Flame-retardant polyester fabric and preparation process thereof

Abstract

The application belongs to the polyester fiber field and particularly relates to a flame-retardant polyester fabric, which is prepared from the following raw materials: PET polyester chip 50-70 parts, modified PET polyester masterbatch 20-30 parts, coupling agent 1-3 parts, nano-silicon dioxide 1-5 parts, antioxidant 0.5-1 part, PEG-400 5-10 parts. The prepared polyester fabric has excellent flame-retardant performance, the initial limiting oxygen index reaches 36.8%, and the vertical flammability UL-94 reaches V0 level. In addition, after 50 times of washing, the limiting oxygen index does not decrease obviously, and the polyester fabric has good washing resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of polyester fibers, and particularly relates to a flame-retardant polyester fabric and a preparation process thereof. BACKGROUND

[0002] Polyethylene terephthalate (PET) is an aromatic polyester, which is prepared from terephthalic acid (PTA) and ethylene glycol (EG) through a condensation polymerization reaction. At present, PET polymers have been widely used in the fields of plastics, films and fibers. In particular, in the field of fibers, polyester chips prepared through condensation polymerization are melted and spun into polyester fibers, which have high breaking strength and elastic modulus, moderate resilience, excellent light resistance, heat resistance and corrosion resistance, and the fabrics thereof have excellent wearability, crispness and wrinkle resistance. Therefore, since the polyester fiber was introduced, it has rapidly developed and has become the largest synthetic fiber in the world.

[0003] Although the polyester fiber has many advantages and a huge market, it has a low LOI and belongs to flammable fibers. In fire accidents, a considerable proportion of fires are caused by textile fibers, and the losses caused by the fires are also increasing, which greatly limits the application range of the polyester fiber. Meanwhile, the polyester fiber produces serious melt dripping during combustion. Although the melt dripping can take away part of the heat from the polymer substrate and is beneficial to the flame retardance of the polyester fiber, the melt dripping causes more serious disasters: on the one hand, the melt dripping can cause the flame to spread to other places and cause larger fires; on the other hand, the melt dripping can easily cause secondary injuries such as burns and scalds. Therefore, it is urgent to develop more polyester fabrics with excellent flame retardance. SUMMARY

[0004] The application aims to provide a polyester fabric with excellent flame retardance and good washing resistance. The application is achieved by the following technical scheme:

[0005] A flame-retardant polyester fabric, the raw materials of which include, by weight:

[0006] PET polyester chips 50-70 parts

[0007] Modified PET polyester masterbatch 20-30 parts

[0008] Coupling agent 1-3 parts

[0009] Nano-silicon dioxide 1-5 parts

[0010] Antioxidant 0.5-1 part

[0011] PEG-400 5-10 parts

[0012] The modified PET polyester master batch is prepared by polymerization of terephthalic acid, ethylene glycol, and a modifier in the presence of a catalyst Sb2O3.

[0013] The structural formula of the modifier is:

[0014] In some embodiments, the coupling agent is selected from one or more of KH-550, KH-560, KH-570, KH-792, KH-791, DL-602, and DL-171.

[0015] In some embodiments, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 1068.

[0016] In some embodiments, the method for preparing the modified PET polyester master batch comprises the following steps:

[0017] terephthalic acid, ethylene glycol, the modifier, and the catalyst Sb2O3 in a molar ratio of 1:1:0.5:0.1 are mixed and then added into a reaction kettle; the air tightness of the system is checked, nitrogen is filled to remove the air in the reaction kettle, the temperature is increased and controlled at 220-260℃, and the pressure in the reaction kettle is controlled at 0.2-0.5 MPa, and the reaction time is 30-60 min; the reaction is continued, the reaction kettle is vacuumed, and the temperature is controlled at 260-300℃, and the polyester is obtained after 15-30 min, and then the modified PET polyester master batch is obtained through extrusion granulation and drying.

[0018] In some embodiments, the rotating speed of the extruder is 40 r / min, the temperature of the first zone of the extruder is 260℃, the temperature of the second zone is 290℃, the temperature of the third zone is 280℃, and the temperature of the fourth zone is 280℃.

[0019] In some embodiments, the raw materials include, by weight:

[0020] PET polyester chip 50 parts

[0021] Modified PET polyester master batch 30 parts

[0022] Coupling agent DL-602 2 parts

[0023] Nano-silica 3 parts

[0024] Antioxidant 168 0.5 parts

[0025] PEG-400 10 parts.

[0026] The application also provides a preparation process of the flame-retardant polyester fabric, comprising the following steps:

[0027] PET polyester chip, modified PET polyester master batch, coupling agent, nano silicon dioxide, antioxidant, PEG-400 are mixed uniformly, and then melt spinning is carried out on a spinning machine, the spinning temperature in the spinning machine is 220-260 DEG C, the screw rotation speed is 500-800 r / min, and the winding speed is 1000-1200 r / min, so that the polyester fiber is obtained; the above-mentioned polyester fiber is spun into a flame-retardant polyester fabric through a textile machine.

[0028] The present application has the following beneficial effects:

[0029] 1) The prepared polyester fabric has excellent flame retardant performance, the initial limiting oxygen index reaches 36.8%, and the vertical combustion UL-94 reaches V0 level; in addition, after 50 times of washing, the limiting oxygen index does not decrease obviously, and has good washing resistance.

[0030] 2) The modifier used in the present application Simultaneously contains B, N and P three kinds of flame-retardant elements, which can realize synergistic high-efficiency flame retardation when introduced into the polyester fabric; and the modifier contains hydroxyl groups at both ends, which is polymerized with terephthalic acid, so that the flame-retardant molecules are introduced into the polymer main chain, so that the polyester fabric has good washing resistance. DETAILED DESCRIPTION

[0031] The technical solutions of the present application will be described below in conjunction with the embodiments, obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0032] The endpoints of the ranges and any values described herein are not limited to the precise values stated. These ranges and values should be construed as being approximate. For ranges, the endpoints are included as well as intervening points not specifically recited. For values, the endpoints are included as well as intervening values not specifically recited.

[0033] Preparation example 1 synthesis of modifier

[0034] Step 1: synthesis of intermediate compound C

[0035]

[0036] Compound A (0.1 mol), triethylamine (0.1 mol) and tetrahydrofuran (100 mL) were added into a reactor, stirred at room temperature until Compound A was completely dissolved. Then Compound B (0.22 mol) and tetrahydrofuran (100 mL) were mixed uniformly, slowly dropped into the reactor at 0°C under nitrogen atmosphere. The temperature was raised to 60°C and the reaction was stirred for 10 h. After the reaction, the mixture was filtered, the filtrate was washed with water three times (200 mL x 3), the organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography to obtain intermediate Compound C, with a yield of 83.6%.

[0037] LC-MS (ESI): [M+H] + = 619.3.

[0038] Step 2: Synthesis of modifier

[0039]

[0040] Intermediate Compound C (0.1 mol), Compound D (0.25 mol) and chloroform (200 mL) were added into a reactor, and the temperature was raised to 60°C and the reaction was stirred for 12 h. After the reaction, the mixture was concentrated under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain a modifier white solid, with a yield of 67.1%.

[0041] LC-MS (ESI): [M+H] + = 705.3.

[0042] 1 H-NMR (500MHz, CDCl3): δ (ppm): 8.60 (s, 2H), 7.87-7.78 (m, 2H), 7.58 (d, 2H), 7.41-7.35 (m, 2H), 7.25-7.14 (m, 5H), 6.10 (t, 4H), 5.02 (s, 2H), 4.35 (t, 4H), 1.21 (s, 24H).

[0043] Preparation of modified PET polyester masterbatch

[0044] Terephthalic acid, ethylene glycol, modifier (obtained in Preparation Example 1) and catalyst Sb2O3 in a molar ratio of 1:1:0.5:0.1 were mixed and added into a reactor. The system was checked for air tightness, nitrogen was filled to remove air in the reactor, the temperature was raised and controlled at 260°C, and the pressure in the reactor was controlled at 0.5 MPa. The reaction time was 60 min. The reactor was vacuumed, and the temperature was controlled at 300°C. After 30 min, the polyester was obtained, and then the polyester was extruded, granulated and dried to obtain a modified PET polyester masterbatch.

[0045] The rotation speed of the extruder is 40 r / min, the temperature of the first zone of the extruder is 260 DEG C, the temperature of the second zone is 290 DEG C, the temperature of the third zone is 280 DEG C, and the temperature of the fourth zone is 280 DEG C.

[0046] Example 1

[0047] A flame-retardant polyester fabric, by weight, the raw materials include:

[0048] PET polyester chip (viscosity 0.68) 60 parts

[0049] Modified PET polyester masterbatch (obtained in Preparation Example 2) 30 parts

[0050] Coupling agent KH-550 1 part

[0051] Nano-silica 2 parts

[0052] Antioxidant 1010 1 part

[0053] PEG-400 10 parts

[0054] The preparation method of the flame-retardant polyester fabric includes the following steps:

[0055] The PET polyester chip, the modified PET polyester masterbatch, the coupling agent, the nano-silica, the antioxidant, and the PEG-400 are uniformly mixed, and then melt spinning is performed on a spinning machine, the spinning temperature in the spinning machine is 260 DEG C, the screw rotation speed is 800 r / min, and the winding speed is 1200 r / min, to obtain a polyester fiber; the polyester fiber is spun into a flame-retardant polyester fabric through a textile machine.

[0056] Example 2

[0057] A flame-retardant polyester fabric, by weight, the raw materials include:

[0058] PET polyester chip (viscosity 0.68) 70 parts

[0059] Modified PET polyester masterbatch (obtained in Preparation Example 2) 20 parts

[0060] Coupling agent KH-560 3 parts

[0061] Nano-silica 2 parts

[0062] Antioxidant 1076 0.5 parts

[0063] PEG-400 8 parts

[0064] The preparation method of the flame-retardant polyester fabric includes the following steps:

[0065] PET polyester chip, modified PET polyester masterbatch, coupling agent, nano-silica, antioxidant, PEG-400 are mixed uniformly, and then melt spinning is carried out on a spinning machine, the spinning temperature in the spinning machine is 260°C, the screw rotation speed is 800 r / min, and the winding speed is 1200 r / min, to obtain polyester fiber; the polyester fiber is spun into flame-retardant polyester fabric through a textile machine.

[0066] Example 3

[0067] A flame-retardant polyester fabric, the raw materials of which include, by weight:

[0068] PET polyester chip (viscosity 0.68) 50 parts

[0069] Modified PET polyester masterbatch (obtained in Preparation Example 2) 30 parts

[0070] Coupling agent DL-602 2 parts

[0071] Nano-silica 3 parts

[0072] Antioxidant 168 0.5 parts

[0073] PEG-400 10 parts

[0074] The preparation method of the flame-retardant polyester fabric includes the following steps:

[0075] PET polyester chip, modified PET polyester masterbatch, coupling agent, nano-silica, antioxidant, PEG-400 are mixed uniformly, and then melt spinning is carried out on a spinning machine, the spinning temperature in the spinning machine is 260°C, the screw rotation speed is 800 r / min, and the winding speed is 1200 r / min, to obtain polyester fiber; the polyester fiber is spun into flame-retardant polyester fabric through a textile machine.

[0076] Comparative Example 1

[0077] The modifier in Preparation Example 2 is replaced with a known modifier in the art Other operations and conditions are the same as in Preparation Example 2, to obtain modified PET polyester masterbatch B.

[0078] Then, on the basis of Example 1, the modified PET polyester masterbatch is replaced with the above modified PET polyester masterbatch B, and other components and preparation methods are the same as in Example 1.

[0079] Flame-retardant performance determination:

[0080] The flame-retardant performance of the polyester fabrics obtained in Examples 1-3 and Comparative Example 1 is determined respectively, and the test method is as follows:

[0081] Limiting oxygen index: The limiting oxygen index of the polyester fabric is detected according to GB / T 5454-1997 Textiles - Determination of the ignition behavior of fabrics - Part 2: Test method - Oxygen index method. Meanwhile, the grade of vertical flammability UL-94 (tested by using CZF-5 type vertical flammability instrument) is used to assist in judgment.

[0082] Washing: One washing is calculated as washing in clean water for 30 min under standard atmospheric conditions (20±2℃, 65±5% RH).

[0083] The results are shown in Table 1.

[0084] Table 1: Results of flame retardant performance test

[0085]

[0086] As shown in the above table, the polyester fabric prepared by the present application has excellent flame retardant performance. The initial limiting oxygen index is 36.8%, and the vertical flammability UL-94 reaches V0 level. In addition, after 50 times of washing, the limiting oxygen index does not decrease obviously, and has good washing resistance. The main reasons are as follows: 1) the modifier selected by the present application contains B, N and P three kinds of flame retardant elements, which can realize synergistic and efficient flame retardation when introduced into the polyester fabric; 2) the modifier of the present application contains hydroxyl groups at both ends, which is polymerized with terephthalic acid, so that the flame retardant molecules are introduced into the polymer main chain, so that the polyester fabric has good washing resistance.

[0087] The above examples are merely examples for clearly illustrating, but not limitation to the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. All the embodiments do not need to be exhausted, and the obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A flame-retardant polyester fabric, comprising, by weight: The modified PET polyester masterbatch is prepared by polymerization of terephthalic acid, ethylene glycol, and a modifier in the presence of a catalyst Sb2O3; The structural formula of the modifier is:

2. The flame retardant polyester fabric according to claim 1, characterized in that: The coupling agent is selected from one or more of KH-550, KH-560, KH-570, KH-792, KH-791, DL-602 and DL-171.

3. The flame retardant polyester fabric according to claim 1, characterized in that: The antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 1068.

4. The flame retardant polyester fabric according to claim 1, characterized in that: The preparation method of the modified PET polyester masterbatch comprises the following steps: Terephthalic acid, ethylene glycol, a modifier and a catalyst Sb2O3 in a molar ratio of 1:1:0.5:0.1 are mixed and added into a reactor; the air tightness of the system is checked, nitrogen is introduced to remove the air in the reactor, the temperature is increased and controlled at 220-260°C, and the pressure in the reactor is controlled at 0.2-0.5 MPa, and the reaction time is 30-60 minutes; the reaction is continued, the reactor is vacuumed, and the temperature is controlled at 260-300°C. After 15-30 minutes, polyester is obtained, which is then extruded, granulated and dried to obtain modified PET polyester masterbatch.

5. The flame retardant polyester fabric according to claim 4, characterized in that: The speed of the extruder is 40 r / min, the temperature of the first zone of the extruder is 260° C., the temperature of the second zone is 290° C., the temperature of the third zone is 280° C., and the temperature of the fourth zone is 280° C.

6. The flame retardant polyester fabric according to claim 1, characterized in that: The raw materials include, by weight:

7. The flame retardant polyester fabric according to claim 1, characterized in that: The raw materials include, by weight:

8. A process for preparing the flame-retardant polyester fabric according to any one of claims 1 to 7, comprising the following steps: PET polyester chips, modified PET polyester masterbatch, coupling agent, nano-silica, antioxidant and PEG-400 are uniformly mixed, and then melt-spinning is carried out on a spinning machine. The spinning temperature in the spinning machine is 220-260° C., the screw speed is 500-800 r / min, and the winding speed is 1000-1200 r / min to obtain polyester fibers; and the above polyester fibers are spun into flame-retardant polyester fabrics through a textile machine.

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