CN110746457B - Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer - Google Patents

Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer Download PDF

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CN110746457B
CN110746457B CN201911100588.7A CN201911100588A CN110746457B CN 110746457 B CN110746457 B CN 110746457B CN 201911100588 A CN201911100588 A CN 201911100588A CN 110746457 B CN110746457 B CN 110746457B
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CN110746457A (en
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王玉忠
吴万寿
段平慧
左晗
黄晨欣
汪秀丽
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3834—Aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6926—Dicarboxylic acids and dihydroxy compounds

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Abstract

The invention discloses an ionic monomer containing a phosphonate structure, a flame-retardant smoke-suppressing ionomer catalyzed by the ionic monomer, a preparation method and application of the flame-retardant smoke-suppressing ionomer, wherein the flame-retardant smoke-suppressing ionomer is prepared from dibasic acid or an esterified product thereof and C2～C8The copolyester monomer of the polyhydric alcohol and the catalyst containing the phosphonate structure ionic monomer with the following structural general formula are prepared by esterification and polycondensation reaction:

Description

Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer
Technical Field
The invention belongs to the technical field of reactive ionic monomers, flame-retardant smoke-suppressing copolyester ionomers and preparation thereof, and particularly relates to an ionic monomer containing a phosphonate structure, a flame-retardant smoke-suppressing ionomer catalytically synthesized by using the ionic monomer, and preparation methods and applications of the ionic monomer and the flame-retardant smoke-suppressing copolyester ionomers.
Background
Polyesters, such as polyethylene terephthalate (PET), are widely used in the fields of packaging materials, textile fibers, engineering plastics, etc., because of their excellent mechanical strength, chemical resistance, thermal stability, transparency, and easy processability. However, most of the catalysts used for polymerization in the production of polyester are antimony-based catalysts. The antimony catalyst has generally low catalytic efficiency, and heavy metal antimony is easy to migrate out of the product in the use process of the polyester product and enter the environment. Studies show that antimony has chronic toxicity and carcinogenicity to human bodies and organisms, and antimony and compounds thereof are the priority pollutants by the United states environmental protection agency and European Union, so that the use of antimony catalysts is strictly limited. Meanwhile, polyester obtained by catalysis of a common antimony catalyst presents gray color, and a whitening agent needs to be added to meet the use requirement, so that the preparation cost is increased. At present, the most widely used antimony-free catalyst is a titanium catalyst, which has high catalytic activity and low toxicity. However, many existing titanium catalysts such as tetrabutyl titanate (TBT) are susceptible to hydrolysis reaction during use, thereby losing catalytic activity, which has certain limitations on storage and use environments. And the polyester obtained by catalysis of a titanium catalyst is generally yellow, and a whitening agent needs to be added to meet the use requirement.
Secondly, pure PET is also a flammable material, and can emit a large amount of heat and dense smoke during combustion, which can cause serious threat to the safety of people's lives and properties, and thus further application of the PET is limited. The most applied flame retardant at present is a halogen flame retardant, and the flame retardant has the advantages of small addition amount, good flame retardant effect and the like. However, halogen-based flame retardants emit hydrogen halide gas (HCl, HBr, etc.) during combustion, which is one of the leading causes of casualties in building fires. And the halogen flame retardant can be decomposed to generate organic matters which are difficult to biodegrade and cause long-term harm to the health of people if the organic matters are enriched in human bodies. Meanwhile, as the crystallization performance of pure PET is better, the crystal region is compact, and the molecular structure mainly comprises a hydrophobic benzene ring, an ester bond and a fatty chain, the cationic dyeing performance of PET polyester fibers is generally poorer, and the currently commonly used cationic dyeing modified fiber (CDP) mostly adopts an isophthalic acid-5-sodium sulfonate ionic monomer to improve the fuel adsorption capacity of the fiber. However, conventional CDP cationic dyeing processes typically require high temperature and pressure conditions, which also increases processing costs.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides an ionic monomer containing a phosphonate structure.
The second purpose of the invention is to provide a preparation method of the ionic monomer containing the phosphonate structure.
The invention also aims to provide a flame-retardant smoke-suppressing ionomer catalytically synthesized by using the phosphonate structure-containing ionic monomer.
The fourth purpose of the invention is to provide a preparation method of the flame-retardant smoke-suppressing ionomer synthesized by catalyzing the phosphonate structure-containing ionic monomer.
The fifth purpose of the invention is to provide an application of the flame-retardant smoke-suppressing ionomer synthesized by catalyzing the phosphonate structure-containing ionic monomer.
The ionic monomer containing a phosphonate structure is characterized in that the structural general formula of the ionic monomer is as follows:
Figure BDA0002269744610000021
in the formula, R1、R2Is a carboxyl group, an ester group, a hydroxyl group or
Figure BDA0002269744610000022
The metal ions can be the same or different, a is an integer of 2-8, M is a metal ion, and n is an integer of 1-3.
In the structural general formula of the ionic monomer, the ester group is a methyl ester group, an ethyl ester group or a phenyl ester group after monohydric alcohol esterification, or is any one of an ethylene glycol ester group, a propylene glycol ester group, a butanediol group, a neopentyl glycol ester group, a glycerol ester group or a pentaerythritol ester group after polyhydric alcohol esterification.
The metal ion in the structural general formula of the ionic monomer is any one of Li, Na, K, Mg, Ca, Mn, Co, Ni, Zn or Al, and Na or K is preferred.
The invention provides a preparation method of the ionic monomer containing the phosphonate structure, which comprises the step of carrying out neutralization reaction on a precursor containing a phosphonic acid group, solvent water and hydroxide, carbonate or bicarbonate containing metal ions according to a conventional molar ratio to prepare the ionic monomer containing the phosphonate structure. The precursor is a compound with the following structural general formula:
Figure BDA0002269744610000031
in the formula, R1、R2Is a carboxyl group, an ester group, a hydroxyl group or
Figure BDA0002269744610000032
Can be the same or different, and a is an integer of 2-8.
The ester group in the precursor containing phosphonic acid group used in the above preparation method is a methyl ester group, an ethyl ester group or a phenyl ester group after esterification of monohydric alcohol, or is any one of an ethylene glycol ester group, a propylene glycol ester group, a butanediol group, a neopentyl glycol ester group, a glycerol ester group or a pentaerythritol ester group after esterification of polyhydric alcohol.
The hydroxide, carbonate or bicarbonate containing a metal ion used in the above production method is a hydroxide, carbonate or bicarbonate containing Li, Na, K, Mg, Ca, Mn, Co, Ni, Zn or Al ion, preferably potassium hydroxide, sodium hydroxide, zinc hydroxide, aluminum hydroxide, nickel hydroxide, potassium carbonate, sodium carbonate, aluminum carbonate, zinc carbonate, nickel carbonate, aluminum carbonate, sodium bicarbonate or potassium bicarbonate, more preferably sodium bicarbonate or potassium bicarbonate.
The phosphonic acid group-containing precursor used in the above production method may be prepared as disclosed in patent US 005498784a, or may be obtained commercially.
The neutralization reaction in the preparation method specifically adopts the following process steps and conditions:
firstly, according to the molar ratio of phosphonic acid groups to metal ions as n: m is 1-3: 1-2, adding a precursor containing a phosphonic acid group, hydroxide containing metal ions, carbonate or bicarbonate and solvent water, stirring to enable the precursor to be completely dissolved, slowly heating to 40-90 ℃, slowly vacuumizing until no bubbles are generated in the reaction, removing the solvent after the reaction is finished, and drying.
The invention provides a flame-retardant smoke-suppressing ionomer synthesized by catalyzing the phosphonate structure-containing ionic monomer, which consists of the following structural units I, II and III or the structural units I, II and IV:
Figure BDA0002269744610000041
in the formula, R3Represents an arylene group or C2～C8Alkylene of (2)
Figure BDA0002269744610000042
In the formula, R4Represents an arylene group or C2～C8The alkylene group of (a) is,
Figure BDA0002269744610000043
in the formula, R1、R2The groups are carboxyl groups or ester groups, which can be the same or different, M is a metal ion, and n is an integer of 1-3.
Figure BDA0002269744610000044
In the formula, R5、R6Is C2～C8The alkylene groups of (A) may be the same or different, M is a metal ion, and n is an integer of 1 to 3.
Wherein, the structural unit number of III is 0.2-15.0% of the structural unit 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 0.2-15.0% of that of the I structural units, and I: the structural unit of [ II + IV ] is 1, each structural unit or formed chain segment is optionally connected and combined according to carboxyl and hydroxyl functional groups, the intrinsic viscosity of the ionomer is [ eta ] of 0.35-0.98 dL/g, and the limiting oxygen index is 22.5-36.0%; the vertical combustion grade is V-2 to V-0 grade; the peak heat release rate p-HRR in the cone calorimetry test is reduced to 18.4-62.9% of that of pure PET; the total smoke release amount is reduced to 20.0-73.5% of that of pure PET.
In the ionomer, the number of structural units III is preferably 2.0 to 8.0% of the structural units I, and the number of structural units II is preferably: the number of structural units of [ i + iii ] is 1; the number of the IV structural units is 2.0-8.0% of that of the I structural units, and I: the structural unit of [ II + IV ] is 1, the intrinsic viscosity of the ionomer is [ eta ] of 0.91-0.98 dL/g, and the limiting oxygen index is 24.5-28.7%; the vertical combustion grade is V-2 to V-0 grade; the peak heat release rate p-HRR in the cone calorimetry test is reduced to 40.6-46.5% of that of pure PET; the total smoke release amount is reduced to 44.5-53.5% of that of pure PET.
The M metal ion in the ionomer structural unit III and the structural unit IV is any one of Li, Na, K, Mg, Ca, Mn, Co, Ni, Zn and Al ions, preferably Li, Na, K, Zn or Mg ions.
The ester group in the ionomer structural unit III is a methyl ester group, an ethyl ester group, or a phenyl ester group after esterification of a monohydric alcohol, or is any one of an ethylene glycol ester group, a propylene glycol ester group, a butanediol group, a neopentyl glycol ester group, a glycerol ester group, or a pentaerythritol ester group after esterification of a polyhydric alcohol.
The invention provides a preparation method of a flame-retardant smoke-suppressing ionomer catalytically synthesized by using the phosphonate structure-containing ionic monomer, which is characterized in that dibasic acid or an esterified product thereof and C2～C8The copolyester monomer of the polyhydric alcohol is prepared by esterification through a direct esterification method or an ester exchange method and then polycondensation, and is characterized in that the ionic monomer containing the phosphonate structure with the molar weight ratio of 0.2-15.0 percent of dibasic acid or esterified substance thereof in the polyester monomer is added into a reaction system before the esterification or before the polycondensation after the esterificationThe catalyst is preferably 2.0 to 8.0%.
The flame-retardant monomer containing a phosphonate structure used in the method is any one of the following structural general formulas:
Figure BDA0002269744610000051
in the formula, R1、R2Is a carboxyl group, an ester group, a hydroxyl group or
Figure BDA0002269744610000052
Any one of which may be the same or different, a is an integer of 2 to 8, M is a metal ion, and n is an integer of 1 to 3.
The ester group in the structural general formula of the ionic monomer used in the method is methyl ester group, ethyl ester group or phenyl ester group after monohydric alcohol esterification, or is any one of ethylene glycol ester group, propylene glycol ester group, butanediol group, neopentyl glycol ester group, glycerol ester group or pentaerythritol ester group after polyhydric alcohol esterification.
The metal ion in the structural general formula of the ionic monomer used in the method is any one of Li, Na, K, Mg, Ca, Mn, Co, Ni, Zn or Al.
The conventional esterification method or ester exchange method adopted by the invention comprises the following process steps and conditions:
the direct esterification method comprises the following steps: adding a polyester monomer and a monomer containing phosphonate ions in a reaction kettle according to a ratio, pressurizing and heating to the temperature of 200-240 ℃ to perform esterification reaction for 1-7 hours; after the esterification is finished, performing polycondensation reaction for 0.3-1.5 hours at the temperature of 240-250 ℃ under low vacuum, then heating to 260 ℃, performing polycondensation reaction for 1-3 hours under high vacuum (the pressure is less than 40Pa), then extruding the product out of the furnace body by using nitrogen, and performing water cooling to obtain the target copolyester. Wherein, the phosphonate ionic monomer can be selectively added into the reaction kettle before esterification or before polycondensation after esterification.
An ester exchange method: adding a polyester monomer and a phosphonate ion-containing monomer into a reaction kettle according to a ratio, carrying out ester exchange reaction for 2-5h at the temperature of 190-210 ℃ under normal pressure, carrying out polycondensation reaction for 0.5-1.5 h at the temperature of 240-250 ℃ under low vacuum after the end of ester exchange and esterification, then heating to 260 ℃, carrying out polycondensation reaction for 1-3 h under high vacuum (the pressure is less than 40Pa), then extruding out of a furnace body by using nitrogen, and carrying out water cooling to obtain the target ionomer. Wherein, the phosphonate structural monomer can be selectively added into the reaction kettle before esterification or before polycondensation after esterification.
The invention provides an application of a flame-retardant smoke-suppressing ionomer catalytically synthesized by using the phosphonate structure-containing ionic monomer, which is used for preparing textile fibers, engineering plastics and packaging materials.
The invention has the following advantages:
1. because the ionic monomer provided by the invention contains a phosphonate structure which has excellent catalytic capability, the method not only can well catalyze the ester exchange reaction and the melt polycondensation reaction in the synthesis process of the polyester to obtain the copolyester ionomer with high polymerization degree, but also can access the methyl ester bond in the ionic monomer into the polyester main chain in the ester exchange process, thereby avoiding the problems that the traditional additive catalyst is easy to migrate out and pollutes the environment.
2. Because the ionic monomer provided by the invention contains a phosphonate structure, the ionic monomer also has a good catalytic char formation effect, when the ionic monomer is introduced into copolyester, the copolyester ionomer can quickly form stable and compact char layers during combustion, and the char layers can play a role in isolating heat, oxygen and combustible micromolecule transmission, so that the copolyester ionomer can be further endowed with good flame-retardant and smoke-suppression effects.
3. The phosphonate structure in the copolyester ionomer provided by the invention is stable in the processing temperature range (220-300 ℃) and does not generate decomposition and chemical reaction, so that the synthesis and processing of polyester are not influenced, the original processing window (220-300 ℃) of polyester can be kept, and the physical crosslinking structure in a molecular chain can realize repeated processing of the obtained ionomer.
4. The phosphonate structure in the structural unit of the copolyester ionomer can improve the thermal stability of a polyester product in the polyester synthesis, reduce the generation of byproducts and improve the whiteness of the product, so that the degradation in the polyester processing process can be avoided, and the preparation cost of the polyester can be reduced.
5. The copolyester ionomer provided by the invention has good thermoplastic processability and spinnability because no additive influencing fiber preparation is added, can be used as copolyester for fibers and films, and also can be used as a macromolecular compatibilizer of an incompatible polymer blending system to generate a physical crosslinking effect with polymers in the blending system, so that the copolyester ionomer can improve the mechanical property of materials and endow the materials with good flame-retardant and smoke-suppression effects.
6. The copolyester ionomer contains a phenylphosphonate structure, so that cationic dye can be well adsorbed, and the cationic dyeing capability of the copolyester ionomer can be obviously improved.
7. The preparation method provided by the invention is basically consistent with the conventional method for synthesizing copolyester, so that the preparation method has a mature process, is simple and convenient to operate and is very easy for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of an ionic monomer containing a potassium phenylphosphonate structure prepared in example 1 of the present invention. The peak between 7.0 and 7.5ppm in the hydrogen spectrum corresponds to the peak on the benzene ring of the ionic monomer, and the peak near 2.3ppm corresponds to the methyl group in the methyl benzoate. The ionic monomer containing the structure of potassium phenylphosphonate is successfully synthesized.
FIG. 2 is a nuclear magnetic phosphorus spectrum of an ionic monomer containing potassium phenylphosphonate structure prepared in example 1 of the present invention. The peak near 13ppm in the phosphorus spectrum corresponds to the phosphorus element in the ionic monomer, and only one peak also indicates that only one kind of phosphorus element in the chemical environment exists in the product. The ionic monomer containing the structure of potassium phenylphosphonate is successfully synthesized.
FIG. 3 is a nuclear magnetic hydrogen spectrum of an ionomer prepared in example 13 of the present invention. The peak between 9.0 and 9.5ppm in the hydrogen spectrum corresponds to the peak on the benzene ring of the ionic monomer, the peak near 4.8ppm corresponds to the ethyl hydrogen in the main chain of the copolyester, and the peak near 8.1ppm corresponds to the hydrogen on the benzene ring in the main chain of the copolyester. Thus showing that the structure containing the phenyl potassium phosphonate is successfully introduced into the molecular chain of the polyester.
FIG. 4 is a nuclear magnetic phosphorus spectrum of an ionomer prepared in example 13 of the present invention. The peak near 19ppm in the phosphorus spectrogram corresponds to the phosphorus element in the ionic monomer, and the result also shows that the structure containing the phenyl potassium phosphonate is successfully introduced into the polyester molecular chain.
FIG. 5 is a graph of the heat release of neat PET prepared in comparative example versus the ionomer prepared in example 13 of the present invention. As can be seen from the results shown in the figure, with the introduction of the ionic monomer, the combustion behavior of the ionomer is changed, the peak heat release rate p-HRR is obviously reduced to 47 percent of that of pure PET, and the excellent flame retardant property is shown.
FIG. 6 is a graph of the smoke density of pure PET prepared in the comparative example versus the ionomer prepared in example 13 of the present invention. From the results shown in the figure, it can be seen that with the introduction of the ionic monomer, the smoke density of the ionomer is significantly reduced to 42% of that of pure PET, showing excellent smoke suppression.
FIG. 7 is a stress-strain plot of neat PET prepared in a comparative example versus an ionomer prepared in example 13 of the present invention. From the results shown in the figure, it can be seen that the breaking strength of the ionomer is obviously improved with the introduction of the ionic monomer, from 55.8MPa to 67.0MPa of pure PET, indicating that the ionic monomer can improve the mechanical properties of the ionomer.
FIG. 8 is a plot of the absorbance of the dye liquor remaining after dyeing for neat PET prepared in comparative example versus ionomer woven fibers prepared in example 13 of the present invention. The cationic dye used in this test was methylene blue, and 1g of the fiber sample was placed in a 100mL round bottom flask with 100mL of buffer solution having a pH of 5 and 0.02g of methylene blue, set to an initiation temperature of 30 ℃, and heated to 95 ℃ at a heating rate of 1 ℃/min, and held at 95 ℃ for 2 hours. And after dyeing is finished, cooling to room temperature. And (3) pouring the dye solution into a 250mL volumetric flask, rinsing the fiber with water until the water is colorless, and pouring the rinsed water into the volumetric flask to reach a constant volume of 250 mL. And (4) carrying out an absorbance test by an ultraviolet-visible spectrophotometer, and taking the absorbance at the position of 665nm as the maximum absorbance. As can be seen from the results shown by comparison in the figure, the absorbance of the dye liquor remaining after dyeing the ionomer fiber obtained in example 13 is significantly lower than that of the dye liquor after dyeing the pure PET fiber, indicating that more dye is adsorbed to the surface of the ionomer fiber during the dyeing process. This result indicates that the incorporation of ionic monomers can impart excellent cationic dyeability to the ionomer.
Detailed Description
The following examples are given to further illustrate the present 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 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 phosphonate structure-containing ionomers obtained in the following examples and the comparative ionomer]Preparing a solution with the concentration of 5g/dL by using phenol/1, 1, 2, 2-tetrachloroethane (1: 1: v: v) as a solvent, and testing the solution at 25 ℃ by using an Ubbelohde viscometer; the limiting oxygen index is 120 × 6.5 × 3.2mm3According to ASTM D2863-97, on an HC-2 oxygen indexer; it was made 125X 12.7X 3.2mm in the vertical burning test3According to UL-94 standard, measured with a model CZF-2 vertical burner; the cone calorimetry is carried out to make it 100X 3mm3According to ISO 5660-1, on an FTT cone calorimeter.
Example 1
Adding 274g of dimethyl isophthalate-5-phosphonic acid, 200g of potassium bicarbonate and 1L of water into a reaction vessel, then completely dissolving the materials under magnetic stirring, slowly heating to 50 ℃, simultaneously vacuumizing by using a water pump to perform neutralization reaction for 60min, stopping stirring, removing water by rotary evaporation, and drying to obtain the dimethyl isophthalate-5-dipotassium phosphate.
Example 2
Adding 274g of dimethyl isophthalate-5-phosphonic acid, 168g of sodium bicarbonate and 1L of water into a reaction container, then completely dissolving the materials under magnetic stirring, slowly heating to 70 ℃, simultaneously vacuumizing by using a water pump to perform neutralization reaction for 40min, stopping stirring, removing water by rotary evaporation, and drying to obtain the dimethyl isophthalate-5-disodium phosphate.
Example 3
Adding 274g of dimethyl isophthalate-5-phosphonic acid, 162g of calcium bicarbonate and 1L of water into a reaction vessel, then completely dissolving the materials under magnetic stirring, slowly heating to 60 ℃, simultaneously vacuumizing by using a water pump to perform neutralization reaction for 50min, stopping stirring, removing water by rotary evaporation, and drying to obtain the dimethyl isophthalate-5-calcium phosphate.
Example 4
Adding 274g of dimethyl isophthalate-5-phosphonic acid, 100g of potassium bicarbonate and 1L of water into a reaction vessel, then completely dissolving the materials under magnetic stirring, slowly heating to 50 ℃, simultaneously vacuumizing by using a water pump to perform neutralization reaction for 40min, stopping stirring, removing water by rotary evaporation, and drying to obtain the potassium isophthalate-5-monohydrogen phosphate.
Example 5
274g of dimethyl terephthalate-2-phosphonic acid, 200g of potassium bicarbonate and 1L of water are added into a reaction vessel, then the materials are completely dissolved under magnetic stirring, the temperature is slowly raised to 50 ℃, meanwhile, the materials are pumped by a water pump to be vacuumized to carry out neutralization reaction for 50min, then the stirring is stopped, the water is removed by rotary evaporation, and the materials are dried to obtain the dimethyl terephthalate-5-dipotassium phosphate.
Example 6
274g of dimethyl terephthalate-2-phosphonic acid, 100g of potassium bicarbonate and 1L of water are added into a reaction vessel, then the materials are completely dissolved under magnetic stirring, the temperature is slowly raised to 45 ℃, meanwhile, the materials are pumped by a water pump to be vacuumized to carry out neutralization reaction for 30min, then the stirring is stopped, the solvent is removed by rotary evaporation, and the materials are dried to obtain the dimethyl terephthalate-5-potassium monohydrogen phosphate.
Example 7
216g of methyl benzoate-4-phosphonic acid, 200g of potassium bicarbonate and 1L of water are added into a reaction vessel, then the mixture is completely dissolved under magnetic stirring, the temperature is slowly raised to 60 ℃, meanwhile, the mixture is pumped by a water pump to perform a neutralization reaction for 30min, then the stirring is stopped, and the water is removed by rotary evaporation and dried, so that the methyl benzoate-4-dipotassium phosphate is obtained.
Example 8
Adding 216g of methyl benzoate-4-phosphonic acid, 100g of potassium bicarbonate and 1L of water into a reaction vessel, then completely dissolving the mixture under magnetic stirring, slowly heating to 70 ℃, simultaneously vacuumizing by using a water pump to perform neutralization reaction for 40min, stopping stirring, removing the solvent by rotary evaporation, and drying to obtain the methyl benzoate-4-potassium monohydrogen phosphate.
Example 9
Adding 210g of methyl benzoate-4-phosphonic acid, 200g of potassium bicarbonate and 1L of water into a reaction vessel, then completely dissolving the mixture under magnetic stirring, slowly heating to 80 ℃, simultaneously vacuumizing by using a water pump to perform neutralization reaction for 30min, stopping stirring, removing water by rotary evaporation, and drying to obtain the methyl benzoate-4-dipotassium phosphate.
Example 10
Adding 582g of dimethyl terephthalate, 465g of ethylene glycol and 2.1g of the ionic monomer obtained in the example 1 into a reaction kettle, and filling nitrogen to remove air in the kettle body; reacting at the normal pressure at 180 ℃ for 2 hours, heating to 200 ℃ for reaction for 1 hour, heating to 225 ℃ for reaction for 2 hours, and finishing the ester exchange reaction; then carrying out low vacuum polycondensation reaction for 1-2h at 240-250 ℃, then carrying out polycondensation reaction for 1-3 h at 260-270 ℃ under high vacuum (the pressure is less than 40Pa), discharging, and carrying out water cooling.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.35 dL/g; the oxygen index is 22.5 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 462kW/m2The total smoke release amount is 11.4m2The amount of residual carbon in cone calorimetry was 11.1 wt%.
Example 11
582g of dimethyl terephthalate, 465g of ethylene glycol and 5.25g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.47 dL/g; the oxygen index is 23.0 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 460kW/m2The total smoke release amount is 10.9m2The amount of residual carbon in cone calorimetry was 11.8 wt%.
Example 12
582g of dimethyl terephthalate, 465g of ethylene glycol and 10.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.61 dL/g; the oxygen index is 23.3 percent, the vertical combustion grade is V-2, and the peak value heat release rate p-HRR in the cone calorimetry test is 379kW/m2The total smoke release amount is 9.9m2The amount of residual carbon in cone calorimetry was 13.0% by weight.
Example 13
582g of dimethyl terephthalate, 465g of ethylene glycol and 21g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.98 dL/g; the oxygen index is 24.5 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 341kW/m2The total smoke release amount is 8.3m2The amount of residual carbon in cone calorimetry was 13.9% by weight.
Example 14
582g of dimethyl terephthalate, 465g of ethylene glycol and 31.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.95 dL/g; the oxygen index is 25 percent, the vertical combustion grade is V-2, and the peak value heat release rate p-HRR in the cone calorimetry test is 323kW/m2The total smoke release amount is 8.0m2The amount of carbon residue in cone calorimetry was 15.4% by weight.
Example 15
582g of dimethyl terephthalate, 465g of ethylene glycol and 52.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.93 dL/g; oxygen index of 26.2%, vertical burning class V-2, cone calorimetry testThe medium peak heat release rate p-HRR is 312kW/m2The total smoke release amount is 7.5m2The amount of residual carbon in cone calorimetry was 17.8 wt%.
Example 16
582g of dimethyl terephthalate, 465g of ethylene glycol and 84g of the ionic monomer obtained in example 1 were charged into a reaction vessel, subjected to transesterification and polycondensation under the procedures and conditions given in example 10, and discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.91 dL/g; the oxygen index is 28.7 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 298kW/m2The total smoke release amount is 6.9m2The amount of carbon residue in cone calorimetry was 20.1% by weight.
Example 17
582g of dimethyl terephthalate, 465g of ethylene glycol and 95.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.87 dL/g; the oxygen index is 29.3 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 275kW/m2The total smoke release amount is 6.2m2The amount of residual carbon in cone calorimetry was 21.1 wt%.
Example 18
582g of dimethyl terephthalate, 465g of ethylene glycol and 105g of the ionic monomer obtained in example 1 were charged into a reaction vessel, subjected to transesterification and polycondensation in accordance with the procedures and conditions given in example 10, and then discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.85 dL/g; the oxygen index is 30.5 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 254kW/m2The total smoke release amount is 5.8m2The amount of carbon residue in cone calorimetry was 22.3% by weight.
Example 19
582g of dimethyl terephthalate, 465g of ethylene glycol and 115.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.81 dL/g; the oxygen index is 31.4 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 244kW/m2The total smoke release amount is 5.0m2The amount of carbon residue in cone calorimetry was 24.5% by weight.
Example 20
582g of dimethyl terephthalate, 465g of ethylene glycol and 126g of the ionic monomer obtained in example 1 were charged into a reaction vessel, subjected to transesterification and polycondensation under the procedures and conditions given in example 10, and discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.79 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 232kW/m2The total smoke release amount is 4.6m2The amount of residual carbon in cone calorimetry was 25.1% by weight.
Example 21
582g of dimethyl terephthalate, 465g of ethylene glycol and 136.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.72 dL/g; the oxygen index is 33.4 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 215kW/m2The total smoke release amount is 4.2m2The amount of residual carbon in cone calorimetry was 26.0% by weight.
Example 22
582g of dimethyl terephthalate, 465g of ethylene glycol and 147g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.63 dL/g; the oxygen index is 34.5 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 164kW/m2The total smoke release amount is 3.7m2The amount of carbon residue in cone calorimetry was 27.3% by weight.
Example 23
582g of dimethyl terephthalate, 465g of ethylene glycol and 157.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.45 dL/g; the oxygen index is 36.0 percent, the vertical combustion grade is V-0, and the peak heat release rate p-HRR in the cone calorimetry test is 135kW/m2The total smoke release amount is 3.1m2The amount of carbon residue in cone calorimetry was 28.1% by weight.
Example 24
582g of dimethyl terephthalate, 380g of 1, 3-propanediol and 31.5g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out according to the procedures and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.90 dL/g; the oxygen index is 24.5 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 540kW/m2The total smoke release amount is 11.8m2The amount of carbon residue in cone calorimetry was 13.5% by weight.
Example 25
582g of dimethyl terephthalate, 450g of 1, 4-butanediol and 42g of the ionic monomer obtained in example 1 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.87 dL/g; the oxygen index is 24.0 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 621kW/m2The total smoke release amount is 10.7m2The amount of carbon residue in cone calorimetry was 12.1% by weight.
Example 26
438g of dimethyl butyrate, 450g of 1, 4-butanediol and 42g of the ionic monomer obtained in example 1 were charged into a reaction vessel, subjected to transesterification and polycondensation under the procedures and conditions given in example 10, and then discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.75 dL/g; the oxygen index is 23.0 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 430kW/m2The total smoke release amount is 11.0m2Cone calorimetry test residueThe carbon content was 10.3 wt%.
Example 27
582g of dimethyl terephthalate, 310g of ethylene glycol and 19.1g of the ionic monomer obtained in example 2 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.97 dL/g; the oxygen index is 24.3 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 422kW/m2The total smoke release amount is 11.1m2The amount of carbon residue in cone calorimetry was 13.5% by weight.
Example 28
582g of dimethyl terephthalate, 310g of ethylene glycol and 18.7g of the ionic monomer obtained in example 4 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.87 dL/g; the oxygen index is 24.0 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 480kW/m2The total smoke release amount is 10.3m2The amount of residual carbon in cone calorimetry was 13.1 wt%.
Example 29
582g of dimethyl terephthalate, 310g of ethylene glycol and 42g of the ionic monomer obtained in example 5 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.95 dL/g; the oxygen index is 24.7 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 364kW/m2The total smoke release amount is 8.8m2The amount of carbon residue in cone calorimetry was 15.5% by weight.
Example 30
582g of dimethyl terephthalate, 310g of ethylene glycol and 28.1g of the ionic monomer obtained in example 6 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.81 dL/g; oxygen index of 24.2%, vertical combustionGrade V-2, peak heat release rate p-HRR in cone calorimetry test 412kW/m2The total smoke release amount is 9.4m2The amount of residual carbon in cone calorimetry was 14.1% by weight.
Example 31
582g of dimethyl terephthalate, 310g of ethylene glycol and 43.8g of the ionic monomer obtained in example 7 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.90 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 330kW/m2The total smoke release amount is 8.1m2The amount of carbon residue in cone calorimetry was 15.7% by weight.
Example 32
582g of dimethyl terephthalate, 3010g of ethylene glycol and 38.1g of the ionic monomer obtained in example 8 were charged in a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedures and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.81 dL/g; the oxygen index is 24.8 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 470kW/m2The total smoke release amount is 8.3m2The amount of residual carbon in cone calorimetry was 14.3% by weight.
Example 33
582g of dimethyl terephthalate, 310g of ethylene glycol and 41.7g of the ionic monomer obtained in example 9 were charged into a reaction vessel, and after transesterification and polycondensation were carried out in accordance with the procedure and conditions given in example 10, they were discharged.
Intrinsic viscosity [ eta ] of the resulting ionomer]0.94 dL/g; the oxygen index is 26.4 percent, the vertical combustion grade is V-2, and the peak heat release rate p-HRR in the cone calorimetry test is 450kW/m2The total smoke release amount is 8.1m2The amount of carbon residue in cone calorimetry was 13.5% by weight.
Comparative example
582g of dimethyl terephthalate, 310g of ethylene glycol, 1g of zinc acetate and 0.8g of antimony trioxide were added to a reaction kettle, and after ester exchange and polycondensation were carried out according to the steps and conditions given in example 10, the product was discharged.
Intrinsic viscosity [ eta ] of the resulting polyester]0.78 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/m2The total smoke release amount is 15.5m2The amount of carbon residue in cone calorimetry was 8.6% by weight.

Claims (5)

1. A preparation method of a flame-retardant smoke-suppressing ionomer catalytically synthesized by ionic monomers containing phosphonate structures is characterized in that the ionomer consists of structural units represented by the following I, II and III or structural units represented by the following I, II and IV:
Figure FDA0003214468580000011
in the formula, R3Represents an arylene group or C2～C8Alkylene of (2)
Figure FDA0003214468580000012
In the formula, R4Represents an arylene group or C2～C8The alkylene group of (a) is,
Figure FDA0003214468580000013
in the formula, R1、R2Is composed of
Figure FDA0003214468580000014
Or any one of-O-, which may be the same or different, M is a metal ion, and n is an integer of 1-3;
Figure FDA0003214468580000021
in the formula, R5、R6Is C2～C8The alkylene groups of (A) may be the same or different, M is a metal ion, n is an integer of 1 to 3,
wherein, the structural unit number of III is 0.2-15.0% of the structural unit 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 0.2-15.0% of that of the I structural units, and I: the structural unit of [ II + IV ] is 1, each structural unit or formed chain segment is optionally connected and combined according to carboxyl and hydroxyl functional groups, the intrinsic viscosity of the ionomer is [ eta ] of 0.35-0.98 dL/g, and the limiting oxygen index is 22.5-36.0%; the vertical combustion grade is V-2 to V-0 grade; the peak heat release rate p-HRR in the cone calorimetry test is reduced to 18.4-62.9% of that of pure PET; the total smoke release amount is reduced to 20.0-73.5% of that of pure PET;
the method comprises mixing dibasic acid or its ester with C2～C8The copolyester monomer of the polyhydric alcohol is prepared by esterification through a direct esterification method or an ester exchange method and then polycondensation, and is characterized in that before the esterification or before the polycondensation after the esterification, a phosphonate structure-containing ionic monomer which is 0.2-15.0% of the molar weight ratio of dibasic acid or esterified matter thereof in the polyester monomer is added into a reaction system as a catalyst, wherein the used phosphonate structure-containing ionic monomer is any one of the following structural general formulas:
，
Figure FDA0003214468580000031
in the formula, R1、R2Is a carboxyl group, an ester group, a hydroxyl group or
Figure FDA0003214468580000032
Any one of which may be the same or different, a is an integer of 2 to 8, M is a metal ion, and n is an integer of 1 to 3.
2. The method according to claim 1, wherein R is1、R2The middle ester group is methyl ester group, ethyl ester group or phenyl ester group after monohydric alcohol esterification, or is any one of ethylene glycol ester group, propylene glycol ester group, butanediol group, neopentyl glycol ester group, glycerol ester group or pentaerythritol ester group after polyhydric alcohol esterification; the M metal ion is any one of Li, Na, K, Mg, Ca, Mn, Co, Ni, Zn or Al.
3. The preparation method according to claim 1, wherein the ionic monomer containing phosphonate structure is prepared by performing neutralization reaction on a precursor containing phosphonate group, solvent water, and hydroxide, carbonate or bicarbonate containing metal ions according to a conventional molar ratio to prepare the ionic monomer containing phosphonate structure, wherein the precursor is a compound of the following structural formula:
Figure FDA0003214468580000033
in the formula, R1、R2Is a carboxyl group, an ester group, a hydroxyl group or
Figure FDA0003214468580000034
Can be the same or different, and a is an integer of 2-8.
4. The method according to claim 3, wherein the ester group in the precursor containing a phosphonic acid group is any one of a methyl ester group, an ethyl ester group or a phenyl ester group after esterification of a monohydric alcohol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol group, a neopentyl glycol ester group, a glycerol ester group or a pentaerythritol ester group after esterification of a polyhydric alcohol; the hydroxide, carbonate or bicarbonate containing metal ions is hydroxide, carbonate or bicarbonate containing Li, Na, K, Mg, Ca, Mn, Co, Ni, Zn or Al ions.
5. The process according to claim 1, wherein the ionomer III has a structural unit number of 2.0 to 8.0% of the structural unit number I, and the ionomer II has a structural unit number of II: the number of structural units of [ i + iii ] is 1; the number of the IV structural units is 2.0-8.0% of that of the I structural units, and I: the structural unit of [ II + IV ] is 1, the intrinsic viscosity of the ionomer is [ eta ] of 0.91-0.98 dL/g, and the limiting oxygen index is 24.5-28.7%; the vertical combustion grade is V-2 to V-0 grade; the peak heat release rate p-HRR in the cone calorimetry test is reduced to 40.6-46.5% of that of pure PET; the total smoke release amount is reduced to 44.5-53.5% of that of pure PET.
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