CN113881044A - High-temperature-resistant cosmetic bottle cap and preparation method thereof - Google Patents
High-temperature-resistant cosmetic bottle cap and preparation method thereof Download PDFInfo
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- CN113881044A CN113881044A CN202111274590.3A CN202111274590A CN113881044A CN 113881044 A CN113881044 A CN 113881044A CN 202111274590 A CN202111274590 A CN 202111274590A CN 113881044 A CN113881044 A CN 113881044A
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- 239000002537 cosmetic Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 33
- 150000004678 hydrides Chemical class 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 17
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 229920012287 polyphenylene sulfone Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 55
- -1 lithium aluminum hydride Chemical group 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052987 metal hydride Inorganic materials 0.000 claims description 7
- 150000004681 metal hydrides Chemical group 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 8
- 150000003839 salts Chemical group 0.000 description 8
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The application relates to the field of new material synthesis, and particularly discloses a high-temperature-resistant cosmetic bottle cap and a preparation method thereof. The high-temperature-resistant cosmetic bottle cap is prepared from the following raw materials in parts by weight: 20-35 parts of 4,4 '-biphenol, 25-45 parts of 4, 4' -dichlorodiphenyl sulfone, 10-20 parts of alkali, 5-10 parts of hydride reducing agent, 50-80 parts of ether solvent and 40-60 parts of sulfolane. The high temperature resistant cosmetic bottle cap of this application has thermoplasticity and good advantage of heat resistance.
Description
Technical Field
The application relates to the field of new material synthesis, in particular to a high-temperature-resistant cosmetic bottle cap and a preparation method thereof.
Background
Common cosmetic packages in the market are mostly made of plastics, and the plastics are generally divided into three types of general plastics, engineering plastics and special plastics according to different use characteristics, wherein the general plastics commonly used in the market are generally polyethylene, polypropylene, polyvinyl chloride, polystyrene and acrylonitrile-butadiene-styrene copolymer.
In the related art, the common cosmetic bottle caps on the market are prepared from polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer and the like, but the synthetic raw materials of general plastics such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer and the like contain low-toxicity bisphenol a, and the bisphenol a is very easily volatilized under the high-temperature condition, and the volatilized bisphenol a may enter the cosmetics. Therefore, the prepared material has better stability at high temperature and is not easy to volatilize bisphenol A; as cosmetics are daily necessities in daily life, the high-temperature resistance of the bottle cap material for cosmetics is extremely important.
Disclosure of Invention
In order to further improve the high temperature resistance of the cosmetic bottle cap material, the application provides a high temperature resistant cosmetic bottle cap and a preparation method thereof.
In a first aspect, the application provides a high temperature resistant cosmetic bottle cap, adopts following technical scheme:
a high-temperature-resistant cosmetic bottle cap is prepared from the following raw materials in parts by weight: 20-35 parts of 4,4 '-biphenol, 25-45 parts of 4, 4' -dichlorodiphenyl sulfone, 10-20 parts of alkali, 5-10 parts of a hydride reducing agent, 50-80 parts of an ether solution and 40-60 parts of sulfolane.
By adopting the technical scheme, the 4,4 ' -biphenyl diphenol and alkali firstly generate biphenyl diphenol, the condition of the further polycondensation reaction of the biphenyl diphenol and the 4,4 ' -dichlorodiphenyl sulfone is high temperature, but S ═ O unsaturated bonds are easily oxidized in the reaction process of the 4 ' -dichlorodiphenyl sulfone at the high temperature, so that the purity of the finally generated polyphenylene sulfone resin is low, and the heat resistance and the thermoplasticity of the polyphenylene sulfone resin are difficult to reach the standard. The addition of the hydride reducing agent inhibits the oxidation of S ═ O and inhibits the oxidation of other unsaturated bonds in the biphenyl diphenolate and the 4,4 '-dichlorodiphenyl sulfone in the process of reacting the biphenyl diphenolate and the 4, 4' -dichlorodiphenyl sulfone, so that the purity of the produced polyphenylene sulfone resin is high, and the bottle cap made of the polyphenylene sulfone resin has good thermoplasticity and heat resistance.
And the raw materials for preparing the polyphenylene sulfone resin do not contain bisphenol A, so that the cosmetic bottle cap prepared from the polyphenylene sulfone resin does not volatilize bisphenol A at high temperature.
Optionally, the weight ratio of the 4, 4' -dichlorodiphenyl sulfone to the hydride reducing agent is (5-6): 1.
By adopting the technical scheme, the integral process of the reaction can be influenced by excessive addition of the hydride reducing agent, the generation of high-purity products is not facilitated, and waste can be caused; the addition amount of the hydride reducing agent is too small, and the reduction effect on substances needing to be reduced in the reaction process cannot be achieved, so that the purity of the finally generated product is low.
Optionally, the hydride reducing agent is a metal hydride reducing agent.
By adopting the technical scheme, the reaction condition of the reaction of the metal hydride reducing agent and the reactant is mild, and the formed by-products are less compared with other reducing agents, so that the purity of the finally prepared product is higher. The metal ions in the metal hydride reducing agent can be further crosslinked with the generated long-chain polymer, so that the molecular weight of the polymer for manufacturing the bottle cap is increased, and the manufactured bottle cap has good mechanical property and heat resistance.
Optionally, the metal hydride reducing agent is lithium aluminum hydride or potassium borohydride.
By adopting the technical scheme, lithium aluminum hydride or potassium borohydride is aluminum hydride tetrahydride AlH4-Or tetrahydroboron ions BH4-The double salt structure of (1) has four negative ions for reaction, so that the double salt structure can gradually react with reactants, ensure that the oxidation reaction of 4,4 '-dichlorodiphenyl sulfone or products is continuously carried out in the reverse reaction direction while the reaction is carried out, prevent the oxidation reaction of 4, 4' -dichlorodiphenyl sulfone or products, and ensure that the purity of the final product is higher.
Optionally, the alkali is one or more of sodium carbonate, calcium carbonate and potassium carbonate.
By adopting the technical scheme, the sodium carbonate, the calcium carbonate and the potassium carbonate are easy to purchase and are cheap; after sodium carbonate, calcium carbonate or potassium carbonate reacts with 4, 4' -biphenol to generate salt, the byproduct is water and carbon dioxide, and the salt is non-toxic and easy to remove, so that the sodium carbonate, calcium carbonate or potassium carbonate is used as the alkali for the reaction, and the method is economical, environment-friendly and pollution-free.
Optionally, the ether solvent is anhydrous tetrahydrofuran or diethyl ether.
By adopting the technical scheme, the metal hydride reducing agent can generate side reaction when meeting water, so the solvent adopts anhydrous ether solvent, the smooth reaction is ensured, no by-product is generated, the purity of the final product is higher, and the prepared cosmetic bottle cap has better thermoplasticity and heat resistance.
In a second aspect, the present application provides a method for preparing a high temperature resistant cosmetic bottle cap, comprising the steps of: step I: heating sulfolane to 70-90 ℃, adding 4, 4' -biphenol and alkali into sulfolane for reaction, extracting the obtained product, removing a water phase, and taking the residual organic phase as a first reaction liquid;
step II: heating the first reaction solution to 105-110 ℃, mixing and heating 4, 4' -dichlorodiphenyl sulfone and an ether solvent, dropwise adding a hydride reducing agent in the heating process, heating until the solvent flows back, and collecting and removing the back-flowed solvent to obtain a second reaction solution; step III: heating the second reaction solution to 190-220 ℃, and then continuously stirring for reaction to obtain a third reaction solution;
step IV: carrying out vacuum filtration on the third reaction liquid to obtain polyphenylene sulfone resin;
step V: and (3) performing hot-press molding on the polyphenylene sulfone resin to prepare the cosmetic bottle cap.
Optionally, in the step iv, the third reaction solution is washed with ethanol, and then is subjected to vacuum filtration to obtain the polyphenylene sulfone resin.
By adopting the technical scheme, the reaction in the step I generates salt, water and carbon dioxide, the salt is the reaction raw material in the step II, and the water is removed by the subsequent extraction step. And in the step II, while the first reaction liquid reacts with the 4,4 ' -dichlorodiphenyl sulfone, a hydride reducing agent is gradually dripped, so that when the first large batch of first reaction liquid reacts with the 4,4 ' -dichlorodiphenyl sulfone, the hydride reducing agent continuously inhibits the oxidation of the first reaction liquid and the 4,4 ' -dichlorodiphenyl sulfone, and the finally obtained reaction product has high purity. And in the step III, raising the temperature again to ensure that a small amount of the remaining first reaction liquid and the 4, 4' -dichlorodiphenyl sulfone are continuously reacted, and the obtained product fragments are continuously polymerized at a high temperature to generate a polymer with a larger molecular weight, so that the thermoplastic property and the heat resistance of the obtained product are better. In the step IV, the polyphenylene sulfone resin is insoluble in ethanol, and the ethanol with stronger polarity can elute and remove other organic matters in the product, so that the obtained polyphenylene sulfone resin has higher purity, and the bottle cap made of the polyphenylene sulfone resin has better thermoplasticity and heat resistance.
Optionally, the dropping time of the hydride reducing agent in the II is 20-40 min.
By adopting the technical scheme, the dropping time of the hydride reducing agent is longer, and the hydride reducing agent can continuously inhibit the oxidation of reactants and polyphenylene sulfone resin in the reaction process of the first reaction liquid and 4, 4' -dichlorodiphenyl sulfone, so that the purity of the produced polyphenylene sulfone resin is higher.
Optionally, the step I, the step II and the step III are all performed under the protection of nitrogen.
By adopting the technical scheme, in the step I, the step II and the step III, the reaction is carried out in a nitrogen protection mode, so that oxygen is isolated in the reaction process, the reactants and the polyphenylene sulfone resin are prevented from being oxidized, the high purity of the polyphenylene sulfone resin is ensured, and the bottle cap prepared from the polyphenylene sulfone resin has good thermoplasticity and heat resistance.
Optionally, cooling is performed immediately after the hot press molding in the step v.
By adopting the technical scheme, the step of cooling is immediately carried out after the hot-press forming, so that the hot-press formed substance can keep the shape of the hot-press forming, and the shape of the prepared cosmetic bottle cap is more standard.
In summary, the present application has the following beneficial effects:
1. by adding the hydride reducing agent, in the process of reacting the biphenyl diphenolate with the 4,4 '-dichlorodiphenyl sulfone, the oxidation of S ═ O is inhibited, and other unsaturated bonds in the biphenyl diphenolate and the 4, 4' -dichlorodiphenyl sulfone are inhibited from being oxidized, so that the purity of the generated polyphenylene sulfone resin is higher, and the bottle cap made of the polyphenylene sulfone resin has better thermoplasticity and heat resistance;
2. lithium aluminum hydride or potassium borohydride is aluminum hydride tetrahydride AlH4-Or tetrahydroboron ions BH4-The double salt structure of (A) has four negative ions for reaction, so that the double salt structure can gradually react with reactants, ensure that the oxidation of 4, 4' -dichlorodiphenyl sulfone or products can be continuously inhibited while the reaction is carried out, and ensure that the final generation is carried outThe purity of the polyphenylene sulfone resin is high;
3. the dripping time of the hydride reducing agent is longer, so that the hydride reducing agent can continuously inhibit the oxidation of reactants and polyphenylene sulfone resin in the process of reacting the first reaction liquid with the 4,4 '-dichlorodiphenyl sulfone, and the finally generated 4, 4' -dichlorodiphenyl sulfone has higher purity.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples. The following examples and comparative examples are provided as raw material sources:
4, 4' -biphenol (content: 99%); 4, 4' -dichlorodiphenyl sulfone (purity: 98%); lithium aluminum hydride (specification: more than or equal to 98 percent) and potassium borohydride (specification: more than or equal to 98 percent); sulfolane (purity: 99%) and the above starting materials were obtained commercially.
Example 1
Preparation method of high-temperature-resistant cosmetic bottle cap
Step I: adding 40g of sulfolane into a round-bottom flask, heating the sulfolane to 80 ℃, adding 35g of 4, 4' -biphenol and 10g of sodium carbonate into the sulfolane, stirring and reacting at 500rpm/min for 20min, extracting the obtained product by using 500mL of dichloromethane, discarding an aqueous phase, heating the residual organic phase to 60 ℃, distilling to remove dichloromethane until no fraction flows out, and stopping heating, wherein the residual organic phase is a first reaction liquid;
step II: heating the first reaction solution to 105 ℃, stirring and reacting 45g of 4, 4' -dichlorodiphenyl sulfone and 50g of anhydrous tetrahydrofuran at the rotating speed of 500rpm/min for 40min, and dropwise adding 10g of lithium aluminum hydride in the reaction process; then heating to 80 ℃, after the solvent is refluxed, collecting and removing the distilled solvent, wherein the residual organic phase is a second reaction solution;
step III: heating the second reaction solution to 200 +/-10 ℃, and continuing stirring at the speed of 800rpm/min for reaction for 1h to obtain a third reaction solution;
step IV: washing the third reaction solution with 500mL of ethanol, and performing vacuum filtration to obtain polyphenylene sulfone resin;
step V: the polyphenylene sulfone resin is fed between pressing dies, the blank is hot-pressed at the temperature of 380 ℃ to be molded, in a shaping area, the product is rapidly cooled to the temperature below 315 ℃, then the product is separated from the pressing path, and the product is tempered at the temperature of 300-340 ℃, so that the high-temperature-resistant cosmetic bottle cap is obtained.
Example 2
Preparation method of high-temperature-resistant cosmetic bottle cap
Step I: adding 60g of sulfolane into a round-bottom flask, heating the sulfolane to 80 ℃, adding 20g of 4, 4' -biphenol and 20g of sodium carbonate into the sulfolane, stirring and reacting at the speed of 500rpm/min for 20min, extracting the obtained product by using 500mL of dichloromethane, discarding an aqueous phase, heating the residual organic phase to 60 ℃, distilling to remove the dichloromethane until no fraction flows out, and stopping heating, wherein the residual organic phase is a first reaction liquid;
step II: heating the first reaction solution to 105 ℃, stirring 25g of 4, 4' -dichlorodiphenyl sulfone and 80g of anhydrous tetrahydrofuran at the rotating speed of 500rpm/min for reacting for 40min, and dropwise adding 5g of lithium aluminum hydride in the reaction process; then heating to 80 ℃, after the solvent is refluxed, collecting and removing the distilled solvent, wherein the residual organic phase is a second reaction solution;
step III: heating the second reaction solution to 200 +/-10 ℃, and continuing stirring at the speed of 800rpm/min for reaction for 1h to obtain a third reaction solution;
step IV: washing the third reaction solution with 500mL of ethanol, and performing vacuum filtration to obtain polyphenylene sulfone resin;
step V: the polyphenylene sulfone resin is fed between pressing dies, the blank is hot-pressed at the temperature of 380 ℃ to be molded, in a shaping area, the product is rapidly cooled to the temperature below 315 ℃, then the product is separated from the pressing path, and the product is tempered at the temperature of 300-340 ℃, so that the high-temperature-resistant cosmetic bottle cap is obtained.
Example 3
Preparation method of high-temperature-resistant cosmetic bottle cap
Step I: adding 50g of sulfolane into a round-bottom flask, heating the sulfolane to 80 ℃, adding 30g of 4, 4' -biphenol and 15g of sodium carbonate into the sulfolane, stirring and reacting at the speed of 500rpm/min for 20min, extracting the obtained product by using 500mL of dichloromethane, discarding an aqueous phase, heating the rest organic phase to 60 ℃, distilling to remove dichloromethane until no fraction flows out, and stopping heating, wherein the rest organic phase is a first reaction liquid;
step II: heating the first reaction solution to 105 ℃, stirring 35g of 4, 4' -dichlorodiphenyl sulfone and 70g of anhydrous tetrahydrofuran at the rotating speed of 500rpm/min for reacting for 40min, and adding 7g of lithium aluminum hydride in the reaction process; heating to 80 ℃, collecting and removing the distilled solvent after the solvent is refluxed, wherein the residual organic phase is a second reaction liquid (the weight ratio of 4, 4' -dichlorodiphenyl sulfone to lithium aluminum hydride is 5: 1);
step III: heating the second reaction solution to 200 +/-10 ℃, and continuing stirring at the speed of 800rpm/min for reaction for 1h to obtain a third reaction solution;
step IV: washing the third reaction solution with 500mL of ethanol, and performing vacuum filtration to obtain polyphenylene sulfone resin;
step V: the polyphenylene sulfone resin is fed between pressing dies, the blank is hot-pressed at the temperature of 380 ℃ to be molded, in a shaping area, the product is rapidly cooled to the temperature below 315 ℃, then the product is separated from the pressing path, and the product is tempered at the temperature of 300-340 ℃, so that the high-temperature-resistant cosmetic bottle cap is obtained.
Example 4
The difference from example 3 is that: in step II, 38.5g of 4,4 '-dichlorodiphenyl sulfone were added (weight ratio of 4, 4' -dichlorodiphenyl sulfone to lithium aluminum hydride was 5.5: 1).
Example 5
The difference from example 3 is that: in step II, 42g of 4,4 '-dichlorodiphenyl sulfone was added (weight ratio of 4, 4' -dichlorodiphenyl sulfone to lithium aluminum hydride was 6: 1).
Example 6
The difference from example 5 is that: in step II, equal weight of potassium borohydride is used to replace equal weight of lithium aluminum hydride.
Example 7
The difference from example 5 is that: in step I, an equal weight of potassium carbonate was used in place of an equal weight of sodium carbonate.
Example 8
The difference from example 5 is that: and adding lithium aluminum hydride in the step II for 30 min.
Comparative example 1
The difference from example 8 is that: and step II, adding no lithium aluminum hydride.
Comparative example 2
The difference from example 8 is that: in step II, equal weight of ferrous chloride is used to replace equal weight of lithium aluminum hydride.
Comparative example 3
The difference from example 8 is that: and replacing equal weight of lithium aluminum hydride with equal weight of carbon powder in the step II.
Comparative example 4
The difference from example 8 is that: and (3) after the reaction in the step I is finished, the extraction step is not carried out, and the generated product is directly used as the first reaction liquid.
Comparative example 5
The difference from example 8 is that: and in the step IV, washing the third reaction solution with 500mL of water, and performing suction filtration under reduced pressure to obtain the polyphenylene sulfone resin.
Comparative example 6
A commercially available cosmetic bottle cap was used.
Performance test
The polyphenylene sulfone resins obtained in examples 1 to 8 and comparative examples 1 to 5 were subjected to a performance test;
thermogravimetric analysis: the blend was subjected to 5% thermogravimetric analysis (T.sub.weight loss) using a TGA 2050 thermogravimetric analyzer from TA of USAd 5) The temperature and the carbon residue rate of the nitrogen gas are represented, the temperature rising speed is 10 ℃/min, the scanning range is 100-800 ℃, and the gas flow is 100 mL/min;
dynamic mechanical analysis: adopting a DMA Q800 type dynamic mechanical analyzer of the American TA company, a film stretching mode, an air atmosphere, a scanning range of 50-350 ℃, an amplitude of 20 mu m, a frequency of 1Hz, a pre-stress of 0.01N and a force tracking of 125 percent, and measuring the temperature of a peak point of a loss modulus curve of an energy storage module of a sample as the glass transition temperature (Tg) of the sample;
and (3) detecting bisphenol A: boiling the prepared plastic bottle cap in boiling water at 100 ℃ for 30min, carrying out high performance liquid detection on the boiling water for boiling the bottle cap, and carrying out chromatographic column: hypersil BDS C185 μm (250 mm. times.4.6 mm); column temperature: 40 ℃; mobile phase: acetonitrile and water are 40: 60; flow rate: 0.7 mL/min; detection wavelength: 238 nm.
The test results are shown in table 1;
TABLE 1
Combining examples 1, 2 and 3, it can be seen that polyphenylene sulfone resin T is prepared by adding appropriate proportions of the starting materialsd 5The temperature is above 500 ℃, and the carbon residue rate is close to 50%; tg is more than 200 ℃, which proves that the cosmetic bottle cap made of polyphenylene sulfone resin is high temperature resistant and high in safety; t of example 3d 5The temperature and Tg were higher than those of examples 1 and 2, which demonstrated that the polyphenylene sulfone resin prepared from the raw material composition of example 3 had the best heat resistance and the best quality of the cosmetic bottle cap.
Combining examples 3, 4 and 5, it can be seen that the ratio of 4,4 ' -dichlorodiphenyl sulfone to lithium aluminum hydride is further optimized such that lithium aluminum hydride acts as a reducing agent to inhibit the possible oxidation of 4,4 ' -dichlorodiphenyl sulfone to polyphenylene sulfone resin, and when the ratio of 4,4 ' -dichlorodiphenyl sulfone to lithium aluminum hydride is 6:1, the resulting polyphenylene sulfone resin has a T ofd 5The temperature and Tg are higher than the T of the polyphenylene sulfone resins prepared in example 3 and example 4d 5Temperature and Tg, it was confirmed that the ratio of 4, 4' -dichlorodiphenyl sulfone to lithium aluminum hydride has a large influence on the heat resistance of polyphenylene sulfone resin.
Combining examples 5, 6 and 7, it can be seen that example 6, replacing lithium aluminum hydride with potassium borohydride, had little effect on the heat resistance of the resulting polyphenylene sulfone resin; in example 7, potassium carbonate was used instead of sodium carbonate in example 5, and the heat resistance of the polyphenylene sulfone resin obtained was hardly affected.
Combining example 5 and example 8, it can be seen that the addition time of the lithium aluminum hydride is increased, so that the lithium aluminum hydride continuously inhibits the oxidation reaction in the process of generating the polyphenylene sulfone resin by the 4, 4' -dichlorodiphenyl sulfone and the first reaction liquid, and the prepared polyphenylene sulfone resin has good heat resistance and good thermoplasticity.
Combining example 8 and comparative example 1, it can be seen that in comparative example 1, without adding a hydride reducing agent, the polyphenylene sulfone resin obtained has Td 5The temperature and Tg temperature were much lower than those in example 8, demonstrating that the hydride reducing agent is important for the heat resistance and thermoplasticity of polyphenylene sulfone resin.
Combining example 8 with comparative examples 2 and 3, it can be seen that Fe is used2+When the reduction is carried out with C, the effect is poorer than that when lithium aluminum hydride and potassium borohydride are adopted for reduction.
In the case of combining example 8 and comparative example 4, it can be seen that when step II is directly performed without performing the extraction step in step I, a large amount of water is contained in the solvent, and a large amount of by-products are produced in the reaction of step II, and the polyphenylene sulfone resin finally obtained has a low purity and is inferior in heat resistance and thermoplasticity.
In combination with example 8 and comparative example 5, it can be seen that washing with water in step IV does not completely elute organic substances except the polyphenylene sulfone resin, and the finally obtained polyphenylene sulfone resin has low purity and poor heat resistance and thermoplasticity.
As can be seen from all the examples and all the comparative examples described above, when potassium borohydride or lithium aluminum hydride is added in synthesizing the polyphenylene sulfone resin, the synthesized polyphenylene sulfone resin does not volatilize bisphenol A at a high temperature, but the reaction of potassium borohydride or lithium aluminum hydride, which is not added, and other reducing agents instead of potassium borohydride or lithium aluminum hydride, volatilizes bisphenol A at a high temperature, proving that the addition of potassium borohydride or lithium aluminum hydride is very important in synthesizing the polyphenylene sulfone resin.
In comparative example 4, if no extraction is performed, the presence of water in the obtained first reaction solution affects the subsequent reduction reaction of potassium borohydride or lithium aluminum hydride, resulting in poor high temperature resistance of the finally prepared polyphenylene sulfone resin; in comparative example 5, the washing liquid composition was changed, and other unreacted materials remained in the polyphenylene sulfone resin, and the unreacted materials were doped in the polyphenylene sulfone resin at high temperature, resulting in low purity of the polyphenylene sulfone resin and poor high temperature resistance.
Comparative example 6 bisphenol a was volatilized when boiled in water at high temperature using a commercially available cosmetic bottle cap.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The high-temperature-resistant cosmetic bottle cap is characterized by being prepared from the following raw materials in parts by weight: 20-35 parts of 4,4 '-biphenol, 25-45 parts of 4, 4' -dichlorodiphenyl sulfone, 10-20 parts of alkali, 5-10 parts of hydride reducing agent, 50-80 parts of ether solvent and 40-60 parts of sulfolane.
2. The high temperature resistant cosmetic bottle cap according to claim 1, wherein the weight ratio of 4, 4' -dichlorodiphenyl sulfone to hydride reducing agent is (5-6): 1.
3. The high temperature resistant cosmetic bottle cap of claim 1, wherein the hydride reducing agent is a metal hydride reducing agent.
4. A high temperature resistant cosmetic bottle cap according to claim 3, wherein said metal hydride reducing agent is lithium aluminum hydride or potassium borohydride.
5. The high temperature resistant cosmetic bottle cap of claim 1, wherein the base is one or more of sodium carbonate, calcium carbonate and potassium carbonate.
6. The high-temperature-resistant cosmetic bottle cap according to claim 1, wherein the ether solvent is anhydrous tetrahydrofuran or diethyl ether.
7. The method for preparing the high-temperature-resistant cosmetic bottle cap according to any one of claims 1 to 6, which is characterized by comprising the following steps:
step I: heating sulfolane to 70-90 ℃, adding 4, 4' -biphenol and alkali into sulfolane for reaction, extracting the obtained product, removing a water phase, and taking the residual organic phase as a first reaction liquid;
step II: heating the first reaction solution to 105-110 ℃, mixing and heating 4, 4' -dichlorodiphenyl sulfone and an ether solvent, dropwise adding a hydride reducing agent in the heating process, heating until the solvent flows back, and collecting and removing the back-flowed solvent to obtain a second reaction solution;
step III: heating the second reaction solution to 190-220 ℃, and then continuously stirring for reaction to obtain a third reaction solution;
step IV: carrying out vacuum filtration on the third reaction liquid to obtain polyphenylene sulfone resin;
step V: and (3) performing hot-press molding on the polyphenylene sulfone resin to prepare the cosmetic bottle cap.
8. The high-temperature-resistant cosmetic bottle cap and the preparation method thereof according to claim 7, wherein in the step IV, the polyphenylene sulfone resin is obtained by washing the third reaction solution with ethanol and then performing suction filtration under reduced pressure.
9. The method for preparing the high-temperature-resistant cosmetic bottle cap according to claim 7, wherein the adding time of the hydride reducing agent in the step II is 20-40 min.
10. The high-temperature-resistant cosmetic bottle cap and the preparation method thereof according to claim 7, wherein the step I, the step II and the step III are carried out under the protection of nitrogen.
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| CN105601926A (en) * | 2015-06-08 | 2016-05-25 | 四川理工学院 | Preparing method for polyethylene sulfone resin |
| CN108329472A (en) * | 2018-01-25 | 2018-07-27 | 威海帕斯砜新材料有限公司 | A kind of synthetic method of polysulfones series plastics |
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