CN115028821B - Preparation method of hydrophilic flame-retardant polyester - Google Patents
Preparation method of hydrophilic flame-retardant polyester Download PDFInfo
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- CN115028821B CN115028821B CN202210971057.0A CN202210971057A CN115028821B CN 115028821 B CN115028821 B CN 115028821B CN 202210971057 A CN202210971057 A CN 202210971057A CN 115028821 B CN115028821 B CN 115028821B
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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
- C08G63/692—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
- C08G63/78—Preparation processes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention discloses a preparation method of hydrophilic flame-retardant polyester, which comprises the following steps: phosphorus oxychloride reacts with pentaerythritol and methyl p-hydroxybenzoate in two steps to prepare phosphorus-nitrogen-containing monomer, and the phosphorus-nitrogen-containing monomer, dimethyl terephthalate and ethylene glycol are subjected to ester exchange and polycondensation to form hydrophilic flame-retardant polyester; the hydrophilic flame-retardant polyester prepared by the invention meets the requirement of lasting flame retardance, simultaneously improves the hydrophilic hygroscopicity of the polyester, keeps good crystallinity and has strong spinnability. In addition, the polyester has controllable viscosity in the polycondensation process, stable product performance and potential application prospect in preparing flame-retardant textiles.
Description
Technical Field
The invention belongs to the field of synthetic fibers, and particularly relates to a preparation method of hydrophilic flame-retardant polyester.
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, entertainment and the like, 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, ning-Kong, phosphorus-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 technical scheme is that tris (2-hydroxyethyl) isocyanurate (THEIC) and Purified Terephthalic Acid (PTA) are used as raw materials to synthesize tris (2-hydroxyethyl) isocyanurate terephthalate (T-ester), the T-ester and ammonium polyphosphate are compounded to form a novel intumescent flame retardant, and the novel intumescent flame retardant and polyethylene glycol terephthalate are subjected to melt blending spinning 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 a preparation method of hydrophilic flame-retardant polyester, which designs and synthesizes a reactive flame retardant meeting the requirements of fiber-grade polyester chips, and performs ester exchange reaction with dimethyl terephthalate and ethylene glycol; the copolyester can still keep good crystallization property while meeting the requirement of durable flame retardance, and the hydrophilicity of the polyester fiber is improved. In addition, the copolyester has controllable viscosity in the polycondensation process, stable performance of the product and potential application prospect in preparing flame-retardant textiles.
The reaction flow and the preparation method of the hydrophilic flame-retardant polyester are as follows:
1. preparation of intermediate A
Adding pentamine, triethylamine and dry chloroform into a reaction bottle provided with a reflux condenser tube, a constant-pressure dropping funnel and a stirrer to ensure that the molar concentration of the pentamine is 1 to 2 mol/L, and stirring to fully dissolve and mix the pentamine; weighing phosphorus oxychloride, dissolving the phosphorus oxychloride in chloroform, putting the chloroform into a constant-pressure dropping funnel, dropwise adding a chloroform solution of phosphorus oxychloride with the molar concentration of 2 mol/L under ice bath, removing an ice bath after 0.5 to 1 hour of dropwise adding, slowly heating to 60 to 80 ℃, refluxing for 4 to 6 hours, distilling under reduced pressure to obtain white powder, washing with cold water for 2 times, and drying for later use to obtain an intermediate A.
The feeding molar ratio of the pentamine to the phosphorus oxychloride is 1: 2 to 5, and preferably, the feeding molar ratio of the pentamine to the phosphorus oxychloride is 1: 2.6 to 3.
The feeding molar ratio of the triethylamine to the pentaenetetramine is 5: 1.
Preferably, the reaction temperature is 60 ℃ and the reaction time is 5 h.
The intermediate A has the following structural formula:
(I)
2. preparation of phosphorus-nitrogen-containing monomer
And at room temperature, dissolving the intermediate A again by using chloroform, adding methyl p-hydroxybenzoate and anhydrous aluminum trichloride, heating to 60-80 ℃ for reflux reaction for 3-6 h after complete dissolution, adding distilled water into the reaction liquid for extraction for 3 times, carrying out reduced pressure distillation to obtain a crude product, and recrystallizing by using acetone to obtain a white powdery solid which is a phosphorus-nitrogen-containing monomer.
The feeding molar ratio of the intermediate A to the methyl p-hydroxybenzoate is 1: 2 to 2.2.
The feeding amount of the anhydrous aluminum trichloride is 0.5 to 0.7 percent of the feeding mass of the intermediate A.
The chloroform is added in an amount such that the molar concentration of the intermediate A is 0.5 to 1 mol/L.
Preferably, the reaction temperature is 80 ℃ and the reaction time is 4 hours.
The phosphorus-nitrogen-containing monomer has the following structural formula:
(II)
3. preparation of hydrophilic flame-retardant polyester chip
Mixing dimethyl terephthalate, phosphorus-nitrogen-containing monomer, ethylene glycol, trimethyl phosphate and antimony acetate according to a certain proportion, putting the mixture into a reaction kettle, and introducing N 2 And carrying out ester exchange reaction at 160-200 ℃ for 4-6 h, wherein 90% of theoretical value of methanol distillation amount is used as the end point of the esterification reaction. Then raising the temperature to 240-260 ℃, starting a vacuum pump, and controlling the vacuum degree within 0.2-0.4 MPa for pre-shrinking for 2-4 h; and continuously heating to 260-280 ℃, controlling the vacuum degree to be lower than 50 Pa, starting final polycondensation for 3-5 h, relieving vacuum with nitrogen, discharging, cooling and slicing to obtain the hydrophilic flame-retardant polyester slice.
The feeding molar ratio of the dimethyl terephthalate to the phosphorus-nitrogen-containing monomer to the ethylene glycol is 100: 2 to 12: 120 to 150, the mass of the antimony acetate is 0.02 to 0.04 percent of that of the dimethyl terephthalate, and the mass of the trimethyl phosphate is 0.02 to 0.04 percent of that of the dimethyl terephthalate.
The invention has the following advantages and beneficial effects:
(1) According to the invention, the phosphorus-nitrogen-containing unit is introduced into the polyester molecular chain to obtain the copolymerization type flame-retardant polyester, so that the in-situ synergistic flame retardance of phosphorus-nitrogen flame-retardant elements is realized, and the problems of timeliness, durability and the like of the flame retardance are fundamentally solved.
(2) The phosphorus-nitrogen-containing unit is introduced into the polyester molecular chain, so that the hydrophilic hygroscopicity of the polyester molecular chain is improved, the affinity and the compatibility of the polyester molecular chain and 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 product performance and good fiber forming property, has synergistic effect with flame retardance of various systems, and can be applied to curtains, carpets, home textile fabrics, medical barrier curtains, energy industrial fabrics, electric power industrial fabrics and water conservancy geotechnical fabrics.
Drawings
FIG. 1 is a drawing showing a mixture of phosphorus and nitrogen-containing monomers and hydrophilic flame-retardant polyester prepared in example 1 1 H-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 content of P and N elements in the sample was measured by using German Elmentar variao EL 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 20 mL/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.
And (3) moisture regain testing: washing 50G of fiber with ethanol for 2 times, putting the fiber into an oven, drying the fiber to constant weight, standing the fiber in a standard atmosphere (the temperature is 20 ℃ and the relative humidity is 65 percent) for 48 hours, taking the fiber out, and recording the mass G; drying in oven to constant weight, and recording mass G 0 Calculating the moisture regain according to the following formula:
example 1
(1) Preparation of intermediate A
30.14 g (0.23 mol) of pentaerythrityl tetramine, 83.75g (0.83 mol) of triethylamine and 230 mL of dry chloroform are added into a reaction bottle provided with a reflux condenser tube, a constant pressure dropping funnel and a stirrer, and stirred to be fully dissolved and mixed; weighing 75.46 g (0.5 mol) of phosphorus oxychloride, dissolving the phosphorus oxychloride in 250 mL of chloroform, putting the chloroform into a constant-pressure dropping funnel, dropwise adding the chloroform in ice bath, removing an ice bath after the dropwise adding is finished within 0.5 h, slowly heating to 60 ℃, refluxing for 5 h, distilling under reduced pressure to obtain white powder, washing the white powder with cold water for 2 times, and drying for later use to obtain an intermediate A.
(2) Preparation of phosphorus-nitrogen-containing monomer
30.05g of the intermediate A, 34.42g of methyl p-hydroxybenzoate and 0.15g of anhydrous aluminum trichloride are respectively weighed and placed in a reaction kettle, 200mL of dry chloroform is added, the mixture is stirred until the solid is completely dissolved, the mixture is heated to 80 ℃ for reflux reaction for 4 hours, distilled water is added into the reaction liquid for extraction for 3 times, a crude product is obtained through reduced pressure distillation, acetone is used for recrystallization, and a white powdery solid which is a phosphorus-nitrogen-containing monomer is obtained, and the yield is 42.2%.
(3) Preparation of hydrophilic flame-retardant polyester
The feeding molar ratio of dimethyl terephthalate, phosphorus-nitrogen-containing monomer and ethylene glycol is 100: 12: 140, the mass of antimony acetate is 0.04% of that of dimethyl terephthalate, and the mass of trimethyl phosphate is 0.03% of that of dimethyl terephthalate.
Controlling the ester exchange reaction temperature at 160 ℃, when the methanol distillate is 91.3 percent of a theoretical value, heating to 250 ℃, and starting a vacuum pump to control the vacuum degree at 0.4 MPa for pre-polycondensation for 3 hours; and continuously heating to 270 ℃, controlling the vacuum degree to be lower than 50 Pa, carrying out final polycondensation, relieving the vacuum with nitrogen after 4 hours, discharging, cooling, and slicing to obtain the hydrophilic flame-retardant polyester.
The phosphorus-nitrogen-containing monomer and the hydrophilic flame-retardant polyester prepared in example 1 were subjected to molecular structure characterization, 1 H-NMR spectra were determined using a Bruker AV-400 NMR spectrometer using DMSO (TMS internal standard) and the results are shown in FIG. 1.
Example 2
Steps (1) and (2) are the same as in example 1.
(3) The feeding molar ratio of the dimethyl terephthalate, the phosphorus-nitrogen-containing monomer and the ethylene glycol is 100: 10: 135, the mass of the antimony acetate is 0.035% of that of the dimethyl terephthalate, and the mass of the trimethyl phosphate is 0.035% of that of the dimethyl terephthalate.
Controlling the ester exchange reaction temperature at 160 ℃, when the methanol distillate is 93.6 percent of a theoretical value, heating to 250 ℃, and starting a vacuum pump to control the vacuum degree at 0.4 MPa for pre-polycondensation for 3 hours; and continuously heating to 280 ℃, controlling the vacuum degree to be lower than 50 Pa, carrying out final polycondensation, relieving the vacuum with nitrogen after 4 hours, discharging, cooling and slicing to obtain the hydrophilic flame-retardant polyester.
Example 3
The steps (1) and (2) are the same as in example 1.
(3) The feeding molar ratio of the dimethyl terephthalate, the phosphorus-nitrogen-containing monomer and the ethylene glycol is 100: 7: 128, the mass of the antimony acetate is 0.03 percent of that of the dimethyl terephthalate, and the mass of the trimethyl phosphate is 0.035 percent of that of the dimethyl terephthalate.
The ester exchange reaction temperature is controlled at 160 ℃, when the methanol distillate is 90.2 percent of the theoretical value, the temperature is raised to 240 ℃, and a vacuum pump is started to control the vacuum degree at 0.4 MPa for pre-polycondensation for 3.5 hours; and continuously heating to 265 ℃, controlling the vacuum degree to be lower than 50 Pa, carrying out final polycondensation, relieving the vacuum by using nitrogen after 4 hours, discharging, cooling, and slicing to obtain the hydrophilic flame-retardant polyester.
Example 4
The steps (1) and (2) are the same as in example 1.
(3) The feeding molar ratio of the dimethyl terephthalate, the phosphorus-nitrogen-containing monomer and the ethylene glycol is 100: 5: 150, the mass of the antimony acetate is 0.04% of that of the dimethyl terephthalate, and the mass of the trimethyl phosphate is 0.035% of that of the dimethyl terephthalate.
Controlling the ester exchange reaction temperature at 180 ℃, when the methanol distillate is 91.7 percent of the theoretical value, heating to 240 ℃, and starting a vacuum pump to control the vacuum degree at 0.4 MPa for pre-polycondensation for 2 hours; and continuously heating to 260 ℃, controlling the vacuum degree to be lower than 50 Pa, carrying out final polycondensation, relieving the vacuum by using nitrogen after 5 hours, discharging, cooling and slicing to obtain the hydrophilic flame-retardant polyester.
Example 5
The steps (1) and (2) are the same as in example 1.
(3) The feeding molar ratio of the dimethyl terephthalate, the phosphorus-nitrogen-containing monomer and the ethylene glycol is 100: 2: 150, the mass of the antimony acetate is 0.02 percent of that of the dimethyl terephthalate, and the mass of the trimethyl phosphate is 0.02 percent of that of the dimethyl terephthalate.
Controlling the ester exchange reaction temperature at 180 ℃, when the distilled amount of methanol is 92.5 percent of a theoretical value, heating to 260 ℃, and starting a vacuum pump to control the vacuum degree at 0.4 MPa for pre-polycondensation for 4 hours; and continuously heating to 280 ℃, controlling the vacuum degree to be lower than 50 Pa, performing final polycondensation, relieving the vacuum with nitrogen after 3.5 hours, discharging, cooling, and slicing to obtain the hydrophilic flame-retardant polyester.
Comparative example 1
Fiber grade polyester chips were purchased from southeast chemical fiber materials ltd, ceremony.
The test results of examples 1 to 4 and comparative example 1 are shown in Table 1.
TABLE 1
Sample(s) | Intrinsic viscosity [ eta ]] ,dL/g | P content% | Content of N% | Limit oxygen index% | Melting Point Tm,. Degree.C | Cold crystallization temperature Tc,. Degree.C | △H,J/g | Moisture regain of% |
Example 1 | 0.76 | 2.86 | 2.59 | 37.7 | 219.1 | 127.9 | 27.1 | 2.4 |
Example 2 | 0.75 | 2.50 | 2.24 | 36.4 | 222.4 | 133.7 | 29.6 | 2.2 |
Example 3 | 0.74 | 1.84 | 1.65 | 34.8 | 227.5 | 138.0 | 30.4 | 1.6 |
Example 4 | 0.75 | 1.37 | 1.26 | 33.4 | 230.8 | 142.9 | 32.1 | 1.5 |
Example 5 | 0.78 | 0.60 | 0.52 | 30.8 | 239.2 | 150.5 | 36.4 | 0.9 |
Comparative example 1 | 0.69 | - | - | 22.8 | 248.0 | 162.3 | 38.2 | 0.5 |
As can be seen from Table 1, the limiting oxygen index and the moisture regain of the hydrophilic flame-retardant polyester are greatly improved compared with those of common fiber-grade polyester chips, but with the increase of the dosage of the phosphorus and nitrogen-containing third monomer in the polyester, tm, tc and Delta H of the system all show a descending trend, but the descending amplitude is not large, because the phosphorus and nitrogen-containing monomer is added, the regularity of the polyester molecular chain is reduced, but the chain segment rigidity of the phosphorus and nitrogen-containing third monomer is stronger, and the chain segment structure of the hydrophilic flame-retardant polyester is similar to that of polyethylene terephthalate. In the addition range of the third monomer, the polyester has good flame retardance, improves the hydrophilic hygroscopicity of the polyester, still keeps ideal crystallinity, has good spinnability, and can be applied to the preparation of flame-retardant fibers.
Claims (3)
1. The preparation method of the hydrophilic flame-retardant polyester is characterized by comprising the following steps:
(1) Preparation of intermediate A
Taking triethylamine as a catalyst and an acid-binding agent, taking chloroform as a reaction solvent, dripping a phosphorus oxychloride solution into a pentaerythrine solution, removing an ice water bath after dripping within 0.5 to 1 h, heating to 60 to 80 ℃, refluxing for 4 to 6 h, and obtaining white powder by reduced pressure distillation, washing and drying, wherein the white powder is marked as an intermediate A;
the intermediate A has a structure shown in a formula (I):
(I)
(2) Preparation of phosphorus-nitrogen containing monomer
Using anhydrous aluminum trichloride as a catalyst and chloroform as a reaction solvent, performing reflux reaction on the intermediate A and methyl p-hydroxybenzoate at 60-80 ℃ for 3-6 h, and performing extraction, distillation and recrystallization to obtain a phosphorus-nitrogen-containing monomer;
the phosphorus-nitrogen-containing monomer has a structure of a formula (II):
(II)
(3) Preparation of hydrophilic flame-retardant polyester
Proportionally weighing dimethyl terephthalate, phosphorus-nitrogen-containing monomer, ethylene glycol, trimethyl phosphate and antimony acetate, putting into a reaction kettle, and introducing N 2 Performing ester exchange reaction at 160 to 200 ℃ for 4 to 6 hours, wherein 90 percent of theoretical value of methanol distillation is used as the end point of the esterification reaction; then raising the temperature to 240 to 260 ℃, starting a vacuum pump, and controlling the vacuum degree within 0.2 to 0.4 MPa for precondensation for 2 to 4 hours; and continuously heating to 260-280 ℃, controlling the vacuum degree to be lower than 50 Pa, starting final polycondensation for 3-5 h, relieving vacuum with nitrogen, discharging, cooling and slicing to obtain the hydrophilic flame-retardant polyester.
2. The method for preparing hydrophilic flame-retardant polyester according to claim 1, wherein the method comprises the following steps:
the feeding molar ratio of the pentamine and the phosphorus oxychloride in the step (1) is 1: 2.6 to 3;
the feeding molar ratio of the triethylamine to the pentaenetetramine in the step (1) is 5: 1;
the pentamine tetramine solution in the step (1) is a pentamine chloroform solution with the molar concentration of 1 to 2 mol/L, and the phosphorus oxychloride solution is a phosphorus oxychloride chloroform solution with the molar concentration of 2 mol/L;
in the step (1), the reaction temperature is 60 ℃, and the reaction time is 5 hours;
the feeding molar ratio of the intermediate A to the methyl p-hydroxybenzoate in the step (2) is 1: 2 to 2.2, and the feeding amount of the anhydrous aluminum trichloride is 0.5 to 0.7 percent of the feeding mass of the intermediate A;
in the step (2), the reaction temperature is 80 ℃, and the reaction time is 4 hours;
the feeding molar ratio of the dimethyl terephthalate, the phosphorus-nitrogen-containing monomer and the ethylene glycol in the step (3) is 100: 2 to 12: 120 to 140, the mass of the antimony acetate is 0.02 to 0.04 percent of the mass of the dimethyl terephthalate, and the mass of the trimethyl phosphate is 0.02 to 0.04 percent of the mass of the dimethyl terephthalate.
3. The preparation method of the hydrophilic flame-retardant polyester as claimed in any one of claims 1 to 2, wherein the preparation method comprises the following steps: the intrinsic viscosity of the polyester was 0.7 to 0.8 dL/g.
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CN102633999A (en) * | 2012-04-26 | 2012-08-15 | 陕西科技大学 | P-N flame retardant and preparation method thereof |
CN103641859A (en) * | 2013-11-22 | 2014-03-19 | 江苏裕兴薄膜科技股份有限公司 | Phosphorus-containing flame retardant monomer, halogen-free flame retardant polyester containing the same and preparation method thereof |
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JPS4879295A (en) * | 1972-01-25 | 1973-10-24 | ||
CN102633999A (en) * | 2012-04-26 | 2012-08-15 | 陕西科技大学 | P-N flame retardant and preparation method thereof |
CN103641859A (en) * | 2013-11-22 | 2014-03-19 | 江苏裕兴薄膜科技股份有限公司 | Phosphorus-containing flame retardant monomer, halogen-free flame retardant polyester containing the same and preparation method thereof |
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Title |
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Polymerization and surface analysis of electrically-conductive polypyrrole on surface-activated polyester fabrics for biomedical applications;Tessier, D;《JOURNAL OF BIOMATERIALS SCIENCE-POLYMER EDITION》;20000101;第11卷(第1期);87-99 * |
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