CN117384209A - Phosphorus-containing dihydric alcohol and preparation method thereof, phosphorus-containing flame-retardant polyester and preparation method and application thereof - Google Patents
Phosphorus-containing dihydric alcohol and preparation method thereof, phosphorus-containing flame-retardant polyester and preparation method and application thereof Download PDFInfo
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- CN117384209A CN117384209A CN202311334596.4A CN202311334596A CN117384209A CN 117384209 A CN117384209 A CN 117384209A CN 202311334596 A CN202311334596 A CN 202311334596A CN 117384209 A CN117384209 A CN 117384209A
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- phosphorus
- dihydric alcohol
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- phosphate
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 63
- 239000011574 phosphorus Substances 0.000 title claims abstract description 63
- 239000003063 flame retardant Substances 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 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 38
- 229920000728 polyester Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 14
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000005886 esterification reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 230000032050 esterification Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 229920000180 alkyd Polymers 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000002009 diols Chemical class 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000002156 mixing Methods 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 229920005862 polyol Polymers 0.000 abstract description 22
- 150000003077 polyols Chemical class 0.000 abstract description 17
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 abstract description 15
- 230000000704 physical effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 208000017257 LMNA-related cardiocutaneous progeria syndrome Diseases 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NXDJCCBHUGWQPG-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;terephthalic acid Chemical compound OCC1CCC(CO)CC1.OC(=O)C1=CC=C(C(O)=O)C=C1 NXDJCCBHUGWQPG-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl 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
- C08G63/68—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
Abstract
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to phosphorus-containing dihydric alcohol and a preparation method thereof, and phosphorus-containing flame-retardant polyester and a preparation method and application thereof. The invention reacts methyl dimethyl phosphate (DMMP) with ethylene glycol to obtain phosphorus-containing polyol, and then one of the phosphorus-containing polyol serving as a raw material is subjected to polycondensation reaction with terephthalic acid and 1, 4-cyclohexanedimethanol to obtain the phosphorus-containing flame-retardant polyester. The invention introduces the high-efficiency flame-retardant structure containing phosphorus into the low-cost polyol through chemical reaction, has obvious flame-retardant effect, does not influence the physical properties of the material, has wide sources of reaction raw materials, is simple and controllable in reaction, and has good industrial prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to phosphorus-containing dihydric alcohol and a preparation method thereof, and phosphorus-containing flame-retardant polyester and a preparation method and application thereof.
Background
Poly (1, 4 cyclohexanedimethanol terephthalate) (PCT) is a new variety of polyesters with properties similar to those of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Has the strength and toughness of PBT, and the heat resistance is better than PET. The 1,4 cyclohexane dimethanol (CHDM) structure marked with a rigid cyclohexane structure can be used as one of the raw materials of the polyester, so that the heat stability and the transparency of the polyester can be greatly improved. PCT has heat resistance lower than polyphenylene sulfide (PPS), high temperature Liquid Crystal Polymer (LCPS) and high temperature resistant polyamide, but higher than medium temperature liquid crystal polymer and other polyesters, and PCT also has good toughness, thermal stability, workability, chemical resistance, and low hygroscopicity, with little impact on PCT's mechanical properties, dimensional stability, and processability under humid conditions. PCT can therefore compete with many polymers such as PPS, LCPS, and high temperature polyamides. Since PCT is commonly used in electric and electronic products, which requires good flame retardancy, unmodified PCT is not flame retardant, which greatly limits PCT use, the present invention relates to increasing the flame retardancy of PCT resins.
The most common use of the prior art for improving the flame retardance of the polyester is an additive flame retardant, and although the method can improve the flame retardance of the polyester to a certain extent, the additive flame retardant generally influences the physical properties of the polyester, has the defects of poor flame retardance and durability, easiness in migration, secondary pollution to the environment and the like, and is limited in use. The organic phosphorus flame retardant is an important organic flame retardant, the product types are various, the application is wide, and common organic phosphorus flame retardants include phosphorus-containing polyol, phosphate esters, phosphorus-containing dihydric alcohol and the like. Compared with halogen flame retardant, the organic phosphorus flame retardant does not generate toxic gas in the flame retardant process, and is an environment-friendly preparation. Meanwhile, the organic phosphorus flame retardant has good flame retardant effect, has small influence on the physical properties of products, and has mature preparation process and sufficient raw materials, so that the products are widely used. Therefore, the preparation of the efficient and low-cost flame-retardant polyol has wide prospect in the development of polyester.
The invention introduces the related high-efficiency flame-retardant structure into the low-cost polyol through chemical reaction mainly by a chemical modification method to obtain the high-efficiency flame-retardant polyol, and applies the flame-retardant polyol to the preparation of the polyester, thereby obtaining the high-flame-retardant polyester product. The dimethyl methylphosphonate (DMMP) is colorless transparent liquid, has the phosphorus content of up to 25%, can be mixed with water and various organic solvents, and has better compatibility compared with inorganic salt flame retardant.
The Chinese patent application with application number 201811454852.2 discloses an engineering plastic with high strength and excellent flame retardance and heat resistance, but the toughness of the modified resin is reduced and the brittleness is increased by adding modified glass fiber, modified expanded vitrified microbeads, sodium lignin sulfonate and other components. The Chinese patent application with the application number of 201910202450.1 discloses a method for enhancing flame retardance by compounding modified PCT with brominated flame retardants and synergistic flame retardants, but the modified PCT and the brominated flame retardants are used in a synergistic way with antimony compounds, and antimony resources are relatively precious and limited, so that the method has high cost and is not suitable for large-scale production and application.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides phosphorus-containing dihydric alcohol and a preparation method thereof, and phosphorus-containing flame-retardant polyester and a preparation method and application thereof. The invention reacts methyl dimethyl phosphate (DMMP) with ethylene glycol to obtain phosphorus-containing polyol, and then one of the phosphorus-containing polyol serving as a raw material is subjected to polycondensation reaction with terephthalic acid and 1, 4-cyclohexanedimethanol to obtain the phosphorus-containing flame-retardant polyester. The invention introduces the high-efficiency flame-retardant structure containing phosphorus into the low-cost polyol through chemical reaction, has obvious flame-retardant effect, does not influence the physical properties of the material, has wide sources of reaction raw materials, is simple and controllable in reaction, and has good industrial prospect.
The technical scheme provided by the invention is as follows:
a phosphorus-containing dihydric alcohol has the following structure:
the invention also provides a preparation method of the phosphorus-containing dihydric alcohol, which comprises the following steps: 1) Adding phosphate and dihydric alcohol in a certain proportion into a round-bottom four-neck flask, adding a certain amount of catalyst while stirring, raising the system temperature to a certain temperature, and reacting for a period of time. The distillate was collected by atmospheric distillation and neutralized to ph=7 with 1mol/L sodium hydroxide solution after the reaction was completed. Distilling and dehydrating under reduced pressure at a certain temperature, separating raw materials which are not completely reacted, and obtaining a target product by suction filtration, namely PO 3 。
Specific:
the phosphate is at least one of methyl dimethyl phosphate, ethyl diethyl phosphate and triphenyl phosphate, preferably methyl dimethyl phosphate (DMMP);
the dihydric alcohol is at least one of 1,4 cyclohexane dimethanol, ethylene glycol, 1,4 butanediol and 1,3 propanediol, preferably ethylene glycol;
the catalyst is one of sodium metal, organic tin and derivatives thereof, potassium carbonate and the like, and preferably sodium metal;
preferably:
the molar ratio of the phosphate to the dihydric alcohol is 1:2;
the catalyst dosage is 0.3 wt ％～0.6 wt Percent, preferably 0.5%;
the reaction temperature is 170 ℃;
the reaction time was 12h.
One synthetic route for the above preparation method is as follows:
the invention also provides a preparation method of the phosphorus-containing flame-retardant polyester, which comprises the following steps.
1) Preparing phosphorus-containing dihydric alcohol according to the method;
2) The dibasic acid, the dihydric alcohol containing phosphorus and the synergistic catalyst are put into a flask according to a certain molar ratio, and are heated to a certain temperature under a certain pressure to carry out esterification reaction, so as to generate mixed alcohol ester of the dibasic acid, and simultaneously, water is removed. Condensing and separating water generated in the reaction process and distilled raw materials through a condenser pipe, collecting byproduct water through the condenser pipe, performing esterification reaction for a period of time, and calculating the esterification rate through the collected byproduct water;
3) When the esterification rate reaches a certain degree and the reaction liquid gradually shows a clear state, the reaction is carried out for a period of time under vacuum and low pressure at an elevated temperature, and when no water is generated, the reaction is ended, thus obtaining the product.
In step 2), specific:
the dibasic acid is one of terephthalic acid, oxalic acid and sebacic acid, and is preferably terephthalic acid;
the dihydric alcohol is at least one of 1, 4-cyclohexane dimethanol, 1, 4-butanediol and polyethylene glycol, preferably 1, 4-cyclohexane dimethanol;
the catalyst is at least one of butyl phthalate, antimony trioxide and germanium dioxide, preferably butyl phthalate;
the molar ratio of the alkyd is 1 (1.0-1.2), preferably 1:1.1;
the reaction pressure is 0.25-0.3 MPa, the temperature is 220-250 ℃, and the reaction time is 3-4 h;
the molar ratio of the dibasic acid, the dihydric alcohol and the phosphorus-containing dihydric alcohol is 1.1: (0.5-0.8): (0.2 to 0.5);
the catalyst dosage is 0.02 of the total amount of dihydric alcohol and dihydric alcohol containing phosphorus wt ％～0.04 wt Percent, preferably 0.03 percent wt ％。
Specifically, the polymerization temperature in step 3) is: the temperature is 240-260 ℃, the pressure is 20-60 Pa, the reaction time is 3h, and the esterification rate in the step 3) is more than 95%.
One synthetic route for the above preparation method is as follows:
n ranges from 40 to 80 and m ranges from 10 to 20.
The invention also provides the phosphorus-containing flame-retardant polyester prepared by the method, and the phosphorus-containing flame-retardant polyester maintains good processing performance of the polyester and is particularly suitable for being used as wireless communication circuit elements such as a perforation card connector, a grid plate, a plug slot plate assembly, a circuit board and the like due to the introduction of a phosphorus-containing high-efficiency flame-retardant structure.
The beneficial effects are that:
1) According to the invention, the high-efficiency related flame-retardant structure is introduced into the low-cost polyol through chemical reaction by a chemical modification method, so that the high-efficiency flame-retardant polyol is obtained.
2) The flame-retardant polyol is applied to the preparation of polyester, so that a high flame-retardant polyester product is obtained.
Drawings
FIG. 1 is a diagram of P-PCT-1 prepared in example 1 of the present invention 1 H-NMR chart.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Comparative example 1
CHDM (1, 4 cyclohexanedimethanol) was heated to 80 ℃ and charged into a four-necked flask after the solid was completely melted, and PTA (terephthalic acid) and n-butyl titanate were charged into the flask with stirring (alkyd ratio: 1:1.1, n-butyl titanate was 0.03 of CHDM) wt And (3%) heating to 220 ℃ for esterification reaction, setting the pressure to 0.3MPa, condensing and separating water generated in the reaction process and distilled CHDM through a condenser pipe, collecting byproduct water through the condenser pipe, calculating the esterification rate through the collected byproduct water, and when the esterification rate reaches 95%, and the reaction liquid is gradually in a clear state, heating to 250 ℃, setting the pressure to 50Pa, and ending the reaction until no water is generated, thereby obtaining the product PCT-0.
Example 1
Adding methyl dimethyl phosphate (DMMP) and ethylene glycol into a round bottom four-neck flask (the molar ratio of methyl dimethyl phosphate (DMMP) to ethylene glycol is 1:2), and adding a certain amount of metal sodium (Na contains) while stirringThe amount of the distillate is 0.5% of that of the glycol, the temperature of the system is increased to 170 ℃, the distillate is collected by adopting an atmospheric distillation method, and after the reaction is finished, the mixture is neutralized to pH=7 by using 1mol/L sodium hydroxide solution. Vacuum distilling at 120deg.C for dehydration, separating raw materials which are not completely reacted, and vacuum filtering to obtain phosphorus-containing dihydric alcohol PO 3 。
Heating CHDM to 80 ℃, adding the mixture into a four-necked flask after the solid is completely melted, stirring the mixture, and adding PTA, phosphorus-containing polyol and n-butyl titanate into the flask (alkyd ratio: 1:1.1, PTA: CHDM: PO 3 1.1:0.8:0.2, n-butyl titanate is CHDM and 0.03 of a phosphorus-containing polyol wt And (3%) heating to 220 ℃ for esterification reaction, setting the pressure to 0.3MPa, condensing and separating water generated in the reaction process and distilled CHDM through a condenser pipe, collecting byproduct water through the condenser pipe, calculating the esterification rate through the collected byproduct water, and when the esterification rate reaches 95%, and the reaction liquid is gradually in a clear state, heating to 250 ℃, setting the pressure to 50Pa, and ending the reaction until no water is generated, thereby obtaining the product P-PCT-1.
Example 2
Adding methyl dimethyl phosphate (DMMP) and ethylene glycol into a round-bottom four-neck flask (the molar ratio of methyl dimethyl phosphate (DMMP) to ethylene glycol is 1:2), adding a certain amount of metal sodium (Na content is 0.5 percent of ethylene glycol) while stirring, raising the system temperature to 170 ℃, collecting distillate by adopting an atmospheric distillation method, neutralizing with 1mol/L sodium hydroxide solution until the reaction is finished to pH= 7.120 ℃, distilling under reduced pressure to dehydrate, separating raw materials which are not completely reacted, and obtaining phosphorus-containing dihydric alcohol PO by suction filtration 3 。
Heating CHDM to 80 ℃, adding the mixture into a four-necked flask after the solid is completely melted, stirring the mixture, and adding PTA, phosphorus-containing polyol and n-butyl titanate into the flask (alkyd ratio: 1:1.1, PTA: CHDM: PO 3 1.1:0.7:0.3, n-butyl titanate is CHDM and 0.03 of a phosphorus-containing polyol wt Heating to 220 ℃ for esterification reaction, setting the pressure to 0.3MPa, condensing water generated in the reaction process and distilled CHDM through a condenser tube, separating, collecting byproduct water through the condenser tube, and collecting the byproduct water through a condenser tubeAnd (3) calculating the esterification rate of the collected byproduct water, when the esterification rate reaches 95%, and the reaction liquid gradually shows a clear state, increasing the temperature to 250 ℃, setting the pressure to be 50Pa, and ending the reaction until no water is generated, thereby obtaining the product P-PCT-2.
Example 3
Adding dimethyl methylphosphonate (DMMP) and ethylene glycol into a round-bottom four-neck flask (the molar ratio of the dimethyl methylphosphonate (DMMP) to the ethylene glycol is 1:2), adding a certain amount of metal sodium (Na content is 0.5 percent of the ethylene glycol) while stirring, raising the system temperature to 170 ℃, collecting distillate by adopting an atmospheric distillation method, neutralizing with 1mol/L sodium hydroxide solution until the reaction is finished to pH= 7.120 ℃, distilling under reduced pressure to dehydrate, separating raw materials which are not completely reacted, and obtaining phosphorus-containing PO by suction filtration 3 。
Heating CHDM to 80 ℃, adding the mixture into a four-necked flask after the solid is completely melted, stirring the mixture, and adding PTA, phosphorus-containing polyol and n-butyl titanate into the flask (alkyd ratio: 1:1.1, PTA: CHDM: PO 3 1.1:0.6:0.4 n-butyl titanate is CHDM and 0.03 of a phosphorus-containing polyol wt And (3%) heating to 220 ℃ for esterification reaction, setting the pressure to 0.3MPa, condensing and separating water generated in the reaction process and distilled CHDM through a condenser pipe, collecting byproduct water through the condenser pipe, calculating the esterification rate through the collected byproduct water, and when the esterification rate reaches 95%, and the reaction liquid is gradually in a clear state, heating to 250 ℃, setting the pressure to 50Pa, and ending the reaction until no water is generated, thereby obtaining the product P-PCT-3.
Example 4
Adding methyl dimethyl phosphate (DMMP) and ethylene glycol into a round-bottom four-neck flask (the molar ratio of methyl dimethyl phosphate (DMMP) to ethylene glycol is 1:2), adding a certain amount of metal sodium (Na content is 0.5 percent of ethylene glycol) while stirring, raising the system temperature to 170 ℃, collecting distillate by adopting an atmospheric distillation method, neutralizing with 1mol/L sodium hydroxide solution until the reaction is finished to pH= 7.120 ℃, distilling under reduced pressure to dehydrate, separating raw materials which are not completely reacted, and obtaining phosphorus-containing dihydric alcohol PO by suction filtration 3 。
Heating CHDM to 80 ℃, adding the mixture into a four-necked flask after the solid is completely melted, stirring the mixture, and adding PTA, phosphorus-containing polyol and n-butyl titanate into the flask (alkyd ratio: 1:1.1, PTA: CHDM: PO 3 1.1:0.5:0.5 n-butyl titanate as CHDM and 0.03 of a phosphorus-containing polyol wt And (3%) heating to 220 ℃ for esterification reaction, setting the pressure to 0.3MPa, condensing and separating water generated in the reaction process and distilled CHDM through a condenser pipe, collecting byproduct water through the condenser pipe, calculating the esterification rate through the collected byproduct water, and when the esterification rate reaches 95%, and the reaction liquid is gradually in a clear state, heating to 250 ℃, setting the pressure to 50Pa, and ending the reaction until no water is generated, thereby obtaining the product P-PCT-4.
Table 1 shows the flame retardant property test results of comparative example 1 and examples 1 to 4 of the present invention.
TABLE 1 limiting oxygen index for examples 1-5 and pure PCT
As can be seen from the results in Table 1, the phosphorus-containing flame-retardant polyester has significantly improved limiting oxygen index and flame retardant grade due to the introduction of phosphorus-containing dihydric alcohol.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A phosphorus-containing diol, characterized by the following structure:
2. a process for the preparation of the phosphorus-containing diol according to claim 1, comprising the steps of: mixing phosphate, dihydric alcohol and a catalyst, raising the temperature of the system to 160-180 ℃ for reaction for 10-14 h, collecting distillate substances by adopting an atmospheric distillation method, neutralizing with sodium hydroxide solution until the pH value is=7 after the reaction is finished, decompressing, distilling and dehydrating, separating raw materials which are not completely reacted, and carrying out suction filtration to obtain a target product, wherein:
the phosphate is at least one of methyl dimethyl phosphate, ethyl diethyl phosphate or triphenyl phosphate;
the dihydric alcohol is at least one of 1,4 cyclohexane dimethanol, ethylene glycol, 1,4 butanediol or 1,3 propanediol;
the catalyst is one of sodium metal, organic tin and its derivative or potassium carbonate;
the mole ratio of the phosphate to the dihydric alcohol is 1 (1.8-2.2), and the catalyst dosage is 0.3 of the dihydric alcohol wt ％～0.6 wt ％。
3. The method for producing phosphorus-containing diol according to claim 2, wherein any one or more of the following conditions are satisfied:
the phosphate is methyl dimethyl phosphate;
the dihydric alcohol is ethylene glycol;
the catalyst is sodium metal;
the mole ratio of the phosphate to the dihydric alcohol is 1:2;
the catalyst dosage is 0.5 of dihydric alcohol wt ％；
The reaction temperature is 170 ℃;
the reaction time was 12h.
4. The preparation method of the phosphorus-containing flame-retardant polyester is characterized by comprising the following steps of:
1) Preparing a phosphorus-containing diol by the method of claim 2 or 3;
2) Mixing dibasic acid, dihydric alcohol, phosphorus-containing dihydric alcohol and a synergistic catalyst according to a certain molar ratio, heating to 220-250 ℃ under the pressure of 0.25-0.3 MPa for esterification reaction for 3-4 h to generate alcohol mixed ester of dibasic acid, and simultaneously removing water, wherein the water generated in the reaction process and the water generated in the reaction process are mixedCondensing and separating the distilled raw materials through a condenser pipe, collecting byproduct water through the condenser pipe, performing esterification reaction for a period of time, and calculating the esterification rate through the collected byproduct water, wherein the mole ratio of the dibasic acid to the dihydric alcohol to the phosphorus-containing dihydric alcohol is 1.1: (0.5-0.8): the molar ratio of the alkyd is 1 (1.0-1.2), and the catalyst dosage is 0.02 of the total glycol and the phosphorus-containing glycol wt ％～0.04 wt ％；
3) When the esterification rate reaches more than 95%, and the reaction liquid gradually shows a clear state, the temperature is increased to 240-260 ℃, the reaction is carried out for 2-4 hours under vacuum low pressure, and when no water is generated, the reaction is finished, thus obtaining the product.
5. The method for producing a phosphorus-containing flame retardant polyester according to claim 4, wherein in step 2), any one or more of the following conditions are satisfied:
the dibasic acid is one of terephthalic acid, oxalic acid or sebacic acid;
the dihydric alcohol is at least one of 1, 4-cyclohexanedimethanol, 1, 4-butanediol or polyethylene glycol;
the catalyst is at least one of n-butyl titanate, antimony trioxide or germanium dioxide;
the vacuum low pressure is 20-60 Pa;
the molar ratio of the alkyd is 1:1.1.
6. The method for producing a phosphorus-containing flame retardant polyester according to claim 5, wherein in step 2), any one or more of the following conditions are satisfied:
the dibasic acid is terephthalic acid;
the dihydric alcohol is 1, 4-cyclohexanedimethanol;
the catalyst is n-butyl titanate;
the mole ratio of the dibasic acid, the dihydric alcohol and the phosphorus-containing dihydric alcohol is 1.1:0.5:0.5;
n-butyl titanate is 0.03 of the total amount of dihydric alcohol and dihydric alcohol containing phosphorus wt ％。
7. The process for preparing a phosphorus-comprising flame retardant polyester according to any one of claims 4 to 6, wherein in step 3), the reaction time is 3 hours.
8. A phosphorus-containing flame retardant polyester prepared by the preparation method according to any one of claims 4 to 7.
9. Use of a phosphorus-containing flame retardant polyester according to claim 8, characterized in that: for making a punched card connector, grid plate, plug and slot plate assembly or circuit board.
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| CN202311334596.4A CN117384209A (en) | 2023-10-16 | 2023-10-16 | Phosphorus-containing dihydric alcohol and preparation method thereof, phosphorus-containing flame-retardant polyester and preparation method and application thereof |
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| CN202311334596.4A CN117384209A (en) | 2023-10-16 | 2023-10-16 | Phosphorus-containing dihydric alcohol and preparation method thereof, phosphorus-containing flame-retardant polyester and preparation method and application thereof |
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