CN114573801A - Preparation method of phenol red type polyarylate material - Google Patents
Preparation method of phenol red type polyarylate material Download PDFInfo
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- CN114573801A CN114573801A CN202210091603.1A CN202210091603A CN114573801A CN 114573801 A CN114573801 A CN 114573801A CN 202210091603 A CN202210091603 A CN 202210091603A CN 114573801 A CN114573801 A CN 114573801A
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- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229960003531 phenolsulfonphthalein Drugs 0.000 title claims abstract description 82
- 229920001230 polyarylate Polymers 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000000243 solution Substances 0.000 claims abstract description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 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 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 25
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000012264 purified product Substances 0.000 claims description 14
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 36
- 238000012545 processing Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 229920001634 Copolyester Polymers 0.000 abstract 1
- 150000007860 aryl ester derivatives Chemical class 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 229940106691 bisphenol a Drugs 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- -1 ester compound Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/79—Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a preparation method of a phenol red polyarylate material, which comprises the following steps: adding phenol red, bisphenol A, sodium hydroxide and benzyltriethylammonium chloride into water, and uniformly stirring to obtain a mixed solution; adding an acyl chloride monomer into dichloromethane to obtain a dichloromethane solution dissolved with acyl chloride; slowly dripping dichloromethane solution dissolved with acyl chloride into the mixed solution for polymerization reaction to obtain a polymerization solution; pouring the polymerization solution into methanol for precipitation and filtration; purifying and drying the product to obtain phenol red type copolymerized aryl ester material; pouring the obtained phenol red polyarylester material into solvents such as dichloromethane and the like for dissolving, and naturally volatilizing to obtain a phenol red polyarylester copolymer film; the aromatic copolyester prepared by the method has excellent heat resistance, good mechanical property and processing fluidity, can be applied to the fields of new 5G materials, aerospace, electronic appliances and the like, and has wide application prospects.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a phenol red type polyarylate material.
Background
Polyarylate (PAR) is a thermoplastic specialty engineering plastic that has gradually developed since the beginning of the last century. The main chain structure of the polymer is regular and has high rigidity, and the main chain structure of the molecular chain is aromatic polymer and is connected by covalent ester bonds to form a stable and rigid molecular weight structure and high molecular weight polymer. The structure endows the polyimide composite material with excellent comprehensive performance, and the heat resistance of the polyimide composite material is outstanding in the engineering plastics, so that the polyimide composite material is positioned at the top of a pyramid of a special engineering high polymer material and is only inferior to a polyimide material. Compared with other resins, the high-strength high-toughness resin has excellent strength, processing precision, modulus, size stability, wear resistance, ultraviolet light resistance and gas barrier property, and has wide application prospects and research values in the fields of special engineering and industry. The polyarylate has wide application range and is mainly applied to the fields of mechanical parts, electronic and electric appliances, medical instruments, automobile parts, films and the like. The total yield of the high-performance polyester in the world is not high, only about 8 percent, but the high-performance polyester has good economic benefit compared with the common polymer material.
The polyarylate has regular main chain structure, high rigidity and excellent comprehensive performance, but has obvious defects, and limits the development of the polyarylate in a certain sense. The polyarylate has a high melting point and a compact aromatic ring structure in the molecule, which results in a high viscosity in a molten state, difficulty in flowing and thus poor processability, and thus, it is necessary to provide a method for preparing a phenol red polyarylate material.
Disclosure of Invention
The invention aims to provide a preparation method of a phenol red polyarylate material to solve the problems of poor solubility and poor processability of the conventional polyarylate material.
The technical scheme of the invention is as follows:
a preparation method of a phenol red type polyarylate material comprises the following steps:
(1) preparing a solution: sequentially adding sodium hydroxide, phenol red, bisphenol A and benzyltriethylammonium chloride into deionized water, stirring and mixing, and obtaining a mixed solution after complete dissolution;
(2) preparing a dichloromethane solution: adding an acyl chloride monomer into a dichloromethane solution, mixing and stirring, and taking out after fully mixing to obtain a dichloromethane solution dissolved with acyl chloride;
(3) polymerization reaction: under the action of protective gas, slowly dropwise adding the dichloromethane solution dissolved with acyl chloride into the mixed solution to carry out stirring polymerization reaction, and after the reaction is finished, taking out the dichloromethane solution to obtain a polymerization solution;
(4) precipitation, filtration and purification: carrying out precipitation filtration treatment and purification treatment on the polymerization solution, and taking out to obtain a purified product;
(5) crushing, washing and drying: carrying out crushing treatment, washing treatment and drying treatment on the purified product, and taking out to obtain a phenol red polyarylate material;
(6) dissolving materials: pouring the polyarylate material into a solvent, stirring, dissolving and filtering, and taking out to obtain a filtrate;
(7) preparing a film: and pouring the filtrate into a glass surface dish, volatilizing, and taking out to obtain the phenol red polyarylate film.
Further, the formula comprises the following components in parts by weight: 4-5 parts of sodium hydroxide, 2-19.7 parts of phenol red, 8-13 parts of bisphenol A, 1 part of benzyltriethylammonium chloride, 167 parts of deionized water, 7.9-11.3 parts of terephthaloyl chloride, 0-3.4 parts of isophthaloyl chloride and 589 parts of dichloromethane 442-.
Further, the sum of the amounts of the phenol red and the bisphenol A material is equal to the amount of the acid chloride monomer material, and the amount of the sodium hydroxide material is twice the sum of the amounts of the bisphenol A and the phenol red material or the amount of the acid chloride monomer material.
Further, in the step (2), the acyl chloride monomer is one or more of terephthaloyl chloride and isophthaloyl chloride.
Further, the reaction time of the stirring polymerization reaction in the step (2) is 3-5 hours, the reaction temperature is 8-12 ℃, and the stirring speed is 2000 rpm/min.
Further, the protective gas in the step (2) is nitrogen.
Further, the detergent for the washing treatment in the step (5) is deionized water.
Further, the drying temperature of the drying treatment in the step (5) is 80 ℃, and the drying time is 12 hours.
Further, in the step (6), the solvent is one or more of dichloromethane and chloroform.
Further, the volatilization time of the volatilization treatment in the step (7) is 8 hours.
The invention provides a preparation method of a phenol red polyarylate material, wherein the prepared phenol red polyarylate material breaks a regular molecular chain structure by adding a certain phenol red monomer in a polyarylate rigid main chain, and the glass transition temperature is reduced, so that the solubility and the processability of the polyarylate material are improved; the adopted interfacial polymerization mode is a synthesis processing mode commonly used in laboratories and industry, the operation is simpler, the required equipment condition is not harsh, the reaction temperature is lower, the molecular weight and the molecular weight distribution of the obtained polyarylate are more ideal, and the method has a certain industrial application prospect; the subsequent solvent can be distilled, separated and recycled by using a rotary evaporator, so that the recycling is realized, and the environment is protected.
Drawings
FIG. 1 is a graph showing infrared spectra of phenol red polyarylate materials prepared in examples 1 to 4 in the method for preparing a phenol red polyarylate material according to the present invention;
FIG. 2 is X-ray diffraction analysis data of the phenol red polyarylate materials prepared in examples 1 to 4 in the method for preparing the phenol red polyarylate material of the present invention;
FIG. 3 is a process flow diagram of a method for preparing a phenol red polyarylate material of the present invention.
Wherein 1 is the phenol red polyarylate material prepared in example 1; 2 is the phenol red polyarylate material prepared in example 2; 3 is the phenol red polyarylate material prepared in example 3; 4 is the phenol red polyarylate material prepared in example 4.
Detailed Description
A preparation method of phenol red polyarylate material, the apparatus of the preparation method comprises a heat collection type magnetic stirrer, a three-neck flask, a constant pressure funnel, a condenser pipe, a collection bottle, a suction filtration device, a magnetic stirrer and the like; the three-mouth flask is respectively connected with a constant pressure funnel and a controllable adjusting condenser pipe; the controllable adjusting condensation pipe is connected with the collecting bottle through a bent pipe; the collecting bottle is connected with three Meng's washing bottles through rubber tubes, the first one is an anti-suck-back device, and sodium hydroxide solution and dry silica gel are respectively filled in the second and third Meng's washing bottles to prevent the overflow of hydrogen chloride gas.
The preparation raw materials are as follows: phenol red, bisphenol-A, terephthaloyl chloride, isophthaloyl chloride, dichloromethane, sodium hydroxide, methanol and benzyltriethylammonium chloride.
A preparation method of a phenol red type polyarylate material comprises the following steps:
the method comprises the following steps: putting a three-neck round-bottom flask with a condenser pipe and a constant-pressure funnel into a constant-temperature water bath kettle, adding a certain amount of deionized water into the water bath kettle, and putting an ice-water mixture into the water bath kettle to keep the temperature; dissolving sodium hydroxide in deionized water to prepare a sodium hydroxide solution, respectively adding bisphenol A and phenol red, stirring and dissolving to obtain a uniform solution, finally adding a catalyst benzyltriethylammonium chloride, and taking out after fully mixing to obtain a mixed solution;
step two: dissolving acyl chloride monomer in dichloromethane solution, mixing and stirring, and taking out after fully mixing to obtain dichloromethane solution dissolved with acyl chloride;
step three: transferring the mixed solution into a three-neck round-bottom flask with a condenser tube and a constant-pressure funnel, pouring a dichloromethane solution dissolved with acyl chloride into a separating funnel, slowly dropwise adding the dichloromethane solution into the three-neck flask of the mixed solution to carry out stirring polymerization reaction, adjusting the temperature to 8-12 ℃ in a nitrogen environment, carrying out constant-temperature stirring reaction at a speed of 2000rpm/min for 3-5 hours, and taking out the obtained product after the reaction is finished to obtain a polymerization solution;
step four: after the reaction is finished, pouring the polymerization solution into a beaker, adding a methanol solution, stirring, precipitating and filtering, and purifying by using dichloromethane and methanol to obtain a purified product;
step five: crushing the purified product, repeatedly washing the precipitate with deionized water after crushing until all impurities are removed, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain a phenol red type polyarylate product;
step six: pouring polyarylate material into a solvent, stirring, dissolving, filtering, and taking out to obtain filtrate;
step seven: pouring the filtrate into a glass surface dish, carrying out volatilization treatment for 8 hours, and taking out to obtain the phenol red polyarylate film.
Wherein the formula comprises the following components in parts by weight: 4-5 parts of sodium hydroxide, 2-19.7 parts of phenol red, 8-13 parts of bisphenol A, 1 part of benzyltriethylammonium chloride, 111-167 parts of deionized water, 7.9-11.3 parts of terephthaloyl chloride, 0-3.4 parts of isophthaloyl dichloride and 589 parts of dichloromethane, wherein the sum of the amounts of the phenol red and the bisphenol A is equal to the amount of a substance of an acid chloride monomer, and the amount of the sodium hydroxide substance is the sum of the amounts of the bisphenol A and the phenol red or twice of the amount of the acid chloride monomer substance; in the second step, the acyl chloride monomer is one or more of terephthaloyl chloride and isophthaloyl chloride; in the sixth step, the solvent is one or more of dichloromethane and chloroform.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The embodiment shows a preparation method of the phenol red polyarylate material according to the following steps:
the method comprises the following steps: putting a three-neck round-bottom flask with a condenser pipe and a constant-pressure funnel into a constant-temperature water bath kettle, adding deionized water into the water bath kettle, and putting an ice-water mixture into the water bath kettle to keep the temperature; dissolving 4.5 parts of sodium hydroxide in 111 parts of deionized water to prepare a sodium hydroxide solution, respectively adding 10.1 parts of bisphenol A and 4 parts of phenol red, stirring and dissolving to obtain a uniform solution, finally adding 1 part of catalyst benzyltriethylammonium chloride, and taking out after fully mixing to obtain a mixed solution;
step two: dissolving 11.3 parts of acyl chloride monomer in 442 parts of dichloromethane solution, mixing and stirring, and taking out after full mixing to obtain a dichloromethane solution dissolved with acyl chloride, wherein the acyl chloride monomer is terephthaloyl chloride;
step three: transferring the mixed solution into a three-neck round-bottom flask with a condenser tube and a constant-pressure funnel, pouring a dichloromethane solution dissolved with acyl chloride into a separating funnel, slowly dropwise adding the dichloromethane solution into the three-neck flask of the mixed solution to carry out stirring polymerization reaction, adjusting the temperature to 8-12 ℃ in a nitrogen environment, carrying out constant-temperature stirring reaction at a speed of 2000rpm/min for 3-5 hours, and taking out the obtained product after the reaction is finished to obtain a polymerization solution;
step four: after the reaction is finished, pouring the polymerization solution into a beaker, adding 150ml of methanol solution, stirring, precipitating, filtering, and purifying by using dichloromethane and methanol to obtain a purified product;
step five: crushing the purified product, repeatedly washing the precipitate with deionized water after crushing until all impurities are removed, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain a phenol red type polyarylate product;
step six: pouring polyarylate material into a solvent, stirring, dissolving, filtering, and taking out to obtain filtrate;
step seven: pouring the filtrate into a glass surface dish, carrying out volatilization treatment for 8 hours, and taking out to obtain the phenol red polyarylate film.
Example 2
The present embodiment shows a method for preparing a phenol red polyarylate material, comprising the following steps:
the method comprises the following steps: putting a three-neck round-bottom flask with a condenser pipe and a constant-pressure funnel into a constant-temperature water bath kettle, adding deionized water into the water bath kettle, and adding an ice-water mixture to keep the temperature; dissolving 4.5 parts of sodium hydroxide in 167 parts of deionized water to prepare a sodium hydroxide solution, respectively adding 19.7 parts of phenol red, stirring and dissolving to obtain a uniform solution, finally adding 1 part of catalyst benzyltriethylammonium chloride, and taking out after fully mixing to obtain a mixed solution;
step two: dissolving 11.3 parts of terephthaloyl chloride in 515 parts of dichloromethane solution, mixing and stirring, and taking out after fully mixing to obtain dichloromethane solution dissolved with acyl chloride;
step three: transferring the mixed solution into a three-neck round-bottom flask with a condenser tube and a constant-pressure funnel, pouring a dichloromethane solution dissolved with acyl chloride into a separating funnel, slowly dropwise adding the dichloromethane solution into the three-neck flask of the mixed solution to carry out stirring polymerization reaction, adjusting the temperature to 8-12 ℃ in a nitrogen environment, carrying out constant-temperature stirring reaction at a speed of 2000rpm/min for 3-5 hours, and taking out the obtained product after the reaction is finished to obtain a polymerization solution;
step four: after the reaction is finished, pouring the polymerization solution into a beaker, adding 150ml of methanol solution, stirring, precipitating, filtering, and purifying by using dichloromethane and methanol to obtain a purified product;
step five: crushing the purified product, repeatedly washing the precipitate with deionized water after crushing until all impurities are washed away, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain a phenol red polyarylate product;
step six: pouring polyarylate material into a solvent, stirring, dissolving, filtering, and taking out to obtain filtrate;
step seven: pouring the filtrate into a glass surface dish, carrying out volatilization treatment for 8 hours, and taking out to obtain the phenol red polyarylate film.
Example 3
The present embodiment shows a method for preparing a phenol red polyarylate material, comprising the following steps:
the method comprises the following steps: putting a three-neck round-bottom flask with a condenser pipe and a constant-pressure funnel into a constant-temperature water bath kettle, adding deionized water into the water bath kettle, and putting an ice-water mixture into the water bath kettle to keep the temperature; dissolving 4.5 parts of sodium hydroxide in 139 parts of deionized water to prepare a sodium hydroxide solution, respectively adding 12 parts of bisphenol A and 2 parts of phenol red, stirring and dissolving to obtain a uniform solution, finally adding 1 part of catalyst benzyltriethylammonium chloride, and taking out after fully mixing to obtain a mixed solution;
step two: dissolving 7.9 parts of terephthaloyl chloride and 3.4 parts of isophthaloyl chloride in 589 parts of dichloromethane solution, mixing and stirring, taking out after fully mixing to obtain dichloromethane solution dissolved with acyl chloride, wherein the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is 7: 3;
step three: transferring the mixed solution into a three-neck round-bottom flask with a condenser pipe and a constant-pressure funnel, pouring a dichloromethane solution dissolved with acyl chloride into a separating funnel, slowly dripping the dichloromethane solution into the three-neck flask of the mixed solution to carry out stirring polymerization reaction, regulating the temperature to 8-12 ℃ in a nitrogen environment, carrying out constant-temperature stirring reaction at the speed of 2000rpm/min for 3-5 hours, and taking out the obtained product after the reaction is finished to obtain a polymerization solution;
step four: after the reaction is finished, pouring the polymerization solution into a beaker, adding 150ml of methanol solution, stirring, precipitating, filtering, and purifying by using dichloromethane and methanol to obtain a purified product;
step five: crushing the purified product, repeatedly washing the precipitate with deionized water after crushing until all impurities are removed, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain a phenol red type polyarylate product;
step six: pouring the polyarylate material into a solvent, stirring, dissolving and filtering, and taking out to obtain a filtrate;
step seven: pouring the filtrate into a glass surface dish, carrying out volatilization treatment for 8 hours, and taking out to obtain the phenol red polyarylate film.
Example 4
The present embodiment shows a method for preparing a phenol red polyarylate material, comprising the following steps:
the method comprises the following steps: putting a three-neck round-bottom flask with a condenser tube and a constant-pressure funnel into a constant-temperature water bath kettle, adding 139 parts of deionized water into the water bath kettle, and putting an ice-water mixture into the water bath kettle to keep the temperature; dissolving 4.5 parts of sodium hydroxide in deionized water to prepare a sodium hydroxide solution, respectively adding 10.1 parts of bisphenol A and 4 parts of phenol red, stirring and dissolving to obtain a uniform solution, finally adding 1 part of catalyst benzyltriethylammonium chloride, and taking out after fully mixing to obtain a mixed solution;
step two: dissolving 7.9 parts of terephthaloyl chloride and 3.4 parts of isophthaloyl chloride in 589 parts of dichloromethane solution, mixing and stirring, taking out after full mixing, and obtaining dichloromethane solution dissolved with acyl chloride, wherein the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is 7: 3;
step three: transferring the mixed solution into a three-neck round-bottom flask with a condenser tube and a constant-pressure funnel, pouring a dichloromethane solution dissolved with acyl chloride into a separating funnel, slowly dropwise adding the dichloromethane solution into the three-neck flask of the mixed solution to carry out stirring polymerization reaction, adjusting the temperature to 8-12 ℃ in a nitrogen environment, carrying out constant-temperature stirring reaction at a speed of 2000rpm/min for 3-5 hours, and taking out the obtained product after the reaction is finished to obtain a polymerization solution;
step four: after the reaction is finished, pouring the polymerization solution into a beaker, adding 150ml of methanol solution, stirring, precipitating, filtering, and purifying by using dichloromethane and methanol to obtain a purified product;
step five: crushing the purified product, repeatedly washing the precipitate with deionized water after crushing until all impurities are removed, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain a phenol red type polyarylate product;
step six: pouring polyarylate material into a solvent, stirring, dissolving, filtering, and taking out to obtain filtrate;
step seven: pouring the filtrate into a glass surface dish, carrying out volatilization treatment for 8 hours, and taking out to obtain the phenol red polyarylate film.
The phenol red polyarylate materials prepared in examples 1 to 4 were tested.
Test 1: infrared spectroscopic analysis
According to GB/T6040-2019, mixing the sample and potassium bromide according to the ratio of 1: 100, grinding and mixing evenly in an agate grinding body, filling the mixture into a die, pressing the mixture into tablets by using an YP-2 tablet press, and testing by using an infrared spectrometer.
And (3) testing 2: x-ray diffraction analysis
According to GB/T37983-.
And (3) testing: mechanical Property measurement
The tensile properties and elongation at break of the film were tested according to GB/T13022-1991 at a tensile speed of 0.5 mm/min.
The following conclusions were drawn from the test results:
referring to FIG. 1, FIG. 1 is a graph showing an infrared spectrum of a phenol red polyarylate material obtained in examples 1 to 4 in the method for preparing a phenol red polyarylate material according to the present invention; 3463cm as shown in FIG. 1-1is-OH hydroxyl stretching vibration peak, 2975cm-1Is C-H stretching vibration peak, 1743cm-1Is a characteristic absorption peak of the ester compound, 1504cm-11300-1200cm, which is a vibration peak of a benzene ring skeleton caused by vibration of a benzene ring skeleton of polyarylate-1Is the asymmetric stretching vibration peak caused by C-O-C, 1170cm-1Is the stretching vibration peak of S ═ O, indicating that the phenol red polyarylate was synthesized successfully.
Referring to FIG. 2, FIG. 2 is X-ray diffraction analysis data of the phenol red polyarylate materials prepared in examples 1 to 4 of the method for preparing a phenol red polyarylate material according to the present invention; as shown in FIG. 2, polyarylate having only a p-benzene structure shows a crystalline structure, but gradually changes to an amorphous state as the content of phenol red increases and isophthaloyl chloride is added, because the introduction of phenol red monomer and m-benzene structure destroys the regularity of the polyarylate molecular chain, prevents the close packing of molecular segments, and thus, it is in an amorphous state. Thereby promoting solvent molecule diffusion, improving its processability, and improving its solubility and processability.
Table 1: mechanical properties of phenol red type polyarylate
| Tensile strength/MPa | Young's modulus/GPa | Elongation at break/% | |
| Example 1 | 48.72 | 1.52 | 20.3％ |
| Example 2 | 46.28 | 1.4 | 25.7％ |
| Example 3 | 56.32 | 1.84 | 18.5％ |
| Example 4 | 59.88 | 1.95 | 19.5％ |
As can be seen from Table 1, the phenol red type polyarylate has excellent mechanical properties, has a huge application prospect in the field of special engineering, has the highest tensile strength of more than 45MPa, and has a greatly improved elongation at break compared with other polyarylates, thereby meeting the requirements of general application.
In conclusion, according to the preparation method of the phenol red polyarylate material, the phenol red polyarylate material and the film thereof are prepared through a series of steps of solution preparation, polymerization reaction, precipitation filtration, purification drying and film preparation dissolution, and by infrared spectrum analysis, X-ray diffraction analysis and mechanical property test, the analysis result shows that regular molecular chain structure is broken, the glass transition temperature is reduced, and the solubility and the processability of the polyarylate material are improved; the adopted interfacial polymerization mode is a synthesis processing mode commonly used in laboratories and industry, the operation is simpler, the required equipment condition is not harsh, the reaction temperature is lower, the molecular weight and the molecular weight distribution of the obtained polyarylate are more ideal, and the method has a certain industrial application prospect; the subsequent solvent can be distilled, separated and recycled by using a rotary evaporator, so that the recycling is realized, and the environment is protected.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a phenol red type polyarylate material is characterized by comprising the following steps:
(1) preparing a solution: sequentially adding sodium hydroxide, phenol red, bisphenol A and benzyltriethylammonium chloride into deionized water, stirring and mixing, and obtaining a mixed solution after complete dissolution;
(2) preparing a dichloromethane solution: adding an acyl chloride monomer into a dichloromethane solution, mixing and stirring, and taking out after fully mixing to obtain a dichloromethane solution dissolved with acyl chloride;
(3) polymerization reaction: under the action of protective gas, slowly dropwise adding the dichloromethane solution dissolved with acyl chloride into the mixed solution to carry out stirring polymerization reaction, and after the reaction is finished, taking out the dichloromethane solution to obtain a polymerization solution;
(4) precipitation, filtration and purification: carrying out precipitation filtration treatment and purification treatment on the polymerization solution, and taking out to obtain a purified product;
(5) crushing, washing and drying: carrying out crushing treatment, washing treatment and drying treatment on the purified product, and taking out to obtain a phenol red polyarylate material;
(6) dissolving materials: pouring the polyarylate material into a solvent, stirring, dissolving and filtering, and taking out to obtain a filtrate;
(7) preparing a film: and pouring the filtrate into a glass surface dish, volatilizing, and taking out to obtain the phenol red polyarylate film.
2. The method of preparing a phenol red polyarylate material as claimed in claim 1, wherein: the formula comprises the following components in parts by weight: 4-5 parts of sodium hydroxide, 2-19.7 parts of phenol red, 8-13 parts of bisphenol A, 1 part of benzyltriethylammonium chloride, 167 parts of deionized water, 7.9-11.3 parts of terephthaloyl chloride or 0-3.4 parts of isophthaloyl chloride, and 589 parts of dichloromethane 442-.
3. The method for preparing a phenol red polyarylate material according to claim 2, wherein: the sum of the amounts of the phenol red and the bisphenol A material is equal to the amount of the acid chloride monomer material, and the amount of the sodium hydroxide material is the sum of the amounts of the bisphenol A and the phenol red material or twice the amount of the acid chloride monomer material.
4. The method of preparing a phenol red polyarylate material as claimed in claim 2, wherein: in the step (2), the acyl chloride monomer is one or more of terephthaloyl chloride and isophthaloyl chloride.
5. The method for preparing a phenol red polyarylate material according to claim 1, wherein: the reaction time of the stirring polymerization reaction in the step (2) is 3-5 hours, the reaction temperature is 8-12 ℃, and the stirring speed is 2000 rpm/min.
6. The method for preparing a phenol red polyarylate material according to claim 1, wherein: and (3) the protective gas in the step (2) is nitrogen.
7. The method for preparing a phenol red polyarylate material according to claim 1, wherein: and (5) the detergent for washing treatment is deionized water.
8. The method for preparing a phenol red polyarylate material according to claim 1, wherein: the drying temperature of the drying treatment in the step (5) is 80 ℃, and the drying time is 12 hours.
9. The method for preparing a phenol red polyarylate material according to claim 1, wherein: in the step (6), the solvent is one or more of dichloromethane and chloroform.
10. The method for preparing a phenol red polyarylate material according to claim 1, wherein: the volatilization time of the volatilization treatment in the step (7) is 8 hours.
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