the invention

[0004] The object of the present invention is to provide a recycled colored regenerated polyester bulked filament prepared based on graded color shading coloring technology, which is used to solve the problems mentioned in the above background technology.

[0005] The purpose of the present invention can be achieved by the following technical solutions: The recycled colored regenerated polyester bulked filament prepared by graded color shading technology comprises the following raw materials: recycled colored polyester modified by reinforcing agent, conventional semi-dull polyester, dark masterbatch of the same color series, wherein the weight proportion is: the formula is: the recycled colored polyester modified by reinforcing agent>51 parts, the conventional semi-dull polyester<49 parts, and 1-10 parts of dark masterbatch of the same color series; The preparation method of the recycled colored regenerated polyester bulked filament comprises the following steps: The first step is to classify the waste colored polyester according to the color system to obtain the recycled colored polyester; The second step is to put the classified recycled colored polyester, zinc acetate and antimony trioxide into a nitrogen-protected reflux reaction vessel, add a homemade enhancer, and pump the pressure in the reaction vessel to 0.01-0.05 KPa, and then perform a polymerization reaction at a temperature of 260-270° C. for 2-4 hours to obtain a recycled colored polyester modified with an enhancer; In the third step, the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system are mixed and added into a twin-screw extruder for melt extrusion and then spun to obtain a recycled colored polyester bulked filament prepared based on graded color shading technology.

[0006] Furthermore, the mass ratio of the classified recycled polyester, zinc acetate, antimony trioxide, and homemade reinforcing agent used in the second step is 100:0.4:0.08-0.1:5.

[0007] Furthermore, in the third step, the mass fraction ratio of the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system is 51-80:20-49:3-10.

[0008] Furthermore, in the third step, the parameters of the twin-screw extruder were set to 290° C. in zone 1, 295° C. in zone 2, 295° C. in zone 3, 300° C. in zone 4, 295° C. in zone 5, 290° C. in zone 6, and a screw speed of 50 rpm.

[0009] Further, the reinforcing agent is prepared by the following steps: Step 1, 4-methylaminobenzoic acid, epichlorohydrin and N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 70-90°C for 2-3h. After the reaction was completed, the solvent was removed by rotary evaporation, and then the intermediate 1 was obtained by silica gel column chromatography; Step 2, the intermediate 1 and triethyl phosphite are mixed in a three-necked flask, a condenser and a thermometer are installed, magnetic stirring is turned on, and the reaction is carried out at a temperature of 140-145° C. for 24 hours. After the reaction is completed, the triethyl phosphite is removed by rotary evaporation to obtain the intermediate 2; Step 3: Mix the intermediate 2, n-propyl bromide and acetonitrile in a three-necked flask, install a condenser and a thermometer, start magnetic stirring, and react at a temperature of 40-60°C for 24 hours. After the reaction is completed, remove the solvent by rotary evaporation, and then obtain the enhancer through silica gel column chromatography.

[0010] Furthermore, the amount ratio of 4-methylaminobenzoic acid, epichlorohydrin and N,N-dimethylformamide used in step 1 is 0.1 mol: 0.1 mol: 80-100 mL.

[0011] Furthermore, the usage ratio of the intermediate 1 and triethyl phosphite used in step 2 is 0.08 mol: 0.12-0.15 mol.

[0012] Furthermore, the usage ratio of the intermediate 2, n-propyl bromide and acetonitrile used in step 3 is 0.04 mol: 0.04-0.06 mol: 40-60 mL.

[0013] Beneficial effects of the present invention: 1) The present invention uses recycled colored polyester, zinc acetate, antimony trioxide, and a homemade reinforcing agent as raw materials to prepare polyester recycled material colored fibers prepared by graded color shading coloring technology. The preparation method of the present invention classifies the waste colored polyester according to color systems, polymerizes and extends the chain together with the homemade reinforcing agent to obtain the reinforcing agent modified recycled colored polyester, and then mixes the reinforcing agent modified recycled colored polyester with conventional semi-dull polyester and dark masterbatch and melt-spins them to obtain polyester recycled material colored fibers prepared by graded color shading coloring technology. The preparation method of the present invention uses the graded color shading coloring technology to directly produce recycled colored polyester fibers from waste polyester, without the need to decolorize the colored waste polyester, and is green and environmentally friendly.

[0014] 2) The present invention uses 4-methylaminobenzoic acid and epichlorohydrin as raw materials, utilizes the imino group of 4-methylaminobenzoic acid and the epoxy group of epichlorohydrin to undergo nucleophilic addition reaction to obtain intermediate 1, then uses intermediate 1 as raw material, utilizes the chlorine atom of intermediate 1 and triethyl phosphite to undergo Michaelis-Arbuzov reaction to obtain intermediate 2, finally uses intermediate 2 as raw material, utilizes the tertiary amine structure of intermediate 2 and n-propyl bromide to undergo quaternary ammonium salt reaction to obtain an enhancer; the enhancer of the present invention has a hydroxyl group and a carboxyl group in its structure, which can be copolymerized with the product of alcoholysis of waste polyester and combined in colored polyester, so as to be effective for a long time and stably; the phosphate structure in the enhancer of the present invention reacts at high temperature to form a dense protective carbon layer, which can give the colored polyester a good flame retardant effect; in addition, the enhancer of the present invention also has a quaternary ammonium salt structure, which can increase the charge density in the colored polyester after polymerization with the colored polyester, and promote charge transfer, which can give the colored polyester a good antistatic effect.

[0015] 3) The polyester recycled material colored fiber prepared based on the graded color shading coloring technology of the present invention is green and environmentally friendly and can be widely used in the field of carpet yarn. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] Example 1 An enhancer is prepared by the following steps: Step 1, 0.1 mol 4-aminobenzoic acid, 0.1 mol epichlorohydrin, and 80 mL N, N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 70° C. for 2 h. After the reaction was completed, the solvent was removed by rotary evaporation, and then the intermediate 1 was obtained by silica gel column chromatography; Step 2, 0.08 mol of intermediate 1 and 0.12 mol of triethyl phosphite were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 140° C. for 24 hours. After the reaction was completed, triethyl phosphite was removed by rotary evaporation to obtain intermediate 2; Step 3: Mix 0.04 mol of intermediate 2, 0.04 mol of n-propyl bromide and 40 mL of acetonitrile in a three-necked flask, install a condenser and a thermometer, turn on magnetic stirring, and react at 40°C for 24 hours. After the reaction is completed, remove the solvent by rotary evaporation, and then obtain the enhancer by silica gel column chromatography.

[0018] Example 2 An enhancer is prepared by the following steps: Step 1, 0.1 mol 4-aminobenzoic acid, 0.1 mol epichlorohydrin, and 90 mL N, N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 80° C. for 2.5 h. After the reaction was completed, the solvent was removed by rotary evaporation, and then the intermediate 1 was obtained by silica gel column chromatography; Step 2, 0.08 mol of intermediate 1 and 0.135 mol of triethyl phosphite were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 142° C. for 24 hours. After the reaction was completed, triethyl phosphite was removed by rotary evaporation to obtain intermediate 2; Step 3, 0.04 mol of intermediate 2, 0.05 mol of n-propyl bromide and 50 mL of acetonitrile were mixed in a three-necked flask, equipped with a condenser and a thermometer, and magnetic stirring was turned on. The reaction was carried out at a temperature of 50° C. for 24 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the enhancer was obtained by silica gel column chromatography.

[0019] Example 3 An enhancer is prepared by the following steps: Step 1, 0.1 mol 4-aminobenzoic acid, 0.1 mol epichlorohydrin, and 100 mL N, N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 90° C. for 3 h. After the reaction was completed, the solvent was removed by rotary evaporation, and then the intermediate 1 was obtained by silica gel column chromatography; Step 2, 0.08 mol of intermediate 1 and 0.15 mol of triethyl phosphite were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 145° C. for 24 hours. After the reaction was completed, triethyl phosphite was removed by rotary evaporation to obtain intermediate 2; Step 3: Mix 0.04 mol of intermediate 2, 0.06 mol of n-propyl bromide and 60 mL of acetonitrile in a three-necked flask, install a condenser and a thermometer, turn on magnetic stirring, and react at 60° C. for 24 hours. After the reaction is completed, remove the solvent by rotary evaporation, and then obtain the enhancer by silica gel column chromatography.

[0020] Example 4 The polyester recycled material colored fiber prepared by graded color shading coloring technology comprises the following raw materials: waste polyester, conventional semi-dull polyester, masterbatch, zinc acetate, antimony trioxide, and the reinforcing agent obtained in Example 1; The method for preparing the polyester recycled colored fiber comprises the following steps: The first step is to classify the waste colored polyester according to the color system to obtain the recycled colored polyester; The second step is to put the classified recycled colored polyester, zinc acetate and antimony trioxide into a reflux reaction container protected by nitrogen, add a homemade enhancer, and pump the pressure in the reaction container to 0.02 KPa, and then carry out a polymerization reaction at a temperature of 260°C for 2 hours to obtain a recycled colored polyester modified with an enhancer; wherein, the mass ratio of the classified recycled polyester, zinc acetate, antimony trioxide and homemade enhancer used in this embodiment is 100:0.4:0.08:5.

[0021] The third step is to mix the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system in a mass ratio of 75:20:5, add them into a twin-screw extruder, melt extrude them, and then spin them to obtain a polyester recycled material colored fiber prepared based on the graded color shading technology, wherein the parameters of the twin-screw extruder in this embodiment are set to 290°C in the first zone, 295°C in the second zone, 295°C in the third zone, 300°C in the fourth zone, 295°C in the fifth zone, 290°C in the sixth zone, and the screw speed is 50rpm; The polyester recycled colored fiber prepared by the graded color shading coloring technology is melt-extruded, then subjected to slow cooling side blowing, oiling, hot drawing, hot jet deformation and air cooling, and then wound to obtain polyester recycled colored fiber carpet yarn.

[0022] Example 5 The polyester recycled material colored fiber prepared by graded color shading coloring technology comprises the following raw materials: waste polyester, conventional semi-dull polyester, masterbatch, zinc acetate, antimony trioxide, and the reinforcing agent obtained in Example 2; The method for preparing the polyester recycled colored fiber comprises the following steps: The first step is to classify the waste colored polyester according to the color system to obtain the recycled colored polyester; The second step is to put the classified recycled colored polyester, zinc acetate and antimony trioxide into a reflux reaction vessel protected by nitrogen, add a homemade enhancer, and pump the pressure in the reaction vessel to 0.02 KPa, and then carry out a polymerization reaction at a temperature of 260°C for 2 hours to obtain a recycled colored polyester modified with an enhancer; wherein, the mass ratio of the classified recycled polyester, zinc acetate, antimony trioxide and homemade enhancer used in this embodiment is 100:0.4:0.1:5.

[0023] In the third step, the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system are mixed in a mass ratio of 60:35:5, added into a twin-screw extruder, melt-extruded and spun to obtain a polyester recycled material colored fiber prepared based on graded color shading technology, wherein the parameters of the twin-screw extruder in this embodiment are set to 290°C in zone 1, 295°C in zone 2, 295°C in zone 3, 300°C in zone 4, 295°C in zone 5, 290°C in zone 6, and a screw speed of 50rpm; The polyester recycled colored fiber prepared by the graded color shading coloring technology is melt-extruded, then subjected to slow cooling side blowing, oiling, hot drawing, hot jet deformation and air cooling, and then wound to obtain polyester recycled colored fiber carpet yarn.

[0024] Example 6 The polyester recycled material colored fiber prepared by graded color shading coloring technology comprises the following raw materials: waste polyester, conventional semi-dull polyester, masterbatch, zinc acetate, antimony trioxide, and the reinforcing agent obtained in Example 3; The method for preparing the polyester recycled colored fiber comprises the following steps: The first step is to classify the waste colored polyester according to the color system to obtain the recycled colored polyester; The second step is to put the classified recycled colored polyester, zinc acetate and antimony trioxide into a reflux reaction container protected by nitrogen, add a homemade enhancer, and pump the pressure in the reaction container to 0.02 KPa, and then carry out a polymerization reaction at a temperature of 260°C for 2 hours to obtain a recycled colored polyester modified with an enhancer; wherein, the mass ratio of the classified recycled polyester, zinc acetate, antimony trioxide and homemade enhancer used in this embodiment is 100:0.4:0.09:5.

[0025] The third step is to mix the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system in a mass ratio of 55:40:5, add them into a twin-screw extruder, melt extrude them, and then spin them to obtain a polyester recycled material colored fiber prepared based on the graded color shading technology, wherein the parameters of the twin-screw extruder in this embodiment are set to 290°C in the first zone, 295°C in the second zone, 295°C in the third zone, 300°C in the fourth zone, 295°C in the fifth zone, 290°C in the sixth zone, and the screw speed is 50rpm; The polyester recycled colored fiber prepared by the graded color shading coloring technology is melt-extruded, then subjected to slow cooling side blowing, oiling, hot drawing, hot jet deformation and air cooling, and then wound to obtain polyester recycled colored fiber carpet yarn.

[0026] Comparative Example 1 A polyester recycled colored fiber prepared based on graded color shading technology, comprising the following raw materials: waste polyester, conventional semi-dull polyester, masterbatch, zinc acetate, antimony trioxide; The method for preparing the polyester recycled colored fiber comprises the following steps: The first step is to classify the waste polyester by color to obtain recycled colored polyester; In the second step, the classified recycled colored polyester, zinc acetate and antimony trioxide are put into a reflux reaction container protected by nitrogen, and the pressure in the reaction container is pumped down to 0.04 KPa, followed by a polymerization reaction at 270°C for 2 hours to obtain the reinforcer-modified recycled colored polyester. Among them, the mass fraction ratio of the classified recycled polyester, zinc acetate and antimony trioxide used in this embodiment is 100:0.4:0.09.

[0027] In the third step, the recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system are mixed in a mass ratio of 80:10:10, and then added into a twin-screw extruder for melt extrusion and spinning to obtain a polyester recycled material colored fiber prepared based on the graded color shading technology, wherein the parameters of the twin-screw extruder in this embodiment are set to 290°C for zone 1, 295°C for zone 2, 295°C for zone 3, 300°C for zone 4, 295°C for zone 5, 290°C for zone 6, and a screw speed of 50rpm.

[0028] Comparative Example 2 This comparative example is commercially available environmentally friendly recycled DTY polyester.

[0029] The recycled colored polyester bulked filaments prepared by the graded color-blocking coloring technology in Examples 4-6 and Comparative Example 1 and the commercially available environmentally friendly recycled polyester bulked filaments in Comparative Example 2 were tested for breaking strength using the national standard GB / T14344-2022 "Test Method for Tensile Strength of Chemical Fiber Filaments", and the thermal shrinkage was tested with reference to the national standard GB / T6505-2017 "Test Method for Thermal Shrinkage of Chemical Fiber Filaments (After Treatment)". The test results are shown in Table 1: Table 1 project Breaking strength (cN / dtex) Thermal shrinkage (%) Example 4 5.7 10 Example 5 4.5 12 Example 6 3.8 14 Comparative Example 1 2.7 17 Comparative Example 2 2.4 18 As can be seen from Table 1, the recycled colored polyester bulked filaments prepared based on the graded color shading coloring technology in Examples 4-6 of the present invention have higher breaking strengths than commercially available regenerated polyester bulked filaments, and lower thermal shrinkages than commercially available regenerated polyester bulked filaments, indicating that the polyester recycled material colored fiber prepared based on the graded color shading coloring technology of the present invention has good mechanical properties. Comparative Example 1 conducted a control experiment on the reinforcing agent used in the present invention. Without using the reinforcing agent of the present invention, the recycled colored polyester bulked filaments obtained had low breaking strength and high thermal shrinkage. This illustrates the effectiveness of the reinforcing agent of the present invention. In summary, the preparation method of the present invention is green and environmentally friendly, and the prepared recycled colored polyester bulked filaments have good performance and can be widely used in the field of carpet yarn.

[0030] The above is a detailed introduction to a polyester recycled material colored fiber prepared based on graded color shading technology provided by the present invention. Specific examples are used in this article to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enables any technician in the field to practice the present invention, including the manufacture and use of any device or system, and the implementation of any combination method. It should be pointed out that for ordinary technicians in this technical field, the present invention can also be improved and modified without departing from the principle of the present invention. In particular, as long as there is no structural conflict, the various features in the embodiments disclosed in the present invention can be combined with each other in any way. The reason why these combinations are not exhaustively described in this specification is only for the consideration of omitting space and saving resources. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. The polyester recycled colored fiber prepared by graded color shading technology is characterized by: The raw materials include: recycled colored polyester modified with reinforcing agent, conventional semi-matt polyester, dark masterbatch of the same color series; Wherein, the reinforcing agent is prepared by the following steps: Step 1, 4-methylaminobenzoic acid, epichlorohydrin and N,N-dimethylformamide are mixed in a container, stirred evenly, and reacted at a temperature of 70-90° C. for 2-3 hours to obtain intermediate 1; Step 2, intermediate 1 and triethyl phosphite are mixed in a container, stirred evenly, and reacted at a temperature of 140-145° C. for 24 hours to obtain intermediate 2; Step 3, the intermediate 2, n-propyl bromide and acetonitrile are mixed in a container, stirred evenly, and reacted at a temperature of 40-60° C. for 24 hours to obtain the enhancer; The reinforcing agent-modified recycled colored polyester is obtained by subjecting the recycled colored polyester to polymerization and chain extension modification with a reinforcing agent.

2. The polyester recycled material colored fiber prepared by the graded color shading coloring technology according to claim 1, characterized in that: The amount ratio of 4-methylaminobenzoic acid, epichlorohydrin and N,N-dimethylformamide used in step 1 is 0.1 mol: 0.1 mol: 80-100 mL.

3. The polyester recycled material colored fiber prepared by the graded color shading coloring technology according to claim 1, characterized in that: The usage ratio of intermediate 1 and triethyl phosphite used in step 2 is 0.08 mol: 0.12-0.15 mol.

4. The polyester recycled material colored fiber prepared by the graded color shading coloring technology according to claim 1, characterized in that: The amount ratio of intermediate 2, n-propyl bromide and acetonitrile used in step 3 is 0.04 mol: 0.04-0.06 mol: 40-60 mL.

5. The polyester recycled material colored fiber prepared by the graded color shading coloring technology according to claim 1, characterized in that: The method for preparing the polyester recycled colored fiber comprises the following steps: The first step is to classify the waste colored polyester according to the color system to obtain the recycled colored polyester; The second step is to put the classified recycled colored polyester, zinc acetate and antimony trioxide into a nitrogen-protected reflux reaction vessel, add a homemade enhancer, and pump the pressure in the reaction vessel to 0.01-0.05 KPa, and then perform a polymerization reaction at a temperature of 260-270° C. for 2-4 hours to obtain a recycled colored polyester modified with an enhancer; In the third step, the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system are mixed and added into a twin-screw extruder for melt extrusion and then spun to obtain a recycled colored polyester bulked filament prepared based on graded color shading technology.

6. The recycled colored polyester bulked filament prepared by the graded color-shading coloring technology according to claim 5, characterized in that: The mass ratio of the classified recycled polyester, zinc acetate, antimony trioxide and homemade reinforcing agent used in the second step is 100:0.4:0.08-0.1:

5.

7. The recycled colored polyester bulked filament prepared based on the graded color-shading coloring technology according to claim 5, characterized in that: The mass fraction ratio of the reinforcing agent-modified recycled colored polyester, conventional semi-dull polyester and dark masterbatch of the same color system in the third step is 51-80:20-49:3-10.

8. The polyester recycled material colored fiber prepared by the graded color shading coloring technology according to claim 5, characterized in that: In the third step, the parameters of the twin-screw extruder were set as 290°C in zone 1, 295°C in zone 2, 295°C in zone 3, 300°C in zone 4, 295°C in zone 5, 290°C in zone 6, and a screw speed of 50 rpm.