Flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking and preparation method and application thereof
阅读说明：本技术 基于高温自交联的阻燃抗熔滴共聚酯及其制备方法和应用 (Flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking and preparation method and application thereof ) 是由 王玉忠 陈琳 倪延朋 付腾 吴万寿 刘博文 赵海波 汪秀丽 于 2020-06-19 设计创作，主要内容包括：本发明公开的基于高温自交联的阻燃抗熔滴共聚酯是由Ⅰ、Ⅱ、Ⅲ、Ⅳ表示的结构单元所组成,该共聚酯的特性黏数[η]为0.20～3.50dL/g,极限氧指数为23.0～60.0％,垂直燃烧等级为V-2～V-0级。本发明还公开了其制备方法和应用。由于本发明引入的高温自交联基团和离子基团在提高共聚酯燃烧时熔体黏度和熔体强度的同时,还有效增强了共聚酯的成炭能力,因此本发明共聚酯表现出优异的阻燃性和抗熔滴性。本发明共聚酯的制备工艺成熟且操作简便,易于控制和工业化生产。(The invention discloses a flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking, which consists of structural units represented by I, II, III and IV, wherein the intrinsic viscosity [ eta ] of the copolyester is 0.20-3.50 dL/g, the limiting oxygen index is 23.0-60.0%, and the vertical combustion grade is V-2-V-0. The invention also discloses a preparation method and application thereof. The high-temperature self-crosslinking group and the ionic group introduced by the invention effectively enhance the char forming capability of the copolyester while improving the melt viscosity and the melt strength of the copolyester during combustion, so the copolyester of the invention has excellent flame retardance and anti-dripping property. The preparation process of the copolyester is mature, simple and convenient to operate, and easy to control and industrially produce.)
1. The flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking is characterized by consisting of the following structural units I, II, III and IV:
in the formula, R1Represents an arylene group;
in the formula, R2Represents an alkylene group;
in the formula, R3、R4Is a carbonyl group, an O atom ora is an integer of 2 to 12, R3、R4The same or different; x1、X2Is any one of H atom, hydroxyl, methyl, ethyl, cyano, methoxy, phenylethynyl or phenyl, and X is1、X2The same or different; y is1Is an O atom or an S atom;
in the formula, R5、R6Is a carbonyl group, an O atom ora is an integer of 2 to 12, R5、R6The same or different; r7Is C1～C12Alkyl, aryl or benzyl of R8Is C1～C8Alkylene or arylene of (a); y is2Is an O atom or an S atom; y is3Is any one of an O atom, an S atom, a secondary amino group, a aminomethyl group or an aminoethyl group; m is any one of metal atoms Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs or Zn, and n is an integer of 1-3;
the number of structural units of [ III ] is 1 to 99% of the number of structural units of [ I ], and the number of structural units of [ IV ] is 0 to 99% of the number of structural units of [ I ].
2. The high temperature self-crosslinking based flame retardant anti-drip copolyester of claim 1, wherein: the intrinsic viscosity [ eta ] of the copolyester is 0.20-3.50 dL/g, the limiting oxygen index is 23.0-60.0%, and the vertical combustion grade is V-2-V-0 grade.
3. The high temperature self-crosslinking based flame retardant anti-drip copolyester of claim 1, wherein: the number of structural units of [ III ] in the copolyester is 2-60% of the number of structural units of [ I ], the number of structural units of [ IV ] is 0.1-60% of the number of structural units of [ I ], and the intrinsic viscosity [ eta ] of the copolyester is 0.30-3.20 dL/g; the limiting oxygen index is 24.0-55.0%; the vertical burning grade is V-2 to V-0 grade.
4. The method for preparing the flame-retardant anti-dripping copolyester based on the high-temperature self-crosslinking is characterized in that 1-99% of high-temperature self-crosslinking flame-retardant monomer and 0-99% of ionic monomer calculated by the mole number of the dibasic acid or dibasic acid ester in the polyester monomer are added into a reaction system before esterification or after polycondensation after the esterification reaction.
5. The preparation method of the flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking according to claim 4, wherein 2-60% of high-temperature self-crosslinking flame-retardant monomer and 0.1-60% of ionic monomer are added according to the mole number of the dibasic acid or dibasic acid ester compound in the polyester monomer.
6. The preparation method of high temperature self-crosslinking based flame retardant anti-dripping copolyester according to claim 4 or 5, wherein the high temperature self-crosslinking flame retardant monomer used in the method is at least one of the following structural formulas:
in the formula, Z1、Z2Is carboxyl, ester, hydroxyl ora is an integer of 2 to 12, Z1、Z2The same or different; x1、X2Is any one of H atom, hydroxyl, methyl, ethyl, cyano, methoxy, phenylethynyl or phenyl, and X is1、X2The same or different; y is1Is an O atom or an S atom.
7. The preparation method of the flame retardant anti-dripping copolyester based on high temperature self-crosslinking according to claim 4 or 5, characterized in that the ionic monomer used in the method is at least one of the following structural formulas:
in the formula, Z1、Z2Is carboxyl, ester, hydroxyl ora is an integer of 2 to 12, Z1、Z2The same or different; z3Is C2～C8An alkylene group of (a); r7Is C1～C12Alkyl, aryl or benzyl of R8Is C1～C8Alkylene or arylene of (a); y is2Is an O atom or an S atom; y is3Is any one of an O atom, an S atom, a secondary amino group, a aminomethyl group or an aminoethyl group; m is any one of metal atoms Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs or Zn, and n is an integer of 1-3.
8. The method for preparing high temperature self-crosslinking based flame retardant anti-dripping copolyester according to claim 6, wherein the ester group in the high temperature self-crosslinking flame retardant monomer used in the method is methyl ester group or ethyl ester group after esterification of monohydric alcohol, or any one of ethylene glycol ester group, propylene glycol ester group, butylene glycol ester group, pentylene glycol ester group, glycerol ester group or pentaerythritol ester group after esterification of polyhydric alcohol.
9. The method for preparing high temperature self-crosslinking based flame retardant anti-dripping copolyester according to claim 7, wherein the ester group in the ionic monomer used in the method is any one of methyl ester group or ethyl ester group after esterification of monohydric alcohol, or any one of ethylene ester group, propylene ester group, butanediol ester group, pentanediol ester group, glycerol ester group or pentaerythritol ester group after esterification of polyhydric alcohol.
10. The application of the flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking according to claim 1 is independently applied to the fields of fibers, non-woven fabrics, engineering plastics, film materials, container materials, self-repairing materials, shape memory materials or 3D printing materials, or is used as a functional additive for modifying high polymer materials.
Technical Field
The invention belongs to the technical field of flame-retardant anti-dripping copolyester and preparation and application thereof, and particularly relates to copolyester with high-temperature self-crosslinking property, flame retardance and anti-dripping property, and a preparation method and application thereof. Under the combined action of the high-temperature self-crosslinking flame-retardant monomer and the ionic monomer, the copolyester not only improves the melt viscosity and the melt strength, but also greatly enhances the char forming capability during combustion through the chemical crosslinking and physical crosslinking action at high temperature, thereby showing excellent flame-retardant and anti-dripping performance.
Background
Semi-aromatic polyesters (polyesters for short), such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), are used as synthetic fibers, films, bottling materials, engineering plastics, etc. because of their excellent thermal stability, mechanical properties, shape retention, corrosion resistance, low gas permeability, etc. However, polyester is a very flammable polymer, which not only releases a large amount of heat and smoke upon combustion, but is also associated with severe flaming dripping behavior. Once a fire disaster occurs, the heat released by polyester combustion can accelerate the propagation of flame, molten drops can cause scalding and secondary fire disasters, dense smoke not only brings inconvenience to rescue and escape, but also can easily cause people to suffocate, and the application of the polyester in the field with flame-retardant requirements, such as public transport, protective clothing, automotive interior, hotel and market decorative fabrics, electronic devices and the like, is greatly limited.
Currently, the most common way of flame retarding polyesters is melt blending or copolymerization with halogen-based flame retardants or phosphorus-based flame retardants. Wherein, the halogen flame retardant can generate poisonous corrosive gases such as hydrogen halide, dioxin and the like during combustion, which are harmful to personal safety and are gradually eliminated by the market. Although phosphorus flame retardants are efficient flame retardants for polyesters, most commercially available phosphorus flame retardants achieve a flame retardant effect by promoting a mode of "heat removal by melt dripping", which brings a difficult-to-reconcile contradiction between flame retardancy and melt dripping resistance of polyesters, and many phosphorus flame retardants also deteriorate smoke emission behavior of polyesters. Therefore, how to simultaneously realize the flame retardancy and the anti-dripping property of the polyester is a problem to be solved which is puzzling the industry and academia at present.
Some of the currently disclosed research results are mainly that an anti-dripping agent is added into polyester, such as polytetrafluoroethylene and derivatives thereof, glass fiber, silicon dioxide and the like, and although the additives can improve certain flame retardant performance and anti-dripping effect of the polyester, the additives can greatly destroy the mechanical property and spinnability of the polyester, and cannot solve the problem of serious smoke release during combustion of the polyester.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide flame-retardant anti-dripping copolyester capable of generating high-temperature self-crosslinking.
The invention also aims to provide a method for preparing the flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking.
The invention also aims to provide application of the flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking.
The invention provides flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking, which consists of the following structural units I, II, III and IV:
in the formula, R1Represents an arylene group;
in the formula, R2Represents an alkylene group;
in the formula, R3、R4Is a carbonyl group, an O atom ora is an integer of 2 to 12, R3、R4The same or different; x1、X2Is any one of H atom, hydroxyl, methyl, ethyl, cyano, methoxy, phenylethynyl or phenyl, and X is1、X2The same or different; y is1Is an O atom or an S atom;
in the formula, R5、R6Is a carbonyl group, an O atom ora is an integer of 2 to 12, R5、R6The same or different; r7Is C1～C12Alkyl, aryl or benzyl of R8Is C1～C8Alkylene or arylene of (a); y is2Is an O atom or an S atom; y is3Is any one of an O atom, an S atom, a secondary amino group, a aminomethyl group or an aminoethyl group; m is any one of metal atoms Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs or Zn, and n is an integer of 1-3;
the number of structural units of [ III ] is 1 to 99% of the number of structural units of [ I ], and the number of structural units of [ IV ] is 0 to 99% of the number of structural units of [ I ].
The intrinsic viscosity [ eta ] of the copolyester is 0.20-3.50 dL/g, the limiting oxygen index is 23.0-60.0%, and the vertical combustion grade is V-2-V-0 grade.
When the number of structural units of the copolyester [ III ] is 2-60% of the number of structural units of [ I ], the number of structural units of [ IV ] is 0.1-60% of the number of structural units of [ I ], and the intrinsic viscosity [ eta ] of the copolyester is 0.30-3.20 dL/g; the limiting oxygen index is 24.0-55.0%; the vertical burning grade is V-2 to V-0 grade.
The invention provides a preparation method of flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking, which is prepared by carrying out esterification on a dibasic acid or dibasic acid ester, a polyester monomer of dihydric alcohol and a catalyst according to a conventional proportion by adopting a conventional direct esterification method or an ester exchange method and then carrying out polycondensation, and is characterized in that 1-99% of high-temperature self-crosslinking flame-retardant monomer and 0-99% of ionic monomer are added into a reaction system before esterification or before polycondensation after esterification, wherein the molar number of the dibasic acid or dibasic acid ester in the polyester monomer is 1-99%; preferably 2-60% of high-temperature self-crosslinking flame-retardant monomer and 0.1-60% of ionic monomer.
The high-temperature self-crosslinking flame-retardant monomer used in the preparation method is at least one of the following structural general formulas:
in the formula, Z1、Z2Is carboxyl, ester, hydroxyl ora is an integer of 2 to 12, Z1、Z2The same or different; x1、X2Is H atom, hydroxyl, methyl, ethyl, cyano, methoxy, phenylacetyleneAny one of a group or a phenyl group, X1、X2The same or different; y is1Is an O atom or an S atom.
The ionic monomer used in the preparation method is at least one of the following structural general formulas:
in the formula, Z1、Z2Is carboxyl, ester, hydroxyl ora is an integer of 2 to 12, Z1、Z2The same or different; z3Is C2～C8An alkylene group of (a); r7Is C1～C12Alkyl, aryl or benzyl of R8Is C1～ C8Alkylene or arylene of (a); y is2Is an O atom or an S atom; y is3Is any one of an O atom, an S atom, a secondary amino group, a aminomethyl group or an aminoethyl group; m is any one of metal atoms Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs or Zn, and n is an integer of 1-3.
The high temperature self-crosslinking flame retardant monomers used in the above method can be referred to Journal of Materials Chemistry,2012, 22, 19849-19857; polymer Chemistry,2016,7, 2698-; prepared by a method disclosed in Chemical Engineering Journal, 2019,374,694-705 and the like; the ionic monomers used in the above method can be found in Polymer Chemistry,2014,5, 1982-1991; polymer,2015,60,50-61, etc.
The ester group in the high-temperature self-crosslinking flame-retardant monomer and the ionic monomer used in the method is a methyl ester group or an ethyl ester group after monohydric alcohol esterification, or any one of an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a pentanediol ester group, a glycerol ester group or a pentaerythritol ester group after polyhydric alcohol esterification.
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 dibasic acid, dihydric alcohol, a catalyst, a high-temperature self-crosslinking flame-retardant monomer and an ionic monomer into a reaction kettle according to a ratio, pressurizing and heating to 190-240 ℃ to perform esterification reaction for 2-5 hours; after esterification, performing polycondensation reaction at 240-250 ℃ for 0.5-2 hours under low vacuum, then performing polycondensation at 250-280 ℃ for 1-4 hours under high vacuum, extruding a copolyester melt by using inert gas (preferably nitrogen), and cooling the melt by water to obtain the target copolyester. Wherein, the high-temperature self-crosslinking flame-retardant monomer and the ionic monomer can be added into the reaction kettle before esterification or before polycondensation after esterification.
An ester exchange method: adding an esterified dibasic acid, dihydric alcohol, a catalyst, a high-temperature self-crosslinking flame-retardant monomer and an ionic monomer 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 0.5-2 hours at 240-250 ℃ under low vacuum, then performing polycondensation for 1-4 hours at 250-280 ℃ under high vacuum, extruding a copolyester melt by using inert gas (preferably adopting nitrogen), and performing water cooling on the melt to obtain the target copolyester. Wherein, the high-temperature self-crosslinking flame-retardant monomer and the ionic monomer can be selectively added into the reaction kettle before the ester exchange reaction or before the polycondensation after the ester exchange reaction.
The catalyst used in the preparation method is at least one of germanium catalyst, titanium catalyst, antimony catalyst, aluminum catalyst, tin catalyst and the like, such as germanium dioxide, antimony acetate, antimony trioxide, ethylene glycol antimony, titanium oxide, titanium potassium oxalate, potassium hexafluorotitanate, titanate, titanium alkoxide, titanium complex, tin oxide, aluminum hydroxide, aluminum acetate, silicon dioxide, zinc acetate, manganese acetate or magnesium acetate and the like.
The flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking can be independently applied to the fields of fibers, non-woven fabrics, engineering plastics, film materials, container materials, self-repairing materials, shape memory materials or 3D printing materials, and can also be used as a functional additive for modifying high polymer materials.
Compared with the prior art, the invention has the following advantages:
1. because the structural units of the flame-retardant anti-dripping copolyester provided by the invention contain structures capable of generating high-temperature self-crosslinking reaction, the self-crosslinking structures are stable and can not be crosslinked in the polymerization process and processing process, but can be rapidly crosslinked at higher temperature or in combustion (figure 1). On one hand, the occurrence of the cross-linking reaction greatly improves the melt viscosity/strength when the polyester is burnt, thereby inhibiting the generation of molten drops; on the other hand, an aromatic condensed ring structure formed by crosslinking can be further evolved to form a stable and compact carbon layer, so that the effects of insulating heat and oxygen and inhibiting volatilization of combustible substances are achieved, and the copolyester is endowed with excellent flame retardant property.
2. The flame-retardant anti-dripping copolyester provided by the invention contains a flame-retardant monomer which has a high-temperature self-crosslinking effect and can effectively improve the melt viscosity and melt strength of the polyester during combustion, so that the generation of dripping is inhibited, and also contains an ionic monomer which can improve the melt viscosity of the polyester through the physical crosslinking generated by an ionic aggregate, so that the flame-retardant copolyester can play a synergistic flame-retardant effect during combustion, and compared with the copolyester only containing a self-crosslinking functional group or an ionic group, the copolyester has more excellent flame-retardant and anti-dripping performances.
3. The flame-retardant anti-dripping copolyester provided by the invention also has good char forming capability, the copolyester can form a stable and compact char layer during combustion, and the char layer can effectively inhibit volatilization of organic smoke, so that the copolyester shows a good smoke suppression effect, which is not possessed by most flame-retardant polyesters.
4. The flame-retardant anti-dripping copolyester provided by the invention contains ionic groups in the structure, so that the copolyester has good antistatic performance and affinity with cationic dyes.
5. The flame-retardant anti-dripping copolyester provided by the invention contains conjugated aromatic groups in the structure, pi-pi stacking interaction can be formed among the conjugated aromatic groups, and pi-pi stacking is used as a dynamic cross-linking point, so that the copolyester can be endowed with certain self-repairing and shape memory properties, the mechanical strength of the copolyester and the adhesion force between melts can be improved, and the copolyester can be used as an intelligent high polymer material and a 3D printing material.
6. The flame-retardant anti-dripping copolyester provided by the invention has good spinnability because no additive influencing fiber preparation is added, and can be directly used as copolyester for fibers and a macromolecular compatibilizer of an incompatible polymer blending system, so that the flame-retardant anti-dripping copolyester can improve the mechanical property of materials and can endow the materials with flame-retardant and anti-dripping properties.
7. The flame-retardant anti-dripping copolyester provided by the invention does not contain halogen elements, so that the flame-retardant anti-dripping copolyester belongs to an environment-friendly green high polymer material.
8. The preparation method of the copolyester provided by the invention is basically consistent with the conventional polyester synthesis method, so that the method has the advantages of mature process, simple and convenient operation, and easy control and industrial production.
Drawings
FIG. 1 is a temperature swing dynamic rheology plot of copolyester prepared in example 4 of the present invention and neat PET prepared in comparative example 1. The higher the complex viscosity of the thermoplastic polymer at high temperature means that the higher the melt viscosity and melt strength of the thermoplastic polymer during combustion, the stronger the corresponding anti-dripping capability. The complex viscosity of pure PET gradually decreases with the increase of temperature, and the rheological behavior of shear thinning is shown; the complex viscosity of the copolyester shows a U-shaped change curve which is increased after being reduced along with the increase of the temperature, which indicates that the copolyester has self-crosslinking reaction at high temperature. The self-crosslinking reaction can effectively improve the melt viscosity and strength when the copolyester is combusted, and plays a role in resisting molten drops.
FIG. 2 is a graph showing the thermal weight loss curves of the copolyester containing phenylacetylene self-crosslinking functional groups and sodium phosphinate ionic groups prepared in example 4 according to the present invention, pure PET prepared in comparative example 1, the copolyester containing phenylacetylene self-crosslinking functional groups only prepared in comparative example 2, and the copolyester containing sodium phosphinate ionic groups only prepared in comparative example 3. As can be seen from the figure, the copolyester of example 4 of the present invention not only maintained good thermal stability in nitrogen atmosphere, but also had a much higher residual carbon content (26.6 wt%) than pure PET (11.8 wt%), comparative example 2(14.9 wt%) and comparative example 3(17.5 wt%) at high temperature (700 deg.C). Although the carbon residue amounts of example 4, comparative example 2 and comparative example 3 were increased by 14.8 wt%, 3.1 wt% and 5.7 wt%, respectively, compared to pure PET, the carbon residue amount increased in example 4 was greater than the sum of the increased amounts of comparative example 2 and comparative example 3, indicating that the char forming ability of the copolyester prepared according to the present invention was further improved due to the synergistic flame retarding effect of the high temperature self-crosslinking functional group and the ionic group.
FIG. 3 is a digital photograph of the copolyester prepared in example 4 of the present invention and pure PET prepared in comparative example 1 in a vertical burning test. From the photographs it can be seen that the PET does not self-extinguish after ignition and is associated with a large number of droplets, the test grade being stepless; the copolyester prepared by the invention can be quickly self-extinguished within 10s after being ignited, no molten drop is generated, and the test grade is V-0 grade. While comparative example 2 only passed the V-2 stage, comparative example 3 was stepless and there was still droplet generation in the test. The copolyester prepared by the method has more excellent flame-retardant and anti-dripping performances compared with the copolyester containing only high-temperature self-crosslinking functional groups or only ionic groups.
FIG. 4 is a graph of heat release rate of cone calorimetry tests of copolyesters prepared in example 4 of the present invention with pure PET prepared in comparative examples 1-3, copolyesters containing only high temperature self-crosslinking functional groups or only ionic groups. The peak heat release rate (p-HRR) is an important parameter for judging the flame retardant property of the material, and the lower the value, the better the flame retardant property of the material. As can be seen from the comparison of the curves in the graph, the p-HRR of example 4 of the present invention was 298kW/m2Compared with pure PET, the reduction is 59.5 percent, and is also far lower than 471kW/m of comparative example 22And 392kW/m for comparative example 32p-HRR of (1). The copolyester prepared by the invention shows more excellent flame retardant property.
FIG. 5 is a graph of total smoke emission (TSR) measured by cone calorimetry of the copolyester of example 4 of the present invention and pure PET prepared in comparative examples 1-3, a copolyester containing only high temperature self-crosslinking functional groups or only ionic groups. From a comparison of the curves in this figure, it can be seen that the TSR of the copolyester of the present invention is 728m2/m2Not only reduced by 58.5% compared to pure PET, but also much lower than 1939m of comparative example 22/m2And 1077m of comparative example 32/m2To show out moreExcellent smoke suppression performance is added.
Detailed Description
Examples are given below and the present invention will be described in further detail, but the embodiments of the present invention are not limited thereto. 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 the art would be able to make modifications and variations of the present invention without departing from the spirit and scope of the present invention.
In addition, it is worth noting that the intrinsic viscosity [. eta. ] of the flame retardant anti-dripping copolyester obtained in the following examples]Phenol/1, 1,2, 2-tetrachloroethane (1:1, v: v) is used as a solvent to prepare a solution with the concentration of 5g/L, and the solution is tested by an Ubbelohde viscometer at 25 ℃; the limiting oxygen index of the copolyester is 120 multiplied by 6.5 multiplied by 3.2mm3According to ASTM D2863-97, on an HC-2 type oxygen index apparatus; the vertical burning test is to make the copolyester 125X 12.7X 3.2mm3According to the UL-94 standard, measured with a model CZF-2 vertical burner (UL-94); the cone calorimetric test is to prepare the copolyester into 100X 3mm3According to ISO 5660-1, at 50kW/m in an FTT cone calorimeter2The power of (c) was measured.
Example 1
Adding 498.0g of terephthalic acid, 220.0g of ethylene glycol, 7.98g of 4- (phenylethynyl) phthalic acid, 36.6 g of 2,8- (2-hydroxyethoxy) carbonyl potassium phenanthrene oxaphosphinite and 0.3g of antimony trioxide into a reaction kettle, filling nitrogen to remove air in the kettle, pressurizing to 0.1MPa, heating to 240 ℃ within 2 hours to start esterification, controlling the pressure in the kettle to be 0.3-0.4 MPa, maintaining for 2-4 hours, then, reducing the pressure to normal pressure, and finishing the esterification; and then carrying out low-vacuum polycondensation reaction at 240 ℃ for 0.5-2 hours, heating to 250-270 ℃, carrying out high-vacuum (pressure is less than 80Pa) polycondensation reaction for 1-4 hours, discharging, and carrying out water cooling.
Intrinsic viscosity [ eta ] of the copolyester]0.85 dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; peak heat release rate in cone calorimetry testThe p-HRR is 320kW/m2The total smoke release amount TSR is 683 m2/m2。
Example 2
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 159.6g of 4- (phenylethynyl) phthalic acid, 25.2g of sodium (3- (2-hydroxyethoxy) -3-oxopropyl) (phenyl) phosphinate, 0.2g of manganese acetate and 0.25g of germanium dioxide are added to a reaction kettle, and nitrogen is filled to remove air in the kettle; reacting for 2-6 hours at the normal pressure of 180-220 ℃, and finishing the ester exchange reaction; then carrying out low vacuum polycondensation reaction at 240-250 ℃ for 0.5-2 h, then carrying out polycondensation reaction at 250-270 ℃ for 1-4 h under high vacuum (the pressure is less than 80Pa), discharging, and carrying out water cooling.
Intrinsic viscosity [ eta ] of the copolyester]0.62 dL/g; the limiting oxygen index is 30.5%; the vertical combustion grade is V-2 grade; the peak heat release rate p-HRR in the cone calorimetry test is 312kW/m2The total smoke release amount TSR is 801 m2/m2。
Example 3
388.0g of dimethyl terephthalate, 194g of dimethyl isophthalate, 400.0g of ethylene glycol, 79.8g of 4- (phenylethynyl) phthalic acid, 52.5g of potassium (3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 40.2g of sodium 5-sulfoisophthalate and 0.28g of isopropyl titanate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedure and conditions of example 2, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.90 dL/g; the limiting oxygen index is 31.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 222kW/m2TSR is 640m2/m2。
Example 4
498.0g of terephthalic acid, 220.0g of ethylene glycol, 159.6g of 4- (phenylethynyl) phthalic acid, 38.7g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinic acid, 0.2g of zinc acetate and 0.3g of antimony trioxide were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.88 dL/g; the limiting oxygen index is 31.0%; vertical combustionThe burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 298kW/m2TSR is 728m2/m2。
Example 5
415.0g of terephthalic acid, 83.0g of phthalic acid, 220.0g of ethylene glycol, 176.4g of dimethyl 5- (phenylethynyl) -1, 3-isophthalate, 47.5g of dimethyl 3, 5-bis (6- (methoxycarbonyl) -1H-benzimidazol-2-yl) benzenesulfonate, 65.9g of dimethyl 5-benzimidophenylacetylene-1, 3-isophthalate, 9.4g of dimethyl 5-benzamido-1, 3-isophthalate, 0.1g of antimony acetate and 0.2g of titanium glycol were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedures and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.70 dL/g; the limiting oxygen index is 32.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 238kW/m2TSR is 709m2/m2。
Example 6
498.0g of terephthalic acid, 220.0g of ethylene glycol, 88.2g of dimethyl 5- (phenylethynyl) -1, 3-isophthalate, 1.8g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthenephosphinate and 0.25g of titanium tartrate were charged in a reaction vessel, and esterification and polycondensation were carried out under the conditions and procedures as in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]1.27 dL/g; the limiting oxygen index is 30.0%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 434kW/m2TSR is 1473m2/m2。
Example 7
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 65.9g of 5-benzimidhenylacetylene-1, 3-isophthalic acid dimethyl ester, 38.7g of 2,8- (2-hydroxyethoxy) carbonyl phenanthrene oxa-phosphinic acid sodium salt and 0.3g of tetrabutyl titanate are added into a reaction kettle, esterification and polycondensation are carried out according to the steps and conditions given in example 2, and then discharging is carried out.
Intrinsic viscosity [ eta ] of the copolyester]0.80 dL/g; the limiting oxygen index is 29.4%; the vertical combustion grade is V-2 grade; cone calorimetryThe p-HRR in the test is 266kW/m2TSR is 770m2/m2。
Example 8
498.0g of terephthalic acid, 220.0g of ethylene glycol, 131.7g of dimethyl 5-benzimidhenylacetylene-1, 3-isophthalate, 28.6g of sodium (3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 25.5g of sodium (3- (2-hydroxyethoxy) -3-oxopropyl) (phenyl) phosphinate, 0.2g of magnesium acetate and 0.2g of titanium dioxide were charged into a reaction vessel, and esterification and polycondensation reactions were carried out under the conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.95 dL/g; the limiting oxygen index is 33.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 248kW/m2TSR is 690m2/m2。
Example 9
498.0g of terephthalic acid, 220.0g of ethylene glycol, 123.3g of 5-benzimide phenylacetylene-1, 3-dibenzoic acid, 42.6g of potassium 5-sulfoisophthalate and 0.3g of ethylene glycol antimony were added into a reaction kettle, and esterification and polycondensation were carried out according to the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.76 dL/g; the limiting oxygen index is 34.6%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 202kW/m2TSR is 688m2/m2。
Example 10
498.0g of terephthalic acid, 220.0g of ethylene glycol, 369.9g of 5-benzimidenphenylacetylene-1, 3-dibenzoic acid, 180.6g of 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) xanthenexanthenesodium phosphinate and 0.3g of tetrabutyl titanate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.84 dL/g; the limiting oxygen index is 46.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 186kW/m2TSR is 440m2/m2。
Example 11
415.0g of terephthalic acid, 53.0g of isophthalic acid, 30.0g of phthalic acid, 220.0g of ethylene glycol, 95.9g of (E) -5- (benzylideneamino) benzene-1, 3-diol, 16.1g of magnesium (3- (2-hydroxyethoxy) -3-oxopropyl (phenyl) phosphinate, 12.9g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinate, 9.5g of sodium (3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 0.27g of titanium dioxide and 0.03g of silica were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedure and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.60 dL/g; the limiting oxygen index is 32.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 482kW/m2TSR is 917m2/m2。
Example 12
498.0g of terephthalic acid, 220.0g of ethylene glycol, 44.6g of (E) -dimethyl 5- (benzylideneamino) benzene-1, 3-isophthalate, 19.1g of sodium (3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 0.15g of zinc acetate, 0.3g of alumina and 0.1g of silica were charged in a reaction vessel, and esterification and polycondensation reactions were carried out under the conditions and the procedures of example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.75 dL/g; the limiting oxygen index is 29.5%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 412kW/m2TSR is 1055m2/m2。
Example 13
388.0g of dimethyl terephthalate, 194.0g of dimethyl isophthalate, 400.0g of ethylene glycol, 178.2 g of (E) -dimethyl 5- (benzylideneamino) benzene-1, 3-isophthalate, 81.6g of potassium 3, 5-bis (6- (methoxycarbonyl) -1H-benzimidazol-2-yl) benzenesulfonate, 0.2g of aluminum acetate and 0.25g of titanium citrate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out under the procedures and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.77 dL/g; the limiting oxygen index is 36.2%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 346kW/m2TSR is 744m2/m2。
Example 14
498.0g of terephthalic acid, 220.0g of ethylene glycol, 109.5g of dimethyl 5- (2, 5-dioxo-3-phenyl-2, 5-dihydro-1H-pyrrol-1-yl) isophthalate, 25.8g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxa-phosphinate and 0.25g of tetraethyl titanate were charged into a reaction vessel, and esterification and polycondensation were carried out under the conditions and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.80 dL/g; the limiting oxygen index is 33.4%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 302kW/m2TSR is 855m2/m2。
Example 15
498.0g of terephthalic acid, 220.0g of ethylene glycol, 88.6g of (1- (3, 5-bis (2-hydroxyethoxy) phenyl) -3-phenyl-1H-pyrrole-2, 5-dione, 19.1g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate and 0.3g of potassium titanium oxalate were charged in a reaction vessel, and esterification and polycondensation were carried out under the conditions and procedures described in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.78 dL/g; the limiting oxygen index is 32.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 398kW/m2TSR is 926m2/m2。
Example 16
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 47.0g of 5-benzamido-1, 3-isophthalic acid dimethyl ester, 26.8g of 2,8- (2-hydroxyethoxy) carbonyl phenanthrene oxaphosphinic acid potassium salt, 0.2g of magnesium acetate and 0.2g of potassium hexafluorotitanate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedure and conditions of example 2, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]1.2 dL/g; the limiting oxygen index is 28.6%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 465kW/m2TSR is 970m2/m2。
Example 17
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 563.4g of 5-benzamido-1, 3-isophthalic acid dimethyl ester, 17.8g of potassium (3- (2-hydroxyethoxy) -3-oxopropyl) (phenyl) phosphinate, 40.2g of isophthalic acid-5-sodium sulfonate and 0.24g of tetraisopropyl titanate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.90 dL/g; the limiting oxygen index is 42.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 195kW/m2TSR is 468m2/m2。
Example 18
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 171.0g of 5-benzamido-1, 3-isophthalic acid, 52.5g of 3, 5-bis (methoxycarbonyl) phenyl) potassium phosphonate and 0.3g of ethylene glycol antimony were added into a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions given in example 2, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]1.12 dL/g; the limiting oxygen index is 33.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 244kW/m2TSR is 787m2/m2。
Example 19
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 85.5g of 5-benzamido-1, 3-isophthalic acid, 24.1g of sodium 5-sulfoisophthalic acid and 0.24g of tetrabutyl titanate were added into a reaction kettle, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]1.03 dL/g; the limiting oxygen index is 30.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 290kW/m2TSR is 733m2/m2。
Example 20
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 95.1g of 95.1g N- (3, 5-bis (2-hydroxyethoxy) phenyl) benzamide, 17.6g of dimethyl 5- (phenylethynyl) -1, 3-isophthalate, 21.0g of potassium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 31.7g of sodium 3, 5-bis (6- (methoxycarbonyl) -1H-benzimidazol-2-yl) benzenesulfonate, 0.2g of nickel acetate and 0.2g of tetrabutoxygermanium were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedures and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.80 dL/g; the limiting oxygen index is 33.4%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 269kW/m2TSR is 676m2/m2。
Example 21
468.0g of terephthalic acid, 30.0g of isophthalic acid, 220.0g of ethylene glycol, 142.7g of 142.7g N- (3, 5-bis (2-hydroxyethoxy) phenyl) benzamide, 90.3g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene xanthene phosphinate, 0.15g of magnesium acetate and 0.35g of aluminum hydroxide were charged into a reaction vessel, and esterification and polycondensation were carried out under the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.74 dL/g; the limiting oxygen index is 34.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 241kW/m2TSR is 532m2/m2。
Example 22
498.0g of terephthalic acid, 220.0g of ethylene glycol, 34.4g of 3, 5-dihydroxy-N-phenylbenzamide, 28.0 g of dimethyl 5- (3-cyanophenoxy) isophthalate, 28.6g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 25.2g of sodium (3- (2-hydroxyethoxy) -3-oxopropyl) (phenyl) phosphinate and 0.3g of titanium dioxide were charged in a reaction vessel, and esterification and polycondensation reactions were carried out under the conditions and conditions of example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.79 dL/g; the limiting oxygen index is 34.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 235kW/m2TSR is 664m2/m2。
Example 23
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 47.6g of 3, 5-bis (2-hydroxyethoxy) -N-phenylbenzamide, 61.4g of dimethyl 5- ((diphenylphosphoryl) amino) isophthalate, 46.8g of methyl 2- (4- (methoxycarbonyl) phenyl) -1H-benzimidazole-5-carboxylate, 31.8g of sodium 3, 5-dihydroxybenzenesulfonate and 0.3g of tetrabutyl titanate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedures and conditions of example 2, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.90 dL/g; the limiting oxygen index is 36.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 202kW/m2TSR is 529m2/m2。
Example 24
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 51.3g of 51.3g N- (3-cyanophenyl) -3, 5-bis (2-hydroxyethoxy) benzamide, 90.3g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene xanthene phosphinate, 10.2g of dimethyl 5-benzimide-1, 3-isophthalate, 0.2g of manganese acetate and 0.2g of tetraisopropyl titanate were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedure and conditions of example 2, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.66 dL/g; the limiting oxygen index is 36.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 250kW/m2TSR is 761m2/m2。
Example 25
498.0g of terephthalic acid, 220.0g of ethylene glycol, 46.7g of dimethyl 5- (3-cyanophenoxy) isophthalate, 40.1g of potassium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinite and 0.3g of titanium citrate were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedure and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.88 dL/g; the limiting oxygen index is 30.0%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 302kW/m2TSR is 893m2/m2。
Example 26
498.0g of terephthalic acid, 220.0g of ethylene glycol, 93.3g of dimethyl 5- (4-cyanophenoxy) isophthalate, 122.7g of dimethyl 5- ((diphenylphosphoryl) amino) isophthalate, 190.8g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate and 0.3g of antimony trioxide were charged in a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.75 dL/g; the limiting oxygen index is 39.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 242kW/m2TSR is 598m2/m2。
Example 27
498.0g of terephthalic acid, 220.0g of ethylene glycol, 94.5g of 4- (3, 5-bis (2-hydroxyethoxy) phenoxy) benzonitrile, 63.6g of sodium 3, 5-dihydroxybenzenesulfonate and 0.25g of titanium glycol were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedure and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.82 dL/g; the limiting oxygen index is 36.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 252kW/m2TSR is 770m2/m2。
Example 28
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 48.2g of 5- (phenylsulfamoyl) isophthalic acid, 40.1g of potassium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinite, 0.2g of cobalt acetate and 0.25g of titanium tartrate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.65 dL/g; the limiting oxygen index is 30.2%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 268kW/m2TSR is 690m2/m2。
Example 29
498.0g of terephthalic acid, 220.0g of ethylene glycol, 159.0g N- (3, 5-dihydroxyphenyl) benzenesulfonamide, 28.1g of methyl 2- (4- (methoxycarbonyl) phenyl) -1H-benzimidazole-5-carboxylate, 47.7g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate and 0.25g of isopropyl titanate were charged in a reaction vessel, and esterification and polycondensation reactions were carried out under the conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.82 dL/g; the limiting oxygen index is 38.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 216kW/m2TSR is 582m2/m2。
Example 30
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 48.2g of 5- (phenylsulfamoyl) isophthalic acid, 80.4g of 5-sodium sulfoisophthalate and 0.3g of tetrabutyl titanate were added into a reaction kettle, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.76 dL/g; the limiting oxygen index is 32.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 331kW/m2TSR is 877m2/m2。
Example 31
498.0g of terephthalic acid, 220.0g of ethylene glycol, 314.1g of dimethyl 5- (N-phenylsulfamoyl) isophthalate, 95.4g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 0.2g of antimony acetate and 0.1g of titanium dioxide were charged in a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.94 dL/g; the limiting oxygen index is 40.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 177kW/m2TSR is 530m2/m2。
Example 32
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 101.7g of 5-benzimide-1, 3-dimethyl isophthalate, 80.4g of sodium 5-sulfoisophthalate, 0.2g of manganese acetate and 0.3g of potassium titanium oxalate were put into a reaction vessel, and esterification and polycondensation were carried out according to the procedure and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.79 dL/g; the limiting oxygen index is 29.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 401kW/m2TSR is933m2/m2。
Example 33
498.0g of terephthalic acid, 220.0g of ethylene glycol, 52.4g of methyl 4- (N- (4- (methoxycarbonyl) phenyl) sulfamoyl) benzoate, 40.2g of sodium 5-sulfonate isophthalate, 38.7g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinic acid, 28.6g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 0.28g of titanium dioxide and 0.015 g of zirconium dioxide were put into a reaction vessel, and esterification and polycondensation were carried out according to the procedure and conditions of example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]1.10 dL/g; the limiting oxygen index is 29.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 266kW/m2TSR is 881m2/m2。
Example 34
498.0g of terephthalic acid, 220.0g of ethylene glycol, 168.3g of methyl 2-cyano-4- ((4- (methoxycarbonyl) phenyl) sulfanyl) benzoate, 81.6g of potassium 3, 5-bis (6- (methoxycarbonyl) -1H-benzimidazol-2-yl) benzenesulfonate, 0.2g of zinc acetate and 0.3g of antimony ethylene glycol were charged into a reaction vessel, and esterification and polycondensation were carried out by the steps and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.88 dL/g; the limiting oxygen index is 35.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 320kW/m2TSR is 686m2/m2。
Example 35
498.0g of terephthalic acid, 220.0g of ethylene glycol, 209.4g of methyl 4- (N- (4- (methoxycarbonyl) phenyl) sulfamoyl) benzoate, 24.5g of dimethyl 5- ((diphenylphosphoryl) amino) isophthalate, 8.0g of sodium 5-sulfoisophthalate, 180.6g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthenephosphinate and 0.26g of tetrabutyl titanate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out by the steps and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]1.30 dL/g; the limiting oxygen index is 44.0%; the vertical burning grade is V-0 grade,no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 155kW/m2TSR is 443m2/m2。
Example 36
498.0g of terephthalic acid, 220.0g of ethylene glycol, 81.0g of 4, 4' -azobenzene dicarboxylate, 64.5g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinic acid and 0.3g of antimony acetate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.70 dL/g; the limiting oxygen index is 30.0%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 402kW/m2TSR is 850m2/m2。
Example 37
498.0g of isophthalic acid, 220.0g of ethylene glycol, 81.0g of 4, 4' -diformylazobenzene, 32.6g of potassium 3, 5-bis (6- (methoxycarbonyl) -1H-benzimidazol-2-yl) benzenesulfonate, 54.2g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthenephosphinate, 0.2g of aluminum acetate and 0.25g of titanium glycol were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedures and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.76 dL/g; the limiting oxygen index is 33.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 220kW/m2TSR is 617m2/m2。
Example 38
498.0g of terephthalic acid, 220.0g of ethylene glycol, 106.5g of 106.5g N- (2-methyl-5-carbomethoxyphenyl) -4-carbomethoxy-benzimide, 95.4g of 3, 5-bis (methoxycarbonyl) phenyl) sodium phosphonate and 0.3g of titanium acetylacetonate were added to a reaction vessel, and esterification and polycondensation reactions were carried out under the conditions and the procedures of example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.66 dL/g; the limiting oxygen index is 33.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 322kW/m2TSR is 885m2/m2。
Example 39
498.0g of terephthalic acid, 220.0g of ethylene glycol, 106.5g of 106.5g N- (2-methyl-5-carbomethoxyphenyl) -4-carbomethoxy-benzimide, 80.4g of sodium 5-isophthalate and 0.28g of antimony acetate were added into a reaction kettle, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.65 dL/g; the limiting oxygen index is 34.2%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 269kW/m2TSR is 764m2/m2。
Example 40
498.0g of terephthalic acid, 270.0g of 1, 3-propanediol, 182.3g of dimethyl 4, 4' - ((1, 3-phenylene-5-cyano) dioxy) dibenzoate, 24.5g of dimethyl 5- ((diphenylphosphoryl) amino) isophthalate, 47.7g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate and 0.2g of tetraisopropyl titanate were charged into a reaction vessel, and esterification and polycondensation were carried out under the conditions and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.80 dL/g; the limiting oxygen index is 30.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 517kW/m2TSR is 1295m2/m2。
EXAMPLE 41
498.0g of isophthalic acid, 270.0g of 1, 3-propanediol, 121.5g of dimethyl 4, 4' - ((1, 3-phenylene-2-cyano) dioxy) dibenzoate, 95.4g of sodium 3, 5-dihydroxybenzenesulfonate, 0.1g of antimony acetate and 0.3g of alumina were charged into a reaction vessel, and esterification and polycondensation were carried out under the procedures and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.76 dL/g; the limiting oxygen index is 32.5%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 468kW/m2TSR is 946m2/m2。
Example 42
498.0g of terephthalic acid, 220.0g of ethylene glycol, 121.5g of dimethyl 4, 4' - ((1, 3-phenylene-5-cyano) dioxy) dibenzoate, 47.7g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 180.6g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthraceneoxaphosphinate and 0.3g of ethylene glycol antimony were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.77 dL/g; the limiting oxygen index is 50.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 166kW/m2TSR is 458m2/m2。
Example 43
498.0g of isophthalic acid, 220.0g of ethylene glycol, 152.1g of methyl 3-cyano-5- ((4- (methoxycarbonyl) phenyl) carbamoyl) benzoate, 47.7g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate and 0.3g of potassium hexafluorotitanate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.80 dL/g; the limiting oxygen index is 34.6%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 270kW/m2TSR is 701m2/m2。
Example 44
498.0g of terephthalic acid, 320.0g of 1, 4-butanediol, 101.4g of methyl 3-cyano-5- ((4- (methoxycarbonyl) phenyl) carbamoyl) benzoate, 40.2g of sodium 5-sulfoisophthalate, 0.2g of zinc acetate and 0.2g of tetraphenyl titanate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedures and conditions of example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.99 dL/g; the limiting oxygen index is 28.0%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 556kW/m2TSR is 1252m2/m2。
Example 45
498.0g of terephthalic acid, 220.0g of ethylene glycol, 46.8g of methyl 2- (4- (methoxycarbonyl) phenyl) -1H-benzimidazole-5-carboxylate, 64.5g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinic acid and 0.3g of tetrabutyl titanate were put into a reaction kettle, and esterification and polycondensation reactions were carried out according to the procedures and conditions of example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]1.23 dL/g; the limiting oxygen index is 30.2%; the vertical combustion grade is V-2 grade; the p-HRR in the cone calorimetry test is 309kW/m2TSR is 956m2/m2。
Example 46
498.0g of terephthalic acid, 220.0g of ethylene glycol, 93.6g of methyl 2- (4- (methoxycarbonyl) phenyl) -1H-benzimidazole-5-carboxylate, 95.4g of sodium 3, 5-bis (methoxycarbonyl) phenyl) phosphonate, 8.9g of potassium (3- (2-hydroxyethoxy) -3-oxopropyl) (phenyl) phosphinate and 0.28g of titanium glycol were charged in a reaction vessel, and esterification and polycondensation were carried out under the conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]Is 1.04 dL/g; the limiting oxygen index is 35.2%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 253kW/m2TSR is 858m2/m2。
Example 47
498.0g of terephthalic acid, 220.0g of ethylene glycol, 93.6g of methyl 2- (4- (methoxycarbonyl) phenyl) -1H-benzimidazole-5-carboxylate, 40.2g of sodium 5-sulfoisophthalate, 0.2g of zinc acetate and 0.3g of ethylene glycol antimony were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.89 dL/g; the limiting oxygen index is 34.6%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 233kW/m2TSR is 651m2/m2。
Example 48
498.0g of terephthalic acid, 220.0g of ethylene glycol, 187.2g of methyl 2- (4- (methoxycarbonyl) phenyl) -1H-benzimidazole-5-carboxylate, 81.6g of potassium 3, 5-bis (6- (methoxycarbonyl) -1H-benzimidazol-2-yl) benzenesulfonate, 0.2g of manganese acetate and 0.2g of potassium titanium oxalate were charged into a reaction vessel, and esterification and polycondensation were carried out under the conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.96 dL/g; the limiting oxygen index is 41.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 173kW/m2TSR is 593m2/m2。
Example 49
498.0g of terephthalic acid, 220.0g of ethylene glycol, 63.9g of methyl 2, 2' - (1, 4-phenylene) bis (1H-benzimidazole-5-carboxylate), 66.9g of potassium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinite and 0.26g of tetraisopropyl titanate were charged into a reaction vessel, and esterification and polycondensation were carried out under the conditions and conditions as in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]1.69 dL/g; the limiting oxygen index is 34.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 311kW/m2TSR is 903m2/m2。
Example 50
498.0g of terephthalic acid, 220.0g of ethylene glycol, 191.7g of 2, 2' - (1, 4-phenylene) bis (1H-benzimidazole-5-carboxylic acid methyl ester), 52.5g of 3, 5-bis (methoxycarbonyl) phenyl) potassium phosphonate and 0.3g of titanium dioxide were charged in a reaction vessel, and esterification and polycondensation reactions were carried out under the conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]Is 1.04 dL/g; the limiting oxygen index is 40.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 199kW/m2TSR is 620m2/m2。
Example 51
498.0g of terephthalic acid, 220.0g of ethylene glycol, 261.9g of 4- ((4-cyanophenyl) ethynyl) phthalic acid and 0.3g of antimony trioxide were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions given in example 1, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]1.22 dL/g; the limiting oxygen index is 34.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 292kW/m2TSR is 1332m2/m2。
Example 52
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 77.3g of dimethyl (E) -5- ((4-cyanobenzylidene) amino) benzene-1, 3-isophthalate and 0.28g of antimony acetate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.72 dL/g; the limiting oxygen index is 30.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 369kW/m2TSR is 946m2/m2。
Example 53
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 102.2g of 2, 2' - (1, 4-phenylene) bis (1H-benzimidazole-5-carboxylic acid methyl ester), 59.9g of 5-benzamido-1, 3-isophthalic acid and 0.3g of tetrabutyl titanate were charged into a reaction vessel, and esterification and polycondensation were carried out under the conditions and by the procedures given in example 2, followed by discharging.
Intrinsic viscosity [ eta ] of the copolyester]0.91 dL/g; the limiting oxygen index is 32.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 321kW/m2TSR is 1257m2/m2。
Example 54
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 76.6g of dimethyl 5- (3-cyanophenoxy) isophthalate, 65.9g of dimethyl 5-benzimidophenylacetylene-1, 3-isophthalate, 0.2g of manganese acetate and 0.2g of titanium glycol were charged into a reaction vessel, and esterification and polycondensation reactions were carried out according to the procedure and conditions of example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.68 dL/g; the limiting oxygen index is 31.0%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 312kW/m2TSR is 1076m2/m2。
Example 55
582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 44.1g of dimethyl 5- (phenylethynyl) -1, 3-isophthalate, 44.6g of (E) -dimethyl 5- (benzylideneamino) benzene-1, 3-isophthalate, 54.8g of dimethyl 5- (2, 5-dioxo-3-phenyl-2, 5-dihydro-1H-pyrrol-1-yl) isophthalate, 0.2g of magnesium acetate, 0.27g of titanium dioxide and 0.03g of silicon dioxide were charged into a reaction vessel, and esterification and polycondensation were carried out in accordance with the procedure and conditions given in example 2, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.76 dL/g; the limiting oxygen index is 31.8%; the vertical burning grade is V-0 grade, and no molten drop is generated in the test; the p-HRR in the cone calorimetry test is 284kW/m2TSR is 1105m2/m2。
Comparative example 1
498.0g of terephthalic acid, 220.0g of ethylene glycol, 0.2g of zinc acetate and 0.3g of antimony trioxide were added to the reaction kettle, and after esterification and polycondensation reactions were carried out according to the procedures and conditions given in example 1, the product was discharged.
The intrinsic viscosity [ eta ] of the PET polyester]0.80 dL/g; the limiting oxygen index is 22.0%; the vertical combustion grade is stepless, and a large amount of molten drops are generated in the test; the p-HRR in the cone calorimetry test is 735kW/m2(ii) a TSR 1756 m2/m2。
Comparative example 2
498.0g of terephthalic acid, 220.0g of ethylene glycol, 159.6g of 4- (phenylethynyl) phthalic acid, 0.2g of zinc acetate and 0.3g of antimony trioxide were charged into a reaction vessel, and esterification and polycondensation were carried out under the conditions and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]0.95 dL/g; the limiting oxygen index is 28.0%; the vertical burning grade is V-2 grade, and a small amount of molten drops are generated in the test; the p-HRR in the cone calorimetry test is 471kW/m2(ii) a TSR 1939m2/m2。
Comparative example 3
498.0g of terephthalic acid, 220.0g of ethylene glycol, 38.7g of sodium 2,8- (2-hydroxyethoxy) carbonylphenanthreneoxaphosphinic acid, 0.2g of zinc acetate and 0.3g of antimony trioxide were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedures and conditions given in example 1, followed by discharge.
Intrinsic viscosity [ eta ] of the copolyester]Is 0.84 dL/g; the limiting oxygen index is 25.5%; the vertical combustion grade is stepless, and more molten drops are generated in the test; the p-HRR in the cone calorimetry test is 392kW/m2(ii) a TSR is 1077m2/m2。