CN111533894A - Phosphorus-nitrogen-containing flame-retardant polyester and preparation method thereof - Google Patents
Phosphorus-nitrogen-containing flame-retardant polyester and preparation method thereof Download PDFInfo
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- CN111533894A CN111533894A CN202010544018.3A CN202010544018A CN111533894A CN 111533894 A CN111533894 A CN 111533894A CN 202010544018 A CN202010544018 A CN 202010544018A CN 111533894 A CN111533894 A CN 111533894A
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- 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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- 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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention discloses a phosphorus-nitrogen-containing flame-retardant polyester and a preparation method thereof, wherein the preparation method comprises the following steps: 1) preparing an esterification reaction product of terephthalic acid and ethylene glycol; 2) preparing an esterification reaction product of bis (2-carboxyethyl) isocyanurate and ethylene glycol; 3) mixing 1) and 2) esterified substances and phosphorus-containing monomers for polycondensation reaction to obtain phosphorus-nitrogen-containing flame-retardant polyester; the phosphorus-containing monomer is dihydric alcohol containing phosphate ester prepared by reacting a flame retardant ODOPB and propylene oxide; the invention introduces the nitrogen-containing monomer and the phosphorus-containing monomer as the third monomer and the fourth monomer, and the monomers are copolymerized with the terephthalic acid and the ethylene glycol to prepare the polyester, the viscosity of the polyester is controllable in the polycondensation process, the performance of the product is stable, the product realizes the in-situ synergistic interaction of the phosphorus-nitrogen flame-retardant elements, and the product has potential application prospect in the preparation of flame-retardant textiles.
Description
Technical Field
The invention belongs to the field of synthetic fibers, and particularly relates to phosphorus-nitrogen-containing flame-retardant polyester and a preparation method thereof.
Background
The flame-retardant polyester fiber has wide market prospect in clothing, ornaments and industrial products, such as children clothing, special industry clothing, textile ornaments used in public places such as hotels and entertainment, textiles for transportation, textiles for packaging and the like. The flame retardants commonly used are classified into halogen-based, nitrogen-based, organic phosphorus-based, inorganic phosphorus-based, boron-based, silicon-based, molybdenum-based, and the like, depending on the kind of the flame retardant element. Halogen-based brominated flame retardants have good flame retardant properties, but can release toxic gaseous hydrogen halide during combustion, causing environmental pollution, and limiting their applications. In contrast, the phosphorus and nitrogen flame retardant is not easy to release corrosive gas in the combustion process, has good smoke suppression performance and has wide application prospect.
The southern Jiangnan university reports that the LOI of the flame-retardant polyester is improved to 28.7 percent by a method of synthesizing a phosphorus-nitrogen flame retardant diethyl-methacrylamide phosphate ester by taking diethyl chlorophosphate and methacrylamide as reactants and finishing the diethyl-methacrylamide phosphate ester on a polyester fabric by a dipping method. (Ding, Nippon, phosphorus and nitrogen flame retardant for flame-retardant finishing of polyester fabrics [ J ]. textile science 2020,41(03):100- & 105.) the method introduces phosphorus flame retardant by means of fabric finishing, but the method can not avoid obvious deterioration of the appearance performance of the textiles. The Beijing clothing college reports that a flame-retardant polyester is synthesized by taking tris (2-hydroxyethyl) isocyanurate (THEIC) and Purified Terephthalic Acid (PTA) as raw materials, and T-ester is compounded with ammonium polyphosphate to form a novel intumescent flame retardant which is subjected to melt blending spinning with polyethylene glycol terephthalate to obtain the flame-retardant polyester. The two above approaches (surface finishing and co-spinning) have the disadvantage that no durable flame retardancy can be obtained.
Disclosure of Invention
The invention aims to provide phosphorus-nitrogen-containing flame-retardant polyester and a preparation method thereof. The nitrogen-containing monomer is di (2-carboxyethyl) isocyanurate, and the phosphorus-containing monomer is a reaction product of a flame retardant ODOPB and propylene oxide. The polyester has controllable viscosity in the polycondensation process, stable product performance and potential application prospect in preparing flame-retardant textiles.
The invention also aims to provide a preparation method of the phosphorus-nitrogen-containing flame-retardant polyester.
The reaction flow and the preparation method of the phosphorus-nitrogen-containing flame-retardant polyester are as follows:
1. preparation of the first ester
Putting terephthalic acid, ethylene glycol and antimony acetate into a reaction kettle according to a certain proportion, and introducing N2Controlling the reaction pressure to be 0.15-0.40 MPa, carrying out esterification reaction for 1-3 h at 180-200 ℃, and stopping the reaction when the esterification rate reaches 90% to obtain a first esterified substance.
The feeding molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.3-1.5, and the using amount of the antimony acetate is 0.03-0.1% of the weight of the terephthalic acid.
The structural formula of the first esterified compound is as follows:
2. preparation of the second diester
Putting a nitrogenous monomer di (2-carboxyethyl) isocyanurate, ethylene glycol and antimony acetate into a reaction kettle according to a certain proportion, and introducing N2And controlling the reaction pressure to be 0.15-0.40 MPa, carrying out esterification reaction for 1-3 h at 180-200 ℃, and stopping the reaction when the esterification rate reaches 80% to obtain a second esterified substance.
The feeding molar ratio of the bis (2-carboxyethyl) isocyanurate to the ethylene glycol is 1: 1.5-2, and the using amount of the antimony acetate is 0.03-0.1% of the weight of the terephthalic acid.
The second diester has the following structural formula:
3. preparation of phosphorus-containing monomer (M1)
Putting a flame retardant ODOPB and propylene oxide into a reaction kettle according to a certain proportion, adding water, fully stirring and dissolving, adjusting the pH to 8-10 by NaOH, reacting for 4 hours at 70-90 ℃, passing through a column, volatilizing a solvent to obtain a phosphorus-containing monomer (M1)
The structural formula of the flame retardant ODOPB is as follows:
the feeding molar ratio of the flame retardant ODOPB, the propylene oxide and the water is 1: 1.3-1.5: 50-60.
The phosphorus-containing monomer (M1) has the following structural formula:
4. preparation of phosphorus-nitrogen-containing flame-retardant polyester by polycondensation
Mixing the second esterification product and the first esterification product according to a certain proportion, adding antimony acetate and trimethyl phosphate, controlling the vacuum degree at 800-1500 Pa, and carrying out pre-polycondensation reaction for 1-3 h at 220-260 ℃; continuously adding M1 and tetrabutyl titanate, uniformly mixing, performing final polycondensation for 4-7 h under the reaction conditions of 15-200 Pa and 240-280 ℃, relieving vacuum by using nitrogen, discharging, cooling, and slicing to obtain the phosphorus-nitrogen-containing flame-retardant polyester.
The mass ratio of the first esterified substance to the second esterified substance to M1 is 200: 5-15: 50-100, the mass of antimony acetate is 0.01-0.025% of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.01-0.025% of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.02-0.04% of the total mass of the first esterified substance and the second esterified substance.
The invention has the following advantages and beneficial effects:
(1) by introducing phosphorus-containing and nitrogen-containing monomers into the flame-retardant polyester polymer, the in-situ synergistic flame retardance of phosphorus-nitrogen flame-retardant elements is realized, and the problems of timeliness, durability and the like of flame retardance are fundamentally solved.
(2) The phosphorus-nitrogen-containing flame-retardant polyester has multiple chain segment structures, so that the affinity and compatibility of the phosphorus-nitrogen-containing flame-retardant polyester with related textile printing and dyeing auxiliaries (such as silicone oil, a delustering agent, an antibacterial agent and a waterproof agent) are increased, the subsequent textile dyeing and finishing processing is easier to carry out, and the preparation of the soft and smooth, antistatic, delustering or matte, antibacterial, waterproof and other functionalized flame-retardant products is facilitated.
(3) The polyester has controllable viscosity in the polycondensation process, stable performance of the product, and synergistic effect with flame retardance of various systems, and can be applied to curtains, carpets, home textile fabrics, medical curtains, energy industry fabrics, electric power industry fabrics and water conservancy geotechnical fabrics.
Drawings
FIG. 1 shows the preparation of the phosphorus-containing monomer (M1) according to example 113C-NMR。
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The test of the invention comprises the following steps:
intrinsic viscosity: the intrinsic viscosity of the polyester was measured by using a phenol/tetrachloroethane solution at a mass ratio of 1:1 and a full-automatic viscometer with a capillary diameter of 1.2 mm.
Elemental analysis: the samples were tested for N, P element content using the German ElmentarVarioEL element Analyzer.
Limiting Oxygen Index (LOI): the test was carried out according to the national standard GB/T2406-1993.
Differential Scanning Calorimetry (DSC): in the nitrogen atmosphere, the nitrogen flow rate is 20mL/min, the temperature is increased from room temperature to 300 ℃, and then the temperature is reduced to 0 ℃ so as to eliminate the heat history; the temperature is raised for the second time from 0 ℃ to 300 ℃, and the heating rate is 20 ℃/min; the cold crystallization temperature Tc, melting temperature Tm, and peak enthalpy of crystallization Δ H for each example are shown in Table 1.
Thermogravimetric analysis (TG): the amount of the sample is 6-8 mg, the nitrogen atmosphere is adopted, the nitrogen flow rate is 100mL/min, the heating rate is 10 ℃/min, the scanning temperature is 30-500 ℃, and the residual ash rate of each example at 500 ℃ is shown in Table 1.
Example 1
(1) Preparation of the first ester: feeding terephthalic acid and ethylene glycol in a molar ratio of 1:1.5, wherein the dosage of antimony acetate is 0.05 percent of the weight of the terephthalic acid; the reaction pressure is 0.4MPa, the reaction temperature is 180 ℃, the esterification reaction time is 1h, and the reaction is stopped when the esterification rate is 92.8 percent.
(2) Preparation of the second diester: the feeding molar ratio of the di (2-carboxyethyl) isocyanurate to the ethylene glycol is 1:1.8, and the using amount of the antimony acetate is 0.1 percent of the weight of the terephthalic acid; the reaction pressure is 0.15MPa, the reaction temperature is 200 ℃, the esterification reaction time is 2h, and the reaction is stopped when the esterification rate is 81.5 percent.
(3) Preparation of phosphorus-containing monomer (M1): weighing the flame retardant ODOPB, the propylene oxide and the deionized water according to the molar ratio of 1:1.5:60, putting the mixture into a reaction kettle, fully stirring and dissolving, adding NaOH solid, adjusting the pH to 8, reacting at 80 ℃ for 4 hours, and separating the mixture through a silica gel column chromatography by using dichloromethane as an eluent to obtain M1 by volatilizing the solvent through the column chromatography.
Of M113C-NMR is shown in FIG. 1.
Example 2
The first esterified product, the second esterified product, and M1 were prepared as in example 1.
The preparation conditions of the phosphorus-nitrogen containing flame-retardant polyester are as follows:
the mass part ratio of the first esterified substance to the second esterified substance is 200:15:100, the mass of antimony acetate is 0.02 percent of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.02 percent of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.02 percent of the total mass of the first esterified substance and the second esterified substance.
The pre-polycondensation reaction conditions are as follows: the reaction pressure is 1500Pa, the reaction temperature is 260 ℃, and the reaction time is 2.5 h; final polycondensation reaction conditions: the reaction pressure is lower than 50Pa, the reaction temperature is 280 ℃, and the reaction time is 5.5 h.
Example 3
The first esterified product, the second esterified product, and M1 were prepared as in example 1.
The preparation conditions of the phosphorus-nitrogen containing flame-retardant polyester are as follows:
the mass part ratio of the first esterified substance to the second esterified substance is 200:10:100, the mass of antimony acetate is 0.02 percent of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.02 percent of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.02 percent of the total mass of the first esterified substance and the second esterified substance.
The pre-polycondensation reaction conditions are as follows: the reaction pressure is 1500Pa, the reaction temperature is 255 ℃, and the reaction time is 3 h; final polycondensation reaction conditions: the reaction pressure is lower than 50Pa, the reaction temperature is 270 ℃, and the reaction time is 7 h.
Example 4
The first esterified product, the second esterified product, and M1 were prepared as in example 1.
The preparation conditions of the phosphorus-nitrogen containing flame-retardant polyester are as follows:
the mass part ratio of the first esterified substance to the second esterified substance is 200:5:100, the mass of antimony acetate is 0.025 percent of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.01 percent of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.04 percent of the total mass of the first esterified substance and the second esterified substance.
The pre-polycondensation reaction conditions are as follows: the reaction pressure is 1200Pa, the reaction temperature is 235 ℃, and the reaction time is 2 h; final polycondensation reaction conditions: the reaction pressure is lower than 50Pa, the reaction temperature is 260 ℃ and the reaction time is 5 h.
Example 5
The first esterified product, the second esterified product, and M1 were prepared as in example 1.
The preparation conditions of the phosphorus-nitrogen containing flame-retardant polyester are as follows:
the mass part ratio of the first esterified substance to the second esterified substance is 200:10:80, the mass of antimony acetate is 0.025 percent of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.025 percent of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.03 percent of the total mass of the first esterified substance and the second esterified substance.
The pre-polycondensation reaction conditions are as follows: the reaction pressure is 800Pa, the reaction temperature is 240 ℃, and the reaction time is 2 h; final polycondensation reaction conditions: the reaction pressure is lower than 50Pa, the reaction temperature is 260 ℃ and the reaction time is 6.5 h.
Example 6
The first esterified product, the second esterified product, and M1 were prepared as in example 1.
The preparation conditions of the phosphorus-nitrogen containing flame-retardant polyester are as follows:
the mass part ratio of the first esterified substance to the second esterified substance is 200:10:50, the mass of antimony acetate is 0.01 percent of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.01 percent of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.03 percent of the total mass of the first esterified substance and the second esterified substance.
The pre-polycondensation reaction conditions are as follows: the reaction pressure is 800Pa, the reaction temperature is 220 ℃, and the reaction time is 3 h; final polycondensation reaction conditions: the reaction pressure is lower than 50Pa, the reaction temperature is 250 ℃, and the reaction time is 4 h.
Comparative example 1
Fiber grade polyester chips were purchased from southeast chemical fiber materials ltd, ceremony.
TABLE 1
As can be seen from Table 1, the limiting oxygen index and the residual ash rate of the phosphorus-nitrogen-containing flame-retardant polyester are greatly improved compared with those of common fiber-grade polyester chips, but with the increase of the content of phosphorus and nitrogen in the polyester, the Tm, Tc and Delta H of the system all have a tendency of decreasing, which is because the regularity of the polyester molecular chain is decreased due to the addition of the phosphorus-nitrogen-containing reaction monomer.
Claims (3)
1. The phosphorus-nitrogen-containing flame-retardant polyester and the preparation method thereof are characterized by comprising the following steps:
(1) preparation of the first ester
Antimony acetate is used as a catalyst, terephthalic acid and ethylene glycol are used as monomers, an esterification reaction is carried out for 1-3 hours at 180-200 ℃ under 0.15-0.40 MPa, and the reaction is stopped when the esterification rate reaches 90%, so that a first esterified substance is obtained.
The first ester has a structure of formula (I):
(2) preparation of the second diester
Antimony acetate is used as a catalyst, a nitrogen-containing monomer bis (2-carboxyethyl) isocyanurate and ethylene glycol are used as monomers, an esterification reaction is carried out for 1-3 hours at 180-200 ℃ under 0.15-0.40 MPa, and the reaction is stopped when the esterification rate reaches 80% to obtain a first esterified substance.
The second diester has the structure of formula (II):
(3) preparation of phosphorus-containing monomer (M1)
Reacting a flame retardant ODOPB and propylene oxide for 4 hours at the alkaline condition of 70-90 ℃, and passing through a column to volatilize a solvent to obtain M1;
the phosphorus-containing monomer (M1) has the structure of formula (III):
(4) preparation of phosphorus-nitrogen-containing flame-retardant polyester by polycondensation
Mixing the second esterification product and the first esterification product according to a certain proportion, adding antimony acetate and trimethyl phosphate, controlling the vacuum degree at 800-1500 Pa, and carrying out pre-polycondensation reaction for 1-3 h at 220-260 ℃; continuously adding M1 and tetrabutyl titanate, uniformly mixing, performing final polycondensation for 4-7 h under the reaction conditions of 15-200 Pa and 240-280 ℃, relieving vacuum by using nitrogen, discharging, cooling, and slicing to obtain the phosphorus-nitrogen-containing flame-retardant polyester.
2. The phosphorus-nitrogen-containing flame-retardant polyester and the preparation method thereof according to claim 1, characterized in that:
the feeding molar ratio of the terephthalic acid to the ethylene glycol in the step (1) is 1: 1.3-1.5, and the using amount of the antimony acetate is 0.03-0.1% of the weight of the terephthalic acid;
the feeding molar ratio of the bis (2-carboxyethyl) isocyanurate to the ethylene glycol in the step (2) is 1: 1.5-2, and the using amount of the antimony acetate is 0.03-0.1% of the weight of the terephthalic acid;
the structural formula of the flame retardant ODOPB in the step (3) is shown as the formula (IV):
the feeding molar ratio of the flame retardant ODOPB, the propylene oxide and the water in the step (3) is 1: 1.3-1.5: 50-60;
the mass part ratio of the first esterified substance, the second esterified substance and the M1 in the step (4) is 200: 5-15: 50-100, the mass of antimony acetate is 0.01-0.025% of the total mass of the first esterified substance and the second esterified substance, the mass of trimethyl phosphate is 0.01-0.025% of the total mass of the first esterified substance and the second esterified substance, and the mass of tetrabutyl titanate is 0.02-0.04% of the total mass of the first esterified substance and the second esterified substance.
3. The phosphorus-nitrogen-containing flame-retardant polyester and the preparation method thereof according to claim 1 or 2, characterized in that: the intrinsic viscosity of the copolyester is 0.8-1.2 dL/g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592468A (en) * | 2020-12-15 | 2021-04-02 | 吴春秋 | Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating |
| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN116948163A (en) * | 2023-09-20 | 2023-10-27 | 山东一诺威新材料有限公司 | Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof |
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2020
- 2020-06-15 CN CN202010544018.3A patent/CN111533894A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592468A (en) * | 2020-12-15 | 2021-04-02 | 吴春秋 | Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating |
| CN112592468B (en) * | 2020-12-15 | 2021-08-27 | 宁波顺声通讯设备有限公司 | Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating |
| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN116948163A (en) * | 2023-09-20 | 2023-10-27 | 山东一诺威新材料有限公司 | Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof |
| CN116948163B (en) * | 2023-09-20 | 2023-12-29 | 山东一诺威新材料有限公司 | Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof |
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