CN111647015A - High-heat-resistance phosphite antioxidant PEPQ and preparation method and application thereof - Google Patents
High-heat-resistance phosphite antioxidant PEPQ and preparation method and application thereof Download PDFInfo
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- CN111647015A CN111647015A CN202010659178.2A CN202010659178A CN111647015A CN 111647015 A CN111647015 A CN 111647015A CN 202010659178 A CN202010659178 A CN 202010659178A CN 111647015 A CN111647015 A CN 111647015A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 51
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 47
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 title claims abstract description 31
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000008096 xylene Substances 0.000 claims abstract description 58
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- FTDZECHQBVIHKZ-UHFFFAOYSA-N 5,5-dibromo-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(Br)(Br)CC=C1C1=CC=CC=C1 FTDZECHQBVIHKZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 14
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims abstract description 8
- VNNCRTPIHMVYNT-UHFFFAOYSA-N OP(O)OP(O)O.C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O VNNCRTPIHMVYNT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000004321 preservation Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 18
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a high heat-resistant phosphite antioxidant PEPQ and a preparation method and application thereof, and the preparation method comprises the following steps: s1: adding 4, 4-dibromobiphenyl, yellow phosphorus and phosphorus tribromide into a reaction vessel to prepare p-phosphorus bromobiphenyl; s2: preparing a xylene solution of 2, 4-di-tert-butylphenol; s3: cooling the reaction container, adding a xylene solution of 2, 4-di-tert-butylphenol into the reaction container, vacuumizing the reaction container, and carrying out reflux reaction to obtain tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite; s4: adding neutralized xylene, n-dibutylamine, triethylamine and triethanolamine into the reaction container to perform neutralization reaction to obtain a product mixed solution; s5: adding filter-aid diatomite, and then carrying out hot filtration; s6: and washing, filtering and drying the antioxidant crystals. The phosphite ester antioxidant PEPQ prepared by the invention has the advantages of outstanding high-temperature oxidation resistance, no pollution, no coloring, excellent hydrolysis resistance, low volatility, high precipitation resistance and good durability.
Description
Technical Field
The invention relates to the field of synthesis of chemical auxiliary agents, and in particular relates to a phosphite antioxidant PEPQ with high heat resistance, and a preparation method and application thereof.
Background
Antioxidants are important stabilizers for polymer resin processing and applications involving almost all polymers and their articles. In recent years, the yield of polymer products in China is increased rapidly, which provides good market prospect for the development and application of antioxidants. The phosphite ester antioxidant is a high-efficiency antioxidant with excellent performance, can improve the processing stability of polymers, and has good color stability, heat-resistant stability and excellent hydrolysis resistance, so that the phosphite ester antioxidant has good application prospect in high polymer materials such as polyolefin, styrene resin, engineering thermoplastic resin and the like.
Phosphite-assisted antioxidants are one of the most active areas of development in polymer stabilization aids in the 90 s of the 20 th century. Over ten years, new structural varieties emerge endlessly, but through the chemical structures, the phosphites with the new structures mostly contain substituted aromatic rings and have more spiro pentaerythritol diphosphite structures and bisphenol phosphite structures, so that the phosphite auxiliary antioxidant in the prior art has serious defects in both high-temperature oxidation resistance and hydrolytic stability; in addition, the production technology of phosphite antioxidants in the current market adopts benzene as a reaction solvent, and has the following problems: 1. benzene has high toxicity and belongs to easily carcinogenic chemicals; 2. the byproducts (aluminum chloride, sodium chloride and the like) are many, the solid waste amount is large, the treatment cost is high, and the environment is not protected; 3. the yield is low.
Disclosure of Invention
The invention aims to provide a high-heat-resistance phosphite ester antioxidant PEPQ and a preparation method and application thereof aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a phosphite antioxidant PEPQ with high heat resistance, which comprises the following steps:
s1: adding 4, 4-dibromobiphenyl, yellow phosphorus and phosphorus tribromide into a reaction vessel, replacing the mixture with nitrogen for three times, sealing the reaction vessel, and performing gradient heating reaction to obtain an intermediate p-phosphorus bromobiphenyl;
s2: adding 2, 4-di-tert-butylphenol and reaction xylene into a beaker, and completely dissolving at normal temperature to obtain a xylene solution of the 2, 4-di-tert-butylphenol;
s3: cooling the reaction container, adding the xylene solution of the 2, 4-di-tert-butylphenol prepared in the step S2 into the reaction container, vacuumizing the reaction container, performing reflux reaction to obtain tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite, distilling out the reaction xylene, and recovering;
s4: adding neutralized xylene, n-dibutylamine, triethylamine and triethanolamine into the reaction container to perform neutralization reaction to obtain a product mixed solution;
s5: adjusting the pH value of the product mixed solution prepared in the step S4 to 8-9, adding filter-aid type diatomite, then carrying out hot filtration, distilling out neutralized xylene for recovery, and simultaneously precipitating tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite crystals;
s6: and (4) adding methanol into the crystal precipitated in the step S5, washing, filtering and drying to obtain the antioxidant PEPQ.
Preferably, the gradient temperature-rising reaction in S1 is: the first stage is as follows: heating and raising the temperature under normal pressure to raise the temperature in the reaction container to 110 ℃ below zero at 100 ℃ below zero, and then carrying out heat preservation reaction at 110 ℃ below zero; and a second stage: heating to raise the temperature to 190 ℃ at 180 ℃, and then carrying out heat preservation reaction at 190 ℃ at 180 ℃; and a third stage: heating to raise the temperature to 260-270 deg.c, and maintaining the temperature at 260-270 deg.c for reaction; a fourth stage: heating to raise the temperature to 290-300 deg.c, and maintaining the temperature at 290-300 deg.c.
Preferably, in the first stage, the duration of the heating and temperature rise is 1.5 to 2 hours, and the duration of the heat preservation reaction is 1 hour; in the second stage, the duration of the heating and temperature rising is 1.5-2 hours, and the duration of the heat preservation reaction is 2 hours; in the third stage, the duration of the heating and temperature rising is 1.5-2 hours, and the duration of the heat preservation reaction is 3 hours; in the fourth stage, the duration of heating and temperature rise is 0.7-1 hour, and the duration of the heat preservation reaction is 2 hours.
Preferably, step S3 includes: reducing the temperature in the reaction container to 110-120 ℃, starting a vacuum pump to pump vacuum, absorbing the tail gas in the reaction container by clear water, alkaline water and a drying agent respectively, then entering a vacuum pump, dropwise adding the xylene solution of the 2, 4-di-tert-butylphenol prepared in the step S2 under the condition that the pressure in the reaction container is-60 to-70 kpa, and carrying out reflux reaction for 4 to 5 hours after dropwise adding is finished within 30 to 40 minutes; step S3 further includes: after the reaction is completed, the reaction xylene in the reaction vessel is distilled out and recovered under the pressure of-60 to-70 kpa and the temperature of 110 ℃ to 120 ℃.
Preferably, step S4 specifically includes: regulating the pressure in the reaction container to be below-93 kpa, raising the temperature to be 120-130 ℃, adding the neutralized xylene, the n-dibutylamine, the triethylamine and the triethanolamine, and carrying out neutralization reaction for 0.5 hour to obtain a product mixed solution.
Preferably, step S5 includes: and distilling the neutralized xylene from the product mixed solution at the temperature of 120 ℃ and 130 ℃ and under the condition of less than or equal to-96 kpa, and recovering.
Preferably, step S6 includes: gradually separating out antioxidant crystals along with the process of evaporating and neutralizing xylene in a three-mouth bottle, adding 600ml of methanol into the three-mouth bottle after the neutralizing xylene is evaporated to wash the antioxidant crystals to form slurry, then reducing the temperature in the three-mouth bottle to 30 ℃ or below, starting filtration, forming a filter cake in a Buchner funnel, and then leaching the filter cake with 60ml of methanol; step S6 further includes: after the filtration is finished, putting the filter cake into a vacuum oven, and drying for 2 hours at the temperature of between 90 and 95 ℃ under the pressure of less than or equal to-96 kpa to obtain a phosphite ester antioxidant finished product; and distilling the filtered mother liquor at normal pressure, and recovering the methanol.
Preferably, the molar ratio of the 4, 4-dibromobiphenyl to the yellow phosphorus is 1 (1.31-1.33); the molar ratio of the 4, 4-dibromobiphenyl to the phosphorus tribromide is 1 (0.65-0.67); the molar ratio of the 4, 4-dibromobiphenyl to the 2, 4-di-tert-butylphenol is 1 (4.03-4.06); the molar ratio of the 4, 4-dibromobiphenyl to the reacted xylene is 1: (11.2-11.5); the molar ratio of the 4, 4-dibromobiphenyl to the neutralized xylene is 1: (11.2-11.5); the molar ratio of the 4, 4-dibromobiphenyl to the di-n-butylamine is 1: (0.05-0.06); the molar ratio of the 4, 4-dibromobiphenyl to the triethylamine is 1: (0.06-0.07); the molar ratio of the 4, 4-dibromobiphenyl to the triethanolamine is 1: (0.13-0.14); the molar ratio of the 4, 4-dibromobiphenyl to the methanol is 1: (51-52).
In a second aspect, the present invention provides a highly heat-resistant phosphite antioxidant PEPQ prepared by the above method.
The third aspect of the invention provides that the phosphite antioxidant PEPQ with high heat resistance is suitable for PS, PP, PA, PU, PC, EVA, PE-LLD, PBT, PET and ABS high polymers.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
1. the phosphite ester antioxidant PEPQ prepared by the method has the advantages of outstanding high-temperature resistance and oxidation resistance, no pollution, no coloring, excellent hydrolysis resistance, low volatility, high precipitation resistance and good durability.
2. The raw and auxiliary materials of the method do not belong to highly toxic substances, no catalyst is needed in the reaction process, three wastes generated by treating the catalyst are avoided, no waste water and waste liquid are generated, and the waste solid content is small due to the addition of the diatomite; the yield is high and is far from the existing production process.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a preparation method of a phosphite antioxidant PEPQ with high heat resistance, which comprises the following steps:
s1: adding 4, 4-dibromobiphenyl, yellow phosphorus and phosphorus tribromide into a reaction vessel, replacing the mixture with nitrogen for three times, sealing the reaction vessel, and performing gradient heating reaction to obtain an intermediate p-phosphorus bromobiphenyl;
s2: adding 2, 4-di-tert-butylphenol and reaction xylene into a beaker, and completely dissolving at normal temperature to obtain a xylene solution of the 2, 4-di-tert-butylphenol;
s3: cooling the reaction container, adding the xylene solution of the 2, 4-di-tert-butylphenol prepared in the step S2 into the reaction container, vacuumizing the reaction container, performing reflux reaction to obtain tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite, distilling out the reaction xylene, and recovering;
s4: adding neutralized xylene, n-dibutylamine, triethylamine and triethanolamine into the reaction container to perform neutralization reaction to obtain a product mixed solution;
s5: adjusting the pH value of the product mixed solution prepared in the step S4 to 8-9, adding filter-aid type diatomite, then carrying out hot filtration, distilling out neutralized xylene for recovery, and simultaneously precipitating tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite crystals;
s6: and (4) adding methanol into the crystal precipitated in the step S5, washing, filtering and drying to obtain the antioxidant PEPQ.
In a preferred embodiment, the gradient temperature-increasing reaction in S1 is: the first stage is as follows: heating and raising the temperature under normal pressure to raise the temperature in the reaction container to 110 ℃ below zero at 100 ℃ below zero, and then carrying out heat preservation reaction at 110 ℃ below zero; and a second stage: heating to raise the temperature to 190 ℃ at 180 ℃, and then carrying out heat preservation reaction at 190 ℃ at 180 ℃; and a third stage: heating to raise the temperature to 260-270 deg.c, and maintaining the temperature at 260-270 deg.c for reaction; a fourth stage: heating to raise the temperature to 290-300 deg.c, and maintaining the temperature at 290-300 deg.c.
In a preferred embodiment, in the first stage, the duration of the heating and temperature rise is 1.5-2 hours, and the duration of the heat preservation reaction is 1 hour; in the second stage, the duration of the heating and temperature rising is 1.5-2 hours, and the duration of the heat preservation reaction is 2 hours; in the third stage, the duration of the heating and temperature rising is 1.5-2 hours, and the duration of the heat preservation reaction is 3 hours; in the fourth stage, the duration of heating and temperature rise is 0.7-1 hour, and the duration of the heat preservation reaction is 2 hours.
In a preferred embodiment, step S3 includes: and (3) reducing the temperature in the reaction container to 110-120 ℃, starting a vacuum pump to pump vacuum, absorbing the tail gas in the reaction container by clear water, alkaline water and a drying agent respectively, then entering a vacuum pump, dropwise adding the xylene solution of the 2, 4-di-tert-butylphenol prepared in the step S2 under the condition that the pressure in the reaction container is-60 to-70 kpa, and carrying out reflux reaction for 4 to 5 hours after dropwise adding is finished within 30 to 40 minutes. Step S3 includes: after the reaction is completed, the reaction xylene in the reaction vessel is distilled out and recovered under the pressure of-60 to-70 kpa and the temperature of 110 ℃ to 120 ℃.
In a preferred embodiment, step S4 is specifically: regulating the pressure in the reaction container to be below-93 kpa, raising the temperature to be 120-130 ℃, adding the neutralized xylene, the n-dibutylamine, the triethylamine and the triethanolamine, and carrying out neutralization reaction for 0.5 hour to obtain a product mixed solution.
In a preferred embodiment, step S5 includes: and distilling the neutralized xylene from the product mixed solution at the temperature of 120 ℃ and 130 ℃ and under the condition of less than or equal to-96 kpa, and recovering.
In a preferred embodiment, step S6 includes: the antioxidant crystals are gradually separated out along with the process of evaporating and neutralizing xylene in a three-neck flask, 600ml of methanol is added into the three-neck flask to wash the antioxidant crystals after the neutralizing xylene is evaporated to form slurry, then the temperature in the three-neck flask is reduced to 30 ℃ or below, the filtration is started, and after a filter cake is formed in a Buchner funnel, the filter cake is rinsed by 60ml of methanol. Step S6 includes: after the filtration is finished, putting the filter cake into a vacuum oven, and drying for 2 hours at the temperature of between 90 and 95 ℃ under the pressure of less than or equal to-96 kpa to obtain a phosphite ester antioxidant finished product; and distilling the filtered mother liquor at normal pressure, and recovering the methanol.
In a preferred embodiment, the molar ratio of the 4, 4-dibromobiphenyl to the yellow phosphorus is 1 (1.31-1.33); the molar ratio of the 4, 4-dibromobiphenyl to the phosphorus tribromide is 1 (0.65-0.67); the molar ratio of the 4, 4-dibromobiphenyl to the 2, 4-di-tert-butylphenol is 1 (4.03-4.06); the molar ratio of the 4, 4-dibromobiphenyl to the reacted xylene is 1: (11.2-11.5); the molar ratio of the 4, 4-dibromobiphenyl to the neutralized xylene is 1: (11.2-11.5); the molar ratio of the 4, 4-dibromobiphenyl to the di-n-butylamine is 1: (0.05-0.06); the molar ratio of the 4, 4-dibromobiphenyl to the triethylamine is 1: (0.06-0.07); the molar ratio of the 4, 4-dibromobiphenyl to the triethanolamine is 1: (0.13-0.14); the molar ratio of the 4, 4-dibromobiphenyl to the methanol is 1: (51-52).
In a second aspect, the present invention provides a highly heat-resistant phosphite antioxidant PEPQ prepared by the above method.
The third aspect of the invention provides that the phosphite antioxidant PEPQ with high heat resistance is suitable for high polymers such as PS, PP, PA, PU, PC, EVA, PE-LLD, PBT, PET, ABS and the like.
The procedures in the following procedure for the preparation of the phosphite antioxidant PEPQ are conventional unless otherwise specified, and the starting materials are commercially available from the open literature unless otherwise specified.
Example 1
A phosphite antioxidant PEPQ was prepared as follows:
s1: adding 90.50g of 4, 4-dibromobiphenyl, 11.99g of yellow phosphorus and 52.42g of phosphorus tribromide into a 1000ml five-port reaction bottle, replacing the mixture with nitrogen with the concentration of 99.99% for three times, sealing the five-port reaction bottle, heating the five-port reaction bottle, carrying out a first-stage reaction, heating the five-port reaction bottle from the normal temperature to 110 ℃ within 1.5-2 hours, and carrying out a heat preservation reaction for 1 hour; the second stage reaction, which is carried out at the temperature of between 100 and 110 ℃ and 180 and 190 ℃ within 1.5 to 2 hours, and the reaction is carried out for 2 hours under the condition of heat preservation; the third stage reaction, which is carried out by heating from 190 ℃ at 180 ℃ to 270 ℃ at 260 ℃ within 1.5-2 hours and carrying out heat preservation reaction for 3 hours; the fourth stage of reaction, wherein the temperature is increased from 260 ℃ to 290 ℃ to 300 ℃ within 0.7-1 hour, and the reaction time is kept for 2 hours to generate an intermediate p-phosphorus bromobiphenyl;
s2: 239g of 2, 4-di-tert-butylphenol and 400ml of reaction xylene (used as a reaction solvent) are put in a beaker to be completely dissolved at normal temperature, so that xylene solution of the 2, 4-di-tert-butylphenol is obtained;
s3: starting a vacuum pump, vacuumizing the five-mouth reaction bottle to-60 to-70 kpa, and before entering the vacuum pump, absorbing tail gas (hydrogen bromide) in the five-mouth reaction bottle by clear water, alkaline water and drying agents (calcium chloride and magnesium chloride) respectively and then entering the vacuum pump, so as to prevent a byproduct of the reaction, namely the hydrogen bromide, from entering the vacuum pump to be corroded. Pouring the prepared xylene solution of 2, 4-di-tert-butylphenol into a dropping funnel on a 1000ml five-mouth reaction bottle, controlling the opening of the dropping funnel by kock, dropping into the five-mouth reaction bottle at a constant speed within 30-40 minutes, and after dropping, carrying out heat preservation reaction for 4-5 hours at the temperature of 110-120 ℃ under the pressure of-60 to-70 kpa to generate a crude product of tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite and a byproduct hydrogen bromide, wherein the xylene has great reflux to ensure that the byproduct hydrogen bromide is pumped away; the hydrogen bromide is absorbed by moisture in three stages to generate hydrobromic acid with different concentrations, and the low-concentration hydrobromic acid continuously absorbs the hydrogen bromide to be changed into concentrated hydrobromic acid, so that the absorption rate of the hydrogen bromide can be controlled to be about 99.9 percent; the reaction xylene in the five-mouth reaction bottle is steamed out at the pressure of-60 to-70 kpa and the temperature of 110 ℃ and 120 ℃ for the next reaction, the reaction xylene is steamed out as completely as possible, and the residual hydrogen bromide is reduced;
s4: when the xylene evaporation reaction of the reaction liquid is finished, controlling the temperature at 120-130 ℃, controlling the pressure below-93 kpa, adding 400ml of neutralized xylene (used as a neutralization solvent), 2g of n-dibutylamine, 2g of triethylamine and 6g of triethanolamine into a five-opening reaction bottle, carrying out neutralization and heat preservation within the temperature range of 120-130 ℃ under the micro-positive pressure condition, and controlling the heat preservation time at 0.5 hour to obtain a product mixed solution;
s5: reacting the added alkaline auxiliary agent with residual hydrogen bromide to make the reaction solution alkaline, controlling the pH value between 8 and 9, adding 3g of filter-aid diatomite, stirring for 10 minutes, then carrying out thermal filtration, filtering out by-products and salt of the reaction, putting the filtrate into another three-mouth bottle, steaming out the neutralized xylene within the temperature range of 120 plus one year and 130 ℃ and under the pressure condition of less than or equal to-96 kpa, and evaporating the xylene to dryness as much as possible for the next batch of production and use;
s6: with the process of distilling and neutralizing xylene, antioxidant crystals are gradually separated out, after the neutralized xylene is distilled, 600ml of methanol is added into a three-neck flask to wash the antioxidant to form slurry material, impurities such as residual xylene, byproducts, salt and the like are dissolved into the methanol, the temperature of the three-neck flask is reduced to be below 30 ℃, the filtration is started, after a filter cake is formed in a Buchner funnel, 60ml of methanol is used for leaching the filter cake, after the filtration is finished, the filter cake is placed into a vacuum oven and is dried for 2 hours at the temperature of between 90 and 95 ℃ under the pressure of less than or equal to-96 kpa, 291.6g of phosphite antioxidant PEPQ finished product is obtained, and the yield of the phosphite antioxidant PEPQ produced by adopting the process disclosed by the invention reaches 97 to 98 percent, and is higher. And distilling the filtered mother liquor at normal pressure to obtain methanol for recycling phosphite antioxidant PEPQ in the next batch.
The specific reaction equation is as follows:
while the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a phosphite antioxidant PEPQ with high heat resistance is characterized by comprising the following steps:
s1: adding 4, 4-dibromobiphenyl, yellow phosphorus and phosphorus tribromide into a reaction vessel, replacing the mixture with nitrogen for three times, sealing the reaction vessel, and performing gradient heating reaction to obtain an intermediate p-phosphorus bromobiphenyl;
s2: adding 2, 4-di-tert-butylphenol and reaction xylene into a beaker, and completely dissolving at normal temperature to obtain a xylene solution of the 2, 4-di-tert-butylphenol;
s3: cooling the reaction container, adding the xylene solution of the 2, 4-di-tert-butylphenol prepared in the step S2 into the reaction container, vacuumizing the reaction container, performing reflux reaction to obtain tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite, distilling out the reaction xylene, and recovering;
s4: adding neutralized xylene, n-dibutylamine, triethylamine and triethanolamine into the reaction container to perform neutralization reaction to obtain a product mixed solution;
s5: adjusting the pH value of the product mixed solution prepared in the step S4 to 8-9, adding filter-aid type diatomite, then carrying out hot filtration, distilling out neutralized xylene for recovery, and simultaneously precipitating tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite crystals;
s6: and (4) adding methanol into the crystal precipitated in the step S5, washing, filtering and drying to obtain the antioxidant PEPQ.
2. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 1, wherein the gradient temperature rising reaction in S1 is as follows: the first stage is as follows: heating and raising the temperature under normal pressure to raise the temperature in the reaction container to 110 ℃ below zero at 100 ℃ below zero, and then carrying out heat preservation reaction at 110 ℃ below zero; and a second stage: heating to raise the temperature to 190 ℃ at 180 ℃, and then carrying out heat preservation reaction at 190 ℃ at 180 ℃; and a third stage: heating to raise the temperature to 260-270 deg.c, and maintaining the temperature at 260-270 deg.c for reaction; a fourth stage: heating to raise the temperature to 290-300 deg.c, and maintaining the temperature at 290-300 deg.c.
3. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 2, wherein in the first stage, the duration of the heating and temperature rise is 1.5-2 hours, and the duration of the heat preservation reaction is 1 hour; in the second stage, the duration of the heating and temperature rising is 1.5-2 hours, and the duration of the heat preservation reaction is 2 hours; in the third stage, the duration of the heating and temperature rising is 1.5-2 hours, and the duration of the heat preservation reaction is 3 hours; in the fourth stage, the duration of heating and temperature rise is 0.7-1 hour, and the duration of the heat preservation reaction is 2 hours.
4. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 1, wherein the step S3 comprises: reducing the temperature in the reaction container to 110-120 ℃, starting a vacuum pump to pump vacuum, absorbing the tail gas in the reaction container by clear water, alkaline water and a drying agent respectively, then entering a vacuum pump, dropwise adding the xylene solution of the 2, 4-di-tert-butylphenol prepared in the step S2 under the condition that the pressure in the reaction container is-60 to-70 kpa, and carrying out reflux reaction for 4 to 5 hours after dropwise adding is finished within 30 to 40 minutes; step S3 further includes: after the reaction is completed, the reacted xylene in the reaction vessel is distilled out and recovered at a pressure of-60-70 kpa and a temperature of 110 ℃ and 120 ℃.
5. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 1, wherein the step S4 is specifically as follows: regulating the pressure in the reaction container to be below-93 kpa, raising the temperature to be 120-130 ℃, adding the neutralized xylene, the n-dibutylamine, the triethylamine and the triethanolamine, and carrying out neutralization reaction for 0.5 hour to obtain a product mixed solution.
6. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 1, wherein the step S5 comprises: and distilling the neutralized xylene from the product mixed solution at the temperature of 120 ℃ and 130 ℃ and under the condition of less than or equal to-96 kpa, and recovering.
7. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 1, wherein the step S6 comprises: gradually separating out antioxidant crystals along with the process of evaporating and neutralizing xylene in a three-mouth bottle, adding 600ml of methanol into the three-mouth bottle after the neutralizing xylene is evaporated to wash the antioxidant crystals to form slurry, then reducing the temperature in the three-mouth bottle to 30 ℃ or below, starting filtration, forming a filter cake in a Buchner funnel, and then leaching the filter cake with 60ml of methanol; step S6 further includes: after the filtration is finished, putting the filter cake into a vacuum oven, and drying for 2 hours at the temperature of between 90 and 95 ℃ under the pressure of less than or equal to-96 kpa to obtain a phosphite ester antioxidant finished product; and distilling the filtered mother liquor at normal pressure, and recovering the methanol.
8. The method for preparing the high heat-resistant phosphite antioxidant PEPQ as claimed in claim 1, wherein the molar ratio of the 4, 4-dibromobiphenyl to the yellow phosphorus is 1 (1.31-1.33); the molar ratio of the 4, 4-dibromobiphenyl to the phosphorus tribromide is 1 (0.65-0.67); the molar ratio of the 4, 4-dibromobiphenyl to the 2, 4-di-tert-butylphenol is 1 (4.03-4.06); the molar ratio of the 4, 4-dibromobiphenyl to the reacted xylene is 1: (11.2-11.5); the molar ratio of the 4, 4-dibromobiphenyl to the neutralized xylene is 1: (11.2-11.5); the molar ratio of the 4, 4-dibromobiphenyl to the di-n-butylamine is 1: (0.05-0.06); the molar ratio of the 4, 4-dibromobiphenyl to the triethylamine is 1: (0.06-0.07); the molar ratio of the 4, 4-dibromobiphenyl to the triethanolamine is 1: (0.13-0.14); the molar ratio of the 4, 4-dibromobiphenyl to the methanol is 1: (51-52).
9. A highly heat-resistant phosphite antioxidant PEPQ obtainable by the process as claimed in any of claims 1 to 8.
10. The high heat-resistant phosphite antioxidant PEPQ as claimed in claim 9, suitable for PS, PP, PA, PU, PC, EVA, PE-LLD, PBT, PET and ABS high polymer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3825629A (en) * | 1970-10-22 | 1974-07-23 | Sandoz Ltd | Benzene phosphonates |
| CN102942592A (en) * | 2012-11-21 | 2013-02-27 | 山东科技大学 | Method for synthesizing 4, 4'-biphenyl double dichloride phosphine |
| CN104860990A (en) * | 2015-05-14 | 2015-08-26 | 营口市风光化工有限公司 | Phosphite antioxidant P-EPQ preparation method |
-
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- 2020-07-09 CN CN202010659178.2A patent/CN111647015A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3825629A (en) * | 1970-10-22 | 1974-07-23 | Sandoz Ltd | Benzene phosphonates |
| CN102942592A (en) * | 2012-11-21 | 2013-02-27 | 山东科技大学 | Method for synthesizing 4, 4'-biphenyl double dichloride phosphine |
| CN104860990A (en) * | 2015-05-14 | 2015-08-26 | 营口市风光化工有限公司 | Phosphite antioxidant P-EPQ preparation method |
Non-Patent Citations (1)
| Title |
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| 王洪亮 等: "抗氧剂P-EPQ的合成", 《天津化工》 * |
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