CN113736074A - Production method of flame-retardant antibacterial PET copolyester - Google Patents
Production method of flame-retardant antibacterial PET copolyester Download PDFInfo
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- CN113736074A CN113736074A CN202111054370.XA CN202111054370A CN113736074A CN 113736074 A CN113736074 A CN 113736074A CN 202111054370 A CN202111054370 A CN 202111054370A CN 113736074 A CN113736074 A CN 113736074A
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- esterification
- phosphorus
- antioxidant
- flame retardant
- containing flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 83
- 230000032050 esterification Effects 0.000 claims abstract description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 51
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 48
- 239000011574 phosphorus Substances 0.000 claims abstract description 48
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 36
- 239000003963 antioxidant agent Substances 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 24
- 239000003381 stabilizer Substances 0.000 claims description 19
- 150000007974 melamines Chemical class 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 36
- 239000005020 polyethylene terephthalate Substances 0.000 description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 239000011787 zinc oxide Substances 0.000 description 9
- 239000004753 textile Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 208000012886 Vertigo Diseases 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- XZAXQWXHBDKYJI-UHFFFAOYSA-N 2-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]butanedioic acid Chemical compound C1=CC=C2P(CC(CC(=O)O)C(O)=O)(=O)OC3=CC=CC=C3C2=C1 XZAXQWXHBDKYJI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- -1 Polyethylene terephthalate Polymers 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A production method of flame-retardant antibacterial PET copolyester is characterized by comprising the following steps: preparing a phosphorus-containing flame retardant pre-esterification solution; preparing an antibacterial agent dispersion liquid, stirring and mixing the nano inorganic metal oxide antibacterial agent and ethylene glycol, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid; ③ esterification reaction; and fourthly, performing polycondensation reaction to obtain the flame-retardant antibacterial PET copolyester. Compared with the prior art, the invention has the advantages of good flame-retardant antibacterial performance, water washing resistance, simple and convenient preparation process and low cost.
Description
Technical Field
The invention relates to PET copolyester, belonging to the technical field of high polymer materials.
Background
Polyethylene terephthalate (PET) is the most prominent type of thermoplastic polyester, commonly known as polyester resin. PET has excellent physical and mechanical properties in a wide temperature range, the long-term use temperature can reach 120 ℃, creep resistance, fatigue resistance, friction resistance and dimensional stability are good, the PET is applied to the field of textiles on a large scale, and the use amount of the PET accounts for more than 50% of the textile fiber market. However, as the specifications and standards of textile applications continue to be revised and supplemented, and as people demand multifunctional high-quality textiles, PET has some drawbacks in performance: PET is flammable material, is flammable when meeting fire, is easy to cause big fire or spread fire, and becomes one of the main hidden dangers for causing various indoor and outdoor fires; the PET textile is easy to breed bacteria and mildew in the long-time use process, and the defects directly limit the development of the application field of PET. Therefore, the PET is endowed with flame-retardant and antibacterial properties, and the multifunctional differentiated fiber is prepared, thereby having important practical significance for expanding the application field of PET.
The prior art discloses a plurality of documents added with halogen-free flame retardant, the halogen-free flame retardant contains phosphorus-containing flame retardant, and Chinese patent application with reference to document application number 201310630773.3 discloses a core-shell toughened and halogen-free flame-retardant modified PET material (publication number: CN 104672812A); reference may also be made to the Chinese patent application publication No. 201410279309.9, entitled "preparation method of flame-retardant and anti-dripping PET nanocomposite" (publication No.: CN 104017190A). However, the phosphorus-containing flame retardant is a reactive flame retardant, but the reaction system added with the polyester can prolong the polymerization time of the polyester, so that the whole production cycle is prolonged. Meanwhile, the addition of the phosphorus-containing flame retardant can also cause the melting point of the PET polyester to be reduced, and the adverse effect is generated on the subsequent spinning stage.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing flame-retardant antibacterial PET copolyester capable of shortening reaction time aiming at the technical current situation.
The technical scheme adopted by the invention for solving the technical problems is as follows: a production method of flame-retardant antibacterial PET copolyester is characterized by comprising the following steps:
firstly, preparing a phosphorus-containing flame retardant pre-esterification liquid, adding a phosphorus-containing flame retardant and ethylene glycol into an esterification kettle according to the mass ratio of 1: 1-4, adding a first catalyst and a first antioxidant, and carrying out esterification reaction for 2-6 hours under the conditions of stirring at the pre-esterification temperature of 140-180 ℃ and the pressure of 0.1-0.4 MPa to obtain the phosphorus-containing flame retardant pre-esterification liquid;
preparing an antibacterial agent dispersion liquid, stirring and mixing the nano inorganic metal oxide antibacterial agent and ethylene glycol according to the mass ratio of 1: 10-50, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid;
thirdly, esterification reaction, namely adding terephthalic acid and ethylene glycol into a polyester esterification device according to the molar ratio of 1: 1.2-2, and performing esterification reaction for 80-240 min under the conditions that the esterification temperature is 220-250 ℃ and the pressure is 0.1-0.4 MPa to obtain an esterified substance of the flame-retardant antibacterial PET copolyester;
fourthly, polycondensation reaction: transferring the esterified product into a polyester polycondensation device, adding a phosphorus-containing flame retardant pre-esterification liquid, an antibacterial agent dispersion liquid, a second catalyst, a second antioxidant, a stabilizer and a melamine derivative, carrying out polycondensation reaction for 2-4 h under the conditions that the polycondensation temperature is 265-280 ℃ and the vacuum degree is less than 100Pa, discharging and granulating when the viscosity of a product reaches 0.65-0.75 dL/g, and drying to obtain the flame-retardant antibacterial PET copolyester.
Preferably, the phosphorus-containing flame retardant is at least one of 2-carboxyethylphenylphosphinic acid, triphenyl phosphate, bisphenol A-bis (diphenyl phosphate), and [ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid.
Preferably, the esterification rate of the phosphorus-containing flame retardant pre-esterification liquid is more than 95%.
Preferably, the first catalyst is at least one of zinc acetate, magnesium acetate and manganese acetate, and the addition amount of the first catalyst is 0.1-0.3 wt% of the mass of the phosphorus-containing flame retardant.
Preferably, the nano inorganic metal oxide antibacterial agents are ZnO, CuO and Cu2At least one of O, the particle size is 10-20 nm.
Preferably, the amount of the phosphorus-containing flame retardant pre-esterification liquid is 1-10 wt% of the mass of the obtained esterification product; the antibacterial agent dispersion liquid accounts for 1-5 wt% of the mass of the obtained ester.
Preferably, the second catalyst is at least one of antimony trioxide, ethylene glycol antimony and tetrabutyl titanate, and the amount of the second catalyst is 0.015 to-0.030 wt% of the mass of the obtained ester.
Preferably, the first antioxidant and the second antioxidant are one of an antioxidant 1010, an antioxidant 1076 and an antioxidant 300, and the total amount of the first antioxidant and the second antioxidant is 0.015-0.030 wt% of the mass of the obtained esterified product.
Preferably, the melamine derivative is at least one of melamine and melamine phosphate, and the amount of the melamine derivative is 0.5-5 wt% of the amount of the obtained ester substance.
Preferably, the stabilizer is at least one of trimethyl phosphate and triphenyl phosphate, and the amount of the stabilizer is 0.015-0.030 wt% of the mass of the obtained ester.
Compared with the prior art, the invention has the advantages that: the phosphorus-containing flame retardant is a reactive flame retardant, is used as a third monomer to enter a PET polyester framework, has the advantages of good flame retardant effect, low toxicity and no corrosion, but the polymerization time of the polyester can be prolonged by adding a reaction system of the polyester, so that the whole production period is prolonged. Meanwhile, the addition of the phosphorus-containing flame retardant can also cause the melting point of the PET polyester to be reduced, and the adverse effect is generated on the subsequent spinning stage. The addition of the inorganic metal oxide can effectively reduce the adverse effect of the phosphorus-containing flame retardant on the performance of the PET polyester. The inorganic metal oxide has synergistic effect when being used as an antibacterial agent, can reduce the polymerization time of the polyester, and can reduce the using amount of a catalyst. In addition, the melting point and the mechanical property of the flame-retardant antibacterial PET copolyester can be improved by adding the inorganic metal oxide, and the subsequent spinning process is facilitated. Therefore, the flame retardant containing phosphorus and the inorganic metal oxide are compounded for use to prepare the flame-retardant antibacterial PET copolyester, so that the flame-retardant and antibacterial properties of the product can be effectively improved, the reaction time can be shortened, and the sample can be ensured to have a proper melting point and viscosity range.
The flame-retardant antibacterial PET copolyester produced by the preparation process has the advantages of high viscosity, good color value and high melting point. In addition, the addition of the inorganic metal oxide not only provides antibacterial performance, but also has catalytic action, effectively shortens polymerization time, reduces the thermal degradation degree of polyester at high temperature, and improves the color value of products.
The flame-retardant antibacterial PET copolyester disclosed by the invention has good flame retardant property and high antibacterial rate, can be added at one time in the polymerization process, and simplifies the process flow. In addition, the flame-retardant antibacterial PET copolyester has short polycondensation time, does not need to add toner or stabilizer, has good color phase, b value within 7 and polyester flame retardant performance LOI not less than 32 percent, and can be widely applied to fibers and textiles, such as clothing, protective clothing, interior decoration and the like.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
(1) Preparing a phosphorus-containing flame retardant pre-esterification solution: taking a phosphorus-containing flame retardant and ethylene glycol according to a mass ratio of 1:1, adding a proper amount of catalyst and antioxidant into an esterification kettle, and carrying out esterification reaction for 3 hours under the conditions of pre-esterification temperature of 150 ℃, pressure of 0.1MPa and stirring to obtain the phosphorus-containing flame retardant pre-esterification liquid. (2) And preparing an antibacterial agent dispersion liquid: taking zinc oxide and ethylene glycol according to a mass ratio of 1:10, stirring and mixing, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid. (3) And esterification reaction: terephthalic acid and ethylene glycol are mixed in a molar ratio of 1: 1.4 adding the mixture into a polyester esterification device, and carrying out esterification reaction for 150min under the conditions that the esterification temperature is 240 ℃ and the pressure is 0.3MPa to obtain the esterification product of the flame-retardant antibacterial PET copolyester. (4) And (3) polycondensation reaction: transferring the esterified product obtained in the step (3) into a polyester polycondensation device, adding the phosphorus-containing flame retardant pre-esterification liquid in the step (1), the antibacterial agent dispersion liquid in the step (2), a proper amount of catalyst, antioxidant, stabilizer and melamine derivative, performing polycondensation reaction for 2.5 hours under the conditions that the polycondensation temperature is 280 ℃ and the vacuum degree is less than 100Pa, discharging and pelletizing when the viscosity of a product reaches 0.65-0.75 dL/g, and drying to obtain the flame-retardant antibacterial PET copolyester. Wherein, the catalyst in the step (1) is zinc acetate, and the addition amount of the catalyst is 0.15 wt% of the phosphorus-containing flame retardant in the step (1); the antioxidant in the step (1) and the step (4) is 1010, and the amount of the antioxidant is 0.02 wt% of the mass of the obtained ester; the particle size of the zinc oxide in the step (2) is 10-20 nm; the using amount of the phosphorus-containing flame retardant pre-esterification liquid in the step (4) is 5 wt% of the mass of the ester in the step (3); the addition amount of the antibacterial agent dispersion liquid in the step (4) is 1 wt% of the mass of the esterification in the step (3); the catalyst in the step (4) is antimony trioxide, and the dosage of the catalyst is 0.02 wt% of the mass of the obtained esterification product. (ii) a The stabilizer in the step (4) is trimethyl phosphate, and the using amount of the stabilizer is 0.01 wt% of the mass of the ester in the step (3); the melamine derivative in the step (4) is melamine phosphate, and the dosage of the melamine derivative is 1 wt% of the mass of the ester in the step (4).
Example 2
(1) Preparing phosphorus-containing flame retardant pre-esterification liquid: taking a phosphorus-containing flame retardant and ethylene glycol according to a mass ratio of 1:1, adding a proper amount of catalyst and antioxidant into an esterification kettle, and carrying out esterification reaction for 3 hours under the conditions of pre-esterification temperature of 150 ℃, pressure of 0.1MPa and stirring to obtain the phosphorus-containing flame retardant pre-esterification liquid. (2) And preparing an antibacterial agent dispersion liquid: taking zinc oxide and ethylene glycol according to a mass ratio of 1: 20, stirring and mixing, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid. (3) And esterification reaction: terephthalic acid and ethylene glycol are mixed in a molar ratio of 1: 1.4 adding the mixture into a polyester esterification device, and carrying out esterification reaction for 150min under the conditions that the esterification temperature is 240 ℃ and the pressure is 0.3MPa to obtain the esterification product of the flame-retardant antibacterial PET copolyester. (4) And (3) polycondensation reaction: transferring the esterified product obtained in the step (3) into a polyester polycondensation device, adding the phosphorus-containing flame retardant pre-esterification liquid in the step (1), the antibacterial agent dispersion liquid in the step (2), a proper amount of catalyst, antioxidant, stabilizer and melamine derivative, performing polycondensation reaction for 3 hours under the conditions that the polycondensation temperature is 280 ℃ and the vacuum degree is less than 100Pa, discharging and granulating when the viscosity of a product reaches 0.65-0.75 dL/g, and drying to obtain the flame-retardant antibacterial PET copolyester. Wherein, the catalyst in the step (1) is zinc acetate, and the addition amount of the catalyst is 0.15 wt% of the phosphorus-containing flame retardant in the step (1); the antioxidant in the step (1) and the step (4) is 1010, and the amount of the antioxidant is 0.02 wt% of the mass of the obtained ester; the particle size of the zinc oxide in the step (2) is 10-20 nm; the using amount of the phosphorus-containing flame retardant pre-esterification liquid in the step (4) is 7 wt% of the mass of the ester in the step (3); the addition amount of the antibacterial agent dispersion liquid in the step (4) is 3 wt% of the mass of the esterification in the step (3); the catalyst in the step (4) is antimony trioxide, and the using amount of the catalyst is 0.024 wt% of the mass of the obtained esterification product. (ii) a The stabilizer in the step (4) is trimethyl phosphate, and the using amount of the stabilizer is 0.012 wt% of the mass of the ester in the step (3); the melamine derivative in the step (4) is melamine phosphate, and the dosage of the melamine derivative is 1 wt% of the mass of the ester in the step (4).
Example 3
(1) Preparing phosphorus-containing flame retardant pre-esterification liquid: taking a phosphorus-containing flame retardant and ethylene glycol according to a mass ratio of 1: 2, adding a proper amount of catalyst and antioxidant into an esterification kettle, and carrying out esterification reaction for 2.5 hours under the conditions of pre-esterification temperature of 170 ℃, pressure of 0.1MPa and stirring to obtain the phosphorus-containing flame retardant pre-esterification liquid. (2) And preparing an antibacterial agent dispersion liquid: taking zinc oxide and ethylene glycol according to a mass ratio of 1: 30, stirring and mixing, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid. (3) And esterification reaction: terephthalic acid and ethylene glycol are mixed in a molar ratio of 1:1.2 adding the mixture into a polyester esterifying device, and carrying out esterification reaction for 180min under the conditions that the esterification temperature is 245 ℃ and the pressure is 0.3MPa to obtain the esterification product of the flame-retardant antibacterial PET copolyester. (4) And (3) polycondensation reaction: transferring the esterified product obtained in the step (3) into a polyester polycondensation device, adding the phosphorus-containing flame retardant pre-esterification liquid in the step (1), the antibacterial agent dispersion liquid in the step (2), a proper amount of catalyst, antioxidant, stabilizer and melamine derivative, performing polycondensation reaction for 3 hours under the conditions that the polycondensation temperature is 270 ℃ and the vacuum degree is less than 100Pa, discharging and granulating when the viscosity of a product reaches 0.65-0.75 dL/g, and drying to obtain the flame-retardant antibacterial PET copolyester. Wherein, the catalyst in the step (1) is zinc acetate, and the addition amount of the catalyst is 0.15 wt% of the phosphorus-containing flame retardant in the step (1); the antioxidant in the step (1) and the step (4) is 1010, and the amount of the antioxidant is 0.02 wt% of the mass of the obtained ester; the particle size of the zinc oxide in the step (2) is 10-20 nm; the using amount of the phosphorus-containing flame retardant pre-esterification liquid in the step (4) is 8 wt% of the mass of the ester in the step (3); the addition amount of the antibacterial agent dispersion liquid in the step (4) is 5 wt% of the mass of the esterification in the step (3); the catalyst in the step (4) is antimony trioxide, and the dosage of the catalyst is 0.025 wt% of the mass of the obtained esterification product. (ii) a The stabilizer in the step (4) is trimethyl phosphate, and the using amount of the stabilizer is 0.01 wt% of the mass of the ester in the step (3); the melamine derivative in the step (4) is melamine phosphate, and the dosage of the melamine derivative is 1 wt% of the mass of the ester in the step (4).
Example 4
(1) Preparing phosphorus-containing flame retardant pre-esterification liquid: taking a phosphorus-containing flame retardant and ethylene glycol according to a mass ratio of 1: 2, adding a proper amount of catalyst and antioxidant into an esterification kettle, and carrying out esterification reaction for 2.5 hours under the conditions of pre-esterification temperature of 170 ℃, pressure of 0.1MPa and stirring to obtain the phosphorus-containing flame retardant pre-esterification liquid. (2) And preparing an antibacterial agent dispersion liquid: taking zinc oxide and ethylene glycol according to a mass ratio of 1: and 40, stirring and mixing, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid. (3) And esterification reaction: terephthalic acid and ethylene glycol are mixed in a molar ratio of 1:1.2 adding the mixture into a polyester esterifying device, and carrying out esterification reaction for 180min under the conditions that the esterification temperature is 245 ℃ and the pressure is 0.3MPa to obtain the esterification product of the flame-retardant antibacterial PET copolyester. (4) And (3) polycondensation reaction: transferring the esterified product obtained in the step (3) into a polyester polycondensation device, adding the phosphorus-containing flame retardant pre-esterification liquid in the step (1), the antibacterial agent dispersion liquid in the step (2), a proper amount of catalyst, antioxidant, stabilizer and melamine derivative, performing polycondensation reaction for 3 hours under the conditions that the polycondensation temperature is 270 ℃ and the vacuum degree is less than 100Pa, discharging and granulating when the viscosity of a product reaches 0.65-0.75 dL/g, and drying to obtain the flame-retardant antibacterial PET copolyester. Wherein, the catalyst in the step (1) is zinc acetate, and the addition amount of the catalyst is 0.15 wt% of the phosphorus-containing flame retardant in the step (1); the antioxidant in the step (1) and the step (4) is 1010, and the amount of the antioxidant is 0.02 wt% of the mass of the obtained ester; the particle size of the zinc oxide in the step (2) is 10-20 nm; the using amount of the phosphorus-containing flame retardant pre-esterification liquid in the step (4) is 10 wt% of the mass of the ester in the step (3); the addition amount of the antibacterial agent dispersion liquid in the step (4) is 5 wt% of the mass of the esterification in the step (3); the catalyst in the step (4) is antimony trioxide, and the dosage of the catalyst is 0.030 wt% of the mass of the obtained ester. (ii) a The stabilizer in the step (4) is trimethyl phosphate, and the using amount of the stabilizer is 0.01 wt% of the mass of the ester in the step (3); the melamine derivative in the step (4) is melamine phosphate, and the dosage of the melamine derivative is 1 wt% of the mass of the ester in the step (4).
Examples 1-4 physical property measurements are shown in Table 1 below:
TABLE 1 table of energy comparisons
Note: in the table, L, b are color values, L represents a luminance component, and b represents a color component from blue to yellow
Note: the viscosity is measured according to the method of GB17931-20, the color value is measured according to the method of GB/17931-2, and the Escherichia coli/Staphylococcus aureus is measured according to GB/T20944.3-2008, evaluation of antibacterial properties of textiles part 3: the method of Oscillating method.
Claims (10)
1. A production method of flame-retardant antibacterial PET copolyester is characterized by comprising the following steps:
firstly, preparing a phosphorus-containing flame retardant pre-esterification liquid, adding a phosphorus-containing flame retardant and ethylene glycol into an esterification kettle according to the mass ratio of 1: 1-4, adding a first catalyst and a first antioxidant, and carrying out esterification reaction for 2-6 hours under the conditions of stirring at the pre-esterification temperature of 140-180 ℃ and the pressure of 0.1-0.4 MPa to obtain the phosphorus-containing flame retardant pre-esterification liquid;
preparing an antibacterial agent dispersion liquid, stirring and mixing the nano inorganic metal oxide antibacterial agent and ethylene glycol according to the mass ratio of 1: 10-50, and performing ultrasonic dispersion to obtain the antibacterial agent dispersion liquid;
thirdly, esterification reaction, namely adding terephthalic acid and ethylene glycol into a polyester esterification device according to the molar ratio of 1: 1.2-2, and performing esterification reaction for 80-240 min under the conditions that the esterification temperature is 220-250 ℃ and the pressure is 0.1-0.4 MPa to obtain an esterified substance of the flame-retardant antibacterial PET copolyester;
fourthly, polycondensation reaction: transferring the esterified product into a polyester polycondensation device, adding a phosphorus-containing flame retardant pre-esterification liquid, an antibacterial agent dispersion liquid, a second catalyst, a second antioxidant, a stabilizer and a melamine derivative, carrying out polycondensation reaction for 2-4 h under the conditions that the polycondensation temperature is 265-280 ℃ and the vacuum degree is less than 100Pa, discharging and granulating when the viscosity of a product reaches 0.65-0.75 dL/g, and drying to obtain the flame-retardant antibacterial PET copolyester.
2. The method according to claim 1, wherein the phosphorus-containing flame retardant is at least one of 2-carboxyethylphenylphosphinic acid, triphenyl phosphate, bisphenol A-bis (diphenyl phosphate), and [ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxyphosphohexan-6-yl) methyl ] succinic acid.
3. The production method according to claim 1, wherein the esterification rate of the phosphorus-containing flame retardant pre-esterification liquid is more than 95%.
4. The production method according to claim 1, wherein the first catalyst is at least one of zinc acetate, magnesium acetate and manganese acetate, and the addition amount is 0.1-0.3 wt% of the phosphorus-containing flame retardant.
5. The method of claim 1, wherein the nanoparticles are producedInorganic metal oxide antibacterial agents ZnO, CuO and Cu2At least one of O, the particle size is 10-20 nm.
6. The production method according to claim 1, wherein the amount of the phosphorus-containing flame retardant pre-esterification liquid is 1-10 wt% of the obtained esterification product; the antibacterial agent dispersion liquid accounts for 1-5 wt% of the mass of the obtained ester.
7. The production process according to claim 1, wherein the second catalyst is at least one of antimony trioxide, antimony ethylene glycol and tetrabutyl titanate, and the amount of the second catalyst is 0.015 to-0.030 wt% based on the mass of the obtained ester.
8. The production method according to claim 1, wherein the first antioxidant and the second antioxidant are one of an antioxidant 1010, an antioxidant 1076 and an antioxidant 300, and the total amount of the first antioxidant and the second antioxidant is 0.015 to 0.030 wt% based on the mass of the obtained ester.
9. The production process according to claim 1, wherein the melamine derivative is at least one of melamine and melamine phosphate, and the amount of the melamine derivative is 0.5 to 5 wt% based on the amount of the obtained ester.
10. The production method according to claim 1, wherein the stabilizer is at least one of trimethyl phosphate and triphenyl phosphate, and the amount of the stabilizer is 0.015 to 0.030 wt% based on the mass of the obtained esterified product.
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| CN111748084A (en) * | 2020-06-30 | 2020-10-09 | 四川东材科技集团股份有限公司 | Antibacterial flame-retardant polyester resin and preparation method thereof |
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| CN111748084A (en) * | 2020-06-30 | 2020-10-09 | 四川东材科技集团股份有限公司 | Antibacterial flame-retardant polyester resin and preparation method thereof |
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