CN108359084B - High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzimide structure and preparation method thereof - Google Patents

High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzimide structure and preparation method thereof Download PDF

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CN108359084B
CN108359084B CN201810132079.1A CN201810132079A CN108359084B CN 108359084 B CN108359084 B CN 108359084B CN 201810132079 A CN201810132079 A CN 201810132079A CN 108359084 B CN108359084 B CN 108359084B
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CN108359084A (en
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王玉忠
刘博文
陈力
郭德明
刘晓锋
龙家伟
罗曦
丁晓敏
史小慧
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Abstract

The invention discloses a high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on a benzimide structure, which is formed by randomly copolymerizing structural units represented by I, II and III or structural units represented by I, II and IV, wherein the intrinsic viscosity [ eta ] of the copolyester is 0.41-1.12 dL/g, and the limiting oxygen index is 24.2-38.7%; vertical combustion grade V-2 to V-0; in a cone calorimetry test, the peak heat release rate p-HRR is reduced by 7.1-72.1% compared with that of pure PET, and the total smoke release amount is reduced by 2.0-59.2% compared with that of the pure PET. The invention also discloses a preparation method thereof, wherein the high-temperature self-crosslinking group introduced in the preparation process is a phenylimide group, and the prepared copolyester can not generate crosslinking action in the processing and polymerization processes, so that the thermoplastic processability of the polyester is kept, and meanwhile, the prepared copolyester has excellent flame retardant, smoke suppression and molten drop resistance effects due to the tackifying effect and high char formation caused by the self-crosslinking action at high temperature or during combustion.

Description

High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzimide structure and preparation method thereof
Technical Field
The invention belongs to the technical field of copolyester and preparation thereof. In particular to copolyester containing a benzimide structure and having high-temperature self-crosslinking flame retardance, smoke suppression and anti-dripping property and a preparation method thereof.
Background
Semi-aromatic polyesters, particularly polyethylene terephthalate (PET), are synthetic fibers with the largest amount and the widest range of applications due to their excellent physical and chemical properties, and are widely used in various fields of daily life. However, polyester materials are themselves extremely flammable and do not self-extinguish upon ignition, severely limiting their use in some areas where flame retardancy is desired. In addition, polyester can generate melt dripping in the combustion process, which threatens the life safety of people and possibly causes a secondary fire disaster; a large amount of dense smoke is usually accompanied in the combustion process, suffocation can be caused, escape of people in fire is seriously influenced, and life safety of people is threatened. Therefore, the polyester has important significance for melt-drip resistance and smoke suppression modification.
For the flame retardance of polyester, phosphorus flame retardants are the most effective flame retardants (Wangyou, polyester fiber flame retardant design, Sichuan scientific and technical Press, 1994), but most of phosphorus-containing copolyesters realize flame retardance modification by means of melting and dripping to remove heat (melting and dripping promoting mechanism), and the entering of phosphorus elements can cause the polyester to generate more smoke and carbon monoxide in the combustion process, so that the problem of contradiction between flame retardance and molten dripping resistance is generated.
In order to solve the contradiction, the invention patent ZL 201410279309.9 introduces zinc borate nano particles into polyester by an in-situ polymerization method to obtain a PET nano composite material, and obtains better flame retardant and anti-dripping performance. However, the introduction of inorganic particles will affect the spinnability of the polyester and limit its application range. The invention patent ZL 201010195998.7 introduces nano montmorillonite and phosphorus flame retardant 2-hydroxyethyl hypophosphorous acid into polyester by an in-situ polymerization method, and can achieve better flame-retardant and anti-dripping effects. However, the existence of the 2-hydroxyethyl hypophosphorous acid can promote the decomposition of a polyester substrate, damage the thermal stability of the polyester and limit the application of the material in some fields.
Disclosure of Invention
The invention aims to provide a high-temperature self-crosslinking copolyester containing a benzimide structure, which does not generate crosslinking action in the processing and polymerization processes, thereby retaining the thermoplastic processability of the polyester and being directly used as engineering plastics, film materials and fiber raw materials; in addition, the flame retardant has excellent flame retardant, smoke inhibiting and molten drop resisting effects due to the tackifying effect and high char forming property brought by self-crosslinking action at high temperature or during combustion.
The invention also aims to provide a preparation method of the high-temperature self-crosslinking copolyester based on the benzimide structure.
The invention is realized by the following technical scheme:
the invention provides a high-temperature self-crosslinking copolyester based on a benzimide structure, which consists of the following structural units represented by I, II and III or I, II and IV:
Figure BDA0001575204960000021
in the formula, R1Represents an arylene group, and is represented by,
Figure BDA0001575204960000022
in the formula, R2Is represented by C2～C8The alkylene group of (a) is,
Figure BDA0001575204960000023
in the formula, Z1Represents hydroxy, methyl, ethyl, methoxy or ethoxy,
Figure BDA0001575204960000031
in the formula, Z2Represents a hydroxyl group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
Wherein, the structural unit number of III is 3 ~ 30% of the structural unit number of I, the structural unit number of II: the number of structural units of [ i + iii ] is 1; the number of the IV structural units is 3-30% of that of the I structural units, and the ratio of I: the number of structural units of [ II + IV ] is 1, each structural unit or a chain segment formed by the structural units are randomly connected and combined according to carboxyl and hydroxyl functional groups, the intrinsic viscosity [ eta ] of the copolyester is 0.41-1.12 dL/g, and the limiting oxygen index is 24.2-38.7%; the vertical combustion grade is V-2 to V-0; in a cone calorimetry test, the peak heat release rate p-HRR is reduced by 7.1-72.1% compared with that of pure PET, and the total smoke release amount is reduced by 2.0-59.2% compared with that of the pure PET.
The structural unit number of III in the copolyester is preferably 5-20% of that of I, and the structural unit number of II is as follows: the number of structural units of [ i + iii ] is 1; the number of the structural units of IV is preferably 5-20% of that of the structural units of I: the number of structural units of [ II + IV ] is 1, the intrinsic viscosity [ eta ] of the copolyester is 0.41-1.12 dL/g, and the limiting oxygen index is 24.2-38.7%; the vertical combustion grade is V-2 to V-0; in a cone calorimetry test, the peak heat release rate p-HRR is reduced by 10.4-72.1% compared with that of pure PET, and the total smoke release amount is reduced by 2.0-59.2% compared with that of the pure PET.
The invention provides a preparation method of the high-temperature self-crosslinking copolyester based on the benzimide structure, which comprises the steps of mixing dibasic acid or an esterified product thereof with C2～C8The polyester monomer and the catalyst of the polyhydric alcohol are prepared by conventional proportioning, esterification is carried out by a conventional direct esterification method or an ester exchange method, and then polycondensation reaction is carried out, before esterification reaction or before polycondensation after esterification reaction, a self-crosslinking flame-retardant monomer containing a benzimide structural unit is added into a reaction system, and the adding amount is 1-30%, preferably 3-30%, and further preferably 5-20% in terms of the mole percentage of dibasic acid or esterified matter thereof in the polyester monomer.
The structural general formula of the monomer containing the benzamide structure used in the method is any one of the following:
Figure BDA0001575204960000041
Figure BDA0001575204960000051
in the formula, X1Represents a carboxyl or ester group, Y1Is represented by C2～C8Primary alcohol group of, Z1Represents hydroxy, methyl, ethyl, methoxy or ethoxy, Z2Represents a hydroxyl group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
The self-crosslinking flame-retardant monomer containing a benzamide structure used in the above method is preferably any one of the following structural formulae:
Figure BDA0001575204960000052
in the formula, X1Represents a carboxyl or ester group, Y1Is represented by C2～C8Primary alcohol group of, Z1Represents a hydroxyl group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
The ester group in the monomer containing the imide structure used in the method is a methyl ester group or an ethyl ester group after esterification of monohydric alcohol, or any one of an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a neopentyl glycol ester group, a glycerol ester group or a pentaerythritol ester group after esterification of polyhydric alcohol.
The conventional direct esterification method or ester exchange method adopted by the invention has the following process steps and conditions:
the direct esterification method comprises the following steps: adding a polyester monomer, a catalyst and a monomer containing a benzimide structure into a reaction kettle according to a ratio, pressurizing and heating to 190-220 ℃ to perform esterification reaction for 3-5 hours; after esterification, carrying out polycondensation reaction at 220-240 ℃ for 0.5-1.5 hours under low vacuum, then carrying out polycondensation at 230-250 ℃ for 1-3 hours under high vacuum, extruding a copolyester melt by using nitrogen, and carrying out water cooling to obtain the high-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester containing the benzimide structure. Wherein, the monomer containing the benzimide structure can be added into the reaction kettle before esterification or before polycondensation after esterification.
An ester exchange method: adding a polyester monomer, a catalyst and a monomer containing a benzimide structure into a reaction kettle according to a ratio, and carrying out ester exchange reaction for 3-6 hours at 180-220 ℃ under normal pressure; after the ester exchange is finished, performing polycondensation for 0.5-1.5 hours at 220-240 ℃ under low vacuum, then performing polycondensation for 1-3 hours at 230-250 ℃ under high vacuum, extruding a copolyester melt by using nitrogen, and performing water cooling to obtain the high-temperature self-crosslinking flame-retardant smoke-suppression molten-drop-resistant copolyester containing the benzimide structure. Wherein, the monomer containing the benzimide structure can be added into the reaction kettle before esterification or before polycondensation after esterification.
The catalyst selected in the method is at least one of phosphoric acid, zinc acetate, manganese acetate, cobalt acetate, antimony trioxide, ethylene glycol antimony and titanate.
The invention has the following advantages:
1. the monomer provided by the invention contains a benzimide structure which is very stable at processing and synthesis temperatures (220-260 ℃) and does not generate self-crosslinking and decomposition, so that the thermoplastic processability of polyester is maintained, the monomer containing the benzimide structure can generate rearrangement reaction at higher temperature or during combustion, chemical crosslinking can be generated among generated rearrangement units, the crosslinking reaction improves the melt viscosity of copolyester, so that the melt is inhibited from dropping, and the carbonization of the copolyester at high temperature is promoted, and the generated carbon layer has the functions of insulating heat, oxygen and organic micromolecules from volatilizing, so that the copolyester is endowed with excellent flame retardant, smoke and molten drop resistant effects.
2. The copolyester provided by the invention can be chemically crosslinked after being melted and before being thermally decomposed, so that the crosslinked copolyester can be obtained by post-curing after being processed and molded, and the crosslinked copolyester has better thermal stability, thermal oxidation stability, chemical corrosion resistance, solvent resistance and char formation property, and can be used as a novel functional polymer material.
3. The high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester provided by the invention has high crosslinking efficiency, so that the copolyester can achieve good flame-retardant anti-dripping effect only by introducing a self-crosslinking flame-retardant monomer with a lower proportion (1-30 mol%) under the condition of no additional addition of traditional flame retardant compounding, and passes the V-0 level of a vertical combustion test.
4. Due to the high-temperature self-crosslinking function of the benzimide structure in the copolyester provided by the invention, the obtained copolyester has excellent smoke suppression effect, which is not possessed by most flame-retardant polyesters.
5. The high-temperature self-crosslinking flame-retardant smoke-inhibiting anti-dripping copolyester provided by the invention is halogen-free and phosphorus-free, and only contains C, H, O and N elements, so that the copolyester belongs to an environment-friendly green high polymer material.
6. The copolyester provided by the invention has good thermoplastic processability and spinnability because no additive influencing fiber preparation is added, and can be directly used as flame retardant, smoke suppression and anti-dripping copolyester for fibers and also can be used as a macromolecular compatibilizer of an incompatible polymer blending system, so that the mechanical property of the material is improved, and the flame retardant, smoke suppression and anti-dripping modification purposes are achieved.
7. The preparation method provided by the invention is basically consistent with the conventional polyester synthesis method, so that the process is mature, the operation is simple and convenient, and the control and industrialization are easy.
Drawings
FIG. 1 is a high temperature self-crosslinking flame retardant smoke suppressant and drip suppressant copolyester P (ET-co-CPI) prepared in example 12 of this invention20And the dynamic rheology diagram of the pure PET prepared in the comparative example (complex viscosity is a direct reason for influencing the flame retardance and the anti-dripping effect of the copolyester is better as the complex viscosity is higher and the melt viscosity is higher in general). As can be seen from the figure, the copolyester P (ET-co-CPI) containing the imide structure20The complex viscosity shows the behavior of firstly decreasing and then increasing along with the increase of the temperature, and the increase of the complex viscosity indicates that the complex viscosity can generate self-crosslinking behavior at high temperature; the complex viscosity of pure PET decreases sharply with increasing temperature, indicating that it does not self-crosslink.
FIG. 2 shows high temperature self-crosslinking flame retardant smoke suppressing anti-dripping copolyester P (ET-co-DHPI) prepared in example 15 of the present invention12.5And the photograph of char formation effect after the limiting oxygen index test of pure PET prepared in comparative example, it can be seen from the figure that copolyester P (ET-co-DHPI) obtained in the present invention12.5The flame-retardant carbon forming effect is obvious, and the anti-dripping performance is very good.
FIG. 3 shows copolyester P (ET-co-HPI) prepared in example 8 of the present invention20Heat release rate profile for cone calorimetry test versus pure PET prepared in comparative example 1. It can be seen that pure PET has a higher peak heat release rate, whereas P (ET-co-HPI)20There is a significant reduction in the peak heat release rate.
FIG. 4 shows copolyester P (ET-co-HPI) prepared in example 8 of the present invention20Total smoke release profile from the pure PET cone calorimetry test prepared in comparative example 1. Can seeTo this end, pure PET has a very high total smoke release, whereas P (ET-co-HPI)20It exhibits a very low total smoke release.
Detailed Description
The following examples are given to further illustrate the invention. It should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that the skilled person in this field could make modifications and variations of the present invention without departing from the spirit or scope of the present invention.
In addition, it is worth mentioning that:
intrinsic viscosity [ eta ] of the high temperature self-crosslinking copolyesters based on a benzimide structure obtained in the examples below]phenol/1, 1,2, 2-tetrachloroethane (1:1, v: v) is used as solvent to prepare solution with concentration of 0.5g/dL, and the solution is tested at 25 ℃ by a Ubbelohde viscometer, and the limiting oxygen index of the tested copolyester is 120 multiplied by 6.5 multiplied by 3.2mm3measured on an HC-2 oxygen index meter according to ASTM D2863-97, and a vertical flame of 125 × 12.7 × 3.2mm3according to the UL-94 standard, measured with a model CZF-2 vertical burner (UL-94), and a cone calorimetry test carried out on the sample to a size of 100 × 6mm3According to ISO 5660-1, on an FTT cone calorimeter.
Example 1
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 53g (0.15mol) of N- (2-methylphenyl) -4, 5-dimethyl phenyl imide, 1.0g of zinc acetate and 0.8g of antimony trioxide are added into a reaction kettle, and nitrogen is filled to remove air in the kettle; reacting at the normal pressure at 180 ℃ for 2 hours, heating to 200 ℃ for 2 hours, then heating to 220 ℃ for 1 hour, and finishing the ester exchange reaction; then carrying out low vacuum polycondensation reaction at 220-240 ℃ for 0.5-1.5 h, then carrying out polycondensation reaction at 230-250 ℃ for 1-3 h under high vacuum (the pressure is less than 60Pa), discharging, and carrying out water cooling.
intrinsic viscosity [ eta ] of the copolyester]1.12 dL/g; the oxygen index is 24.2 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 658kW/m2Total smoke release amount is 1713m2/m2。
Example 2
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 106g (0.3mol) of N- (2-methylphenyl) -4, 5-dimethyl-phthalimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and polycondensation were carried out according to the procedure and conditions given in example 1, the product was discharged.
intrinsic viscosity [ eta ] of the copolyester]1.01 dL/g; the oxygen index is 26.3 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 531kW/m2The total smoke release amount is 1584m2/m2。
Example 3
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 159g (0.45mol) of N- (2-methylphenyl) -4, 5-dimethyl-phthalimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and polycondensation were carried out by the procedure and conditions given in example 1, the product was discharged.
intrinsic viscosity [ eta ] of the copolyester]1.05 dL/g; the oxygen index is 28.0 percent, the vertical combustion grade is V-1, and the peak heat release rate p-HRR in the cone calorimetry test is 462kW/m2The total smoke release amount is 1426m2/m2。
Example 4
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 212g (0.6mol) of N- (2-methylphenyl) -4, 5-dimethyl-phthalimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and polycondensation were carried out according to the procedure and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.95 dL/g; the oxygen index is 30.8 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 395kW/m2The total smoke release amount is 1348m2/m2。
Example 5
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 53.3g (0.15mol) of N- (2-hydroxy-5-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.75 dL/g; the oxygen index is 28.2 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 456kW/m2The total smoke release amount is 1610m2/m2。
Example 6
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 106.6g (0.3mol) of N- (2-hydroxy-5-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.62 dL/g; the oxygen index is 30.0 percent, the vertical combustion grade is V-2, and the peak value heat release rate p-HRR in the cone calorimetry test is 421kW/m2The total smoke release amount is 1529m2/m2。
Example 7
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 159.9g (0.45mol) of N- (2-hydroxy-5-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.57 dL/g; the oxygen index is 33.5 percent, the vertical combustion grade is V-1, and the peak heat release rate p-HRR in the cone calorimetry test is 387kW/m2Total smoke release amount is 1452m2/m2。
Example 8
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 213.2g (0.6mol) of N- (2-hydroxy-5-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
The characteristics of the copolyesterviscosity number [ eta ]]0.43 dL/g; the oxygen index is 37.3 percent, the vertical combustion grade is V-0, and the peak value heat release rate p-HRR in the cone calorimetry test is 276kW/m2The total smoke release amount is 1395m2/m2。
Example 9
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 31.77g (0.09mol) of N- (2-methyl-4-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.82 dL/g; the oxygen index is 26.0 percent, the vertical combustion grade is V-2, and the peak value heat release rate p-HRR in the cone calorimetry test is 682kW/m2Total smoke release amount is 1467m2/m2。
Example 10
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 106.0g (0.3mol) of N- (2-methyl-4-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.77 dL/g; the oxygen index is 27.3 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 548kW/m2The total smoke release amount is 1284m2/m2。
Example 11
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 212.0g (0.6mol) of N- (2-methyl-4-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.79 dL/g; the oxygen index is 28.5 percent, the vertical combustion grade is V-1, and the peak heat release rate p-HRR in the cone calorimetry test is 407kW/m2Total smoke release amount is 1037m2/m2。
Example 12
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 317.7g (0.9mol) of N- (2-methyl-4-carbomethoxyphenyl) -4-carbomethoxybenzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester interchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.74 dL/g; the oxygen index is 29.8 percent, the vertical combustion grade is V-1, and the peak heat release rate p-HRR in the cone calorimetry test is 312kW/m2Total smoke release volume of 913m2/m2。
Example 13
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 76.2g (0.15mol) of N, N-bis (2-ethyl-5-carbomethoxyphenyl) -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out according to the procedure and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.44 dL/g; the oxygen index is 30.1 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 482kW/m2The total smoke release amount is 1417m2/m2。
Example 14
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 152.4g (0.3mol) of N, N-bis (2-ethyl-5-carbomethoxyphenyl) -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out according to the procedure and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.66 dL/g; the oxygen index is 33.5 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 359kW/m2The total smoke release amount is 1361m2/m2。
Example 15
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 190.5g (0.375mol) of N, N-bis (2-ethyl-5-carbomethoxyphenyl) -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out according to the procedure and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.42 dL/g; the oxygen index is 36.1 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 267kW/m2The total smoke release amount is 981m2/m2。
Example 16
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 85.8g (0.15mol) of N, N-bis (2-ethoxy-4-carbomethoxyphenyl) -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out by the procedure and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.55 dL/g; the oxygen index is 29.8 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 452kW/m2Total smoke release amount of 1377m2/m2。
Example 17
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 171.6g (0.3mol) of N, N-bis (2-ethoxy-4-carbomethoxyphenyl) -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out according to the procedure and conditions given in example 1, the materials were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.47 dL/g; the oxygen index is 32.5 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 331kW/m2The total smoke release amount is 1054m2/m2。
Example 18
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 214.5g (0.375mol) of N, N-bis (2-ethoxy-4-carbomethoxyphenyl) -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out according to the procedure and conditions given in example 1, the materials were discharged.
Intrinsic viscosity of the copolyester[η]0.43 dL/g; the oxygen index is 35.4 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 207kW/m2The total smoke release amount is 795m2/m2。
Example 19
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 53.9g (0.15mol) of N- [ 2-hydroxy-5- (2-hydroxyethoxy) phenyl ] -4- (2-hydroxyethoxy) benzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedure and conditions given in example 1, they were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.77 dL/g; the oxygen index is 28.1 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 433kW/m2The total smoke release amount is 1571m2/m2。
Example 20
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 215.6g (0.6mol) of N- [ 2-hydroxy-5- (2-hydroxyethoxy) phenyl ] -4- (2-hydroxyethoxy) benzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedure and conditions given in example 1, they were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.48 dL/g; the oxygen index is 36.2 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 291kW/m2The total smoke release amount is 1228m2/m2。
Example 21
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 214.2g (0.6mol) of N- [ 2-methyl-4- (2-hydroxyethoxy) phenyl ] -4- (2-hydroxyethoxy) benzimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedure and conditions given in example 1, they were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.92 dL/g; the oxygen index is 32.8 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 311kW/m2Total smoke release amount is 1462m2/m2。
Example 22
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 204g (0.375mol) of N, N-bis [ 2-ethyl-5- (2-hydroxyethoxy) ] -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out by the steps and conditions given in example 1, they were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.43 dL/g; the oxygen index is 37.5 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 297kW/m2The total smoke release amount is 986m2/m2。
Example 23
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 216g (0.375mol) of N, N-bis [ 2-ethoxy-4- (2-hydroxyethoxy) ] -pyromellitic diimide, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and the polycondensation were carried out by the steps and conditions given in example 1, they were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.44 dL/g; the oxygen index is 36.7 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 282kW/m2The total smoke release amount is 998m2/m2。
Example 24
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 186g (0.3mol) of N, N-bis [ 2-hydroxy-4-carbomethoxyphenyl ] -4,4 ', 5, 5' -diphenylimidobenzophenone, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and polycondensation were carried out according to the procedure and conditions given in example 1, they were discharged.
intrinsic viscosity [ eta ] of the copolyester]0.41 dL/g; the oxygen index is 38.7 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 205kW/m2The total smoke release amount is 714m2/m2。
Example 25
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 177.6g (0.3mol) of 3,3 '-dihydroxy-4, 4' -bis [ 4-carbomethoxyphthalimido ] benzidine, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after the ester exchange reaction and polycondensation were carried out according to the procedures and conditions given in example 1, the product was discharged.
intrinsic viscosity [ eta ] of the copolyester]0.42 dL/g; the oxygen index is 37.7 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 211kW/m2Total smoke release amount is 735m2/m2。
Comparative example 1
582g (3mol) of dimethyl terephthalate, 310g (5mol) of ethylene glycol, 1.0g of zinc acetate and 0.8g of antimony trioxide were charged into a reaction vessel, and after esterification and polycondensation were carried out according to the procedure and conditions given in example 1, the product was discharged.
the intrinsic viscosity [ eta ] of the polyester]0.72 dL/g; the oxygen index is 22.0 percent, the vertical combustion grade is stepless, and the peak value heat release rate p-HRR in the cone calorimetry test is 734kW/m2Total smoke release amount is 1748m2/m2。

Claims (10)

1. A high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on a benzimide structure is characterized in that: the copolyester is composed of the following structural units represented by I, II and III or I, II and IV:
Figure FDA0002522177760000011
in the formula, R1Represents an arylene group;
Figure FDA0002522177760000012
in the formula, R2Is represented by C2～C8An alkylene group of (a);
Figure FDA0002522177760000013
in the formula, Z1Represents hydroxy, methyl, ethyl, methoxy or ethoxy;
Figure FDA0002522177760000021
in the formula, Z2Represents a hydroxyl group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
2. The high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 1, wherein: the structural unit number of III is 3-30% of that of I, and the structural unit number of II: the number of structural units of [ i + iii ] is 1; the number of the IV structural units is 3-30% of that of the I structural units, and the ratio of I: the number of structural units of [ ii + iv ] is 1; each structural unit or the chain segment formed by the structural units is combined according to the random connection of carboxyl and hydroxyl functional groups.
3. The high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 2, wherein: the intrinsic viscosity [ eta ] of the copolyester is 0.41-1.12 dL/g, and the limiting oxygen index is 24.2-38.7%; the vertical combustion grade is V-2 to V-0; in a cone calorimetry test, the peak heat release rate p-HRR is reduced by 7.1-72.1% compared with that of pure PET, and the total smoke release amount is reduced by 2.0-59.2% compared with that of the pure PET.
4. The high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure according to claim 2, characterized in that: the structural unit number of III in the copolyester is 5-20% of that of I, and the structural unit number of II: the number of structural units of [ i + iii ] is 1; the number of the structural units of IV is 5-20% of that of the structural units of I, and I: the number of structural units of [ ii + iv ] is 1.
5. A process for preparing the high-temp self-crosslinking flame-retarding smoke-suppressing molten-drop-resisting copolyester based on the benzimide structure as claimed in claim 1-4, which is prepared from dibasic acid or its esterified product and C2～C8The polyester monomer and the catalyst of the polyhydric alcohol are prepared by conventional proportioning, esterification is carried out by a conventional direct esterification method or ester exchange method, and then polycondensation reaction is carried out, and the polyester is characterized in that: before esterification or before polycondensation after esterification, a self-crosslinking flame-retardant monomer containing a benzimide structural unit is added into a reaction system.
6. The preparation method of the high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 5, which is characterized in that: before esterification or before polycondensation after esterification, the self-crosslinking flame-retardant monomer containing the phthalimide structural unit added into the reaction system accounts for 3-30% of the mole percentage of the dibasic acid or the esterified product thereof in the copolyester monomer.
7. The preparation method of the high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 6, which is characterized in that: before esterification or before polycondensation after esterification, the self-crosslinking flame-retardant monomer containing the phthalimide structural unit added into the reaction system accounts for 5-20% of the mole percentage of the dibasic acid or the esterified product thereof in the copolyester monomer.
8. The preparation method of the high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 5, which is characterized in that: the structural general formula of the self-crosslinking flame-retardant monomer containing the benzimide structural unit is any one of the following formulas:
Figure FDA0002522177760000031
Figure FDA0002522177760000041
in the formula, X1Represents a carboxyl or ester group, Y1Is represented by C2～C8Primary alcohol group of, Z1Represents a hydroxyl group, a methyl group, or a ethyl groupRadical, methoxy or ethoxy, Z2Represents a hydroxyl group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
9. The preparation method of the high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 8, which is characterized in that: the structural general formula of the self-crosslinking flame-retardant monomer containing the benzimide structural unit is any one of the following formulas:
Figure FDA0002522177760000042
Figure FDA0002522177760000051
in the formula, X1Represents a carboxyl or ester group, Y1Is represented by C2～C8Primary alcohol group of, Z1Represents hydroxy, methyl, ethyl, methoxy or ethoxy, Z2Represents a hydroxyl group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
10. The preparation method of the high-temperature self-crosslinking flame-retardant smoke-suppressing anti-dripping copolyester based on the benzimide structure as claimed in claim 8 or 9, which is characterized in that: the ester group in the self-crosslinking flame-retardant monomer containing the imide structural unit is a methyl ester group or an ethyl ester group after monohydric alcohol esterification, or is any one of an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a neopentyl glycol ester group, a glycerol ester group or a pentaerythritol ester group after polyhydric alcohol esterification.
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