CN113861400B - Hyperbranched polyarylester and preparation method thereof - Google Patents
Hyperbranched polyarylester and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 229920001230 polyarylate Polymers 0.000 claims abstract description 50
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 33
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 33
- 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 description 27
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 20
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 15
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 12
- 229930185605 Bisphenol Natural products 0.000 claims description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims description 10
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 9
- 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 9
- 229960002479 isosorbide Drugs 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002685 polymerization catalyst Substances 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 229920001610 polycaprolactone Polymers 0.000 abstract 1
- 239000004632 polycaprolactone Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000004580 weight loss Effects 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 8
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 7
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 7
- 102100021202 Desmocollin-1 Human genes 0.000 description 7
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 7
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 bisphenol a Chemical compound 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229920000587 hyperbranched polymer Polymers 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—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
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
Abstract
The invention provides hyperbranched polyarylate with a structure (I), and also provides a preparation method of the hyperbranched polyarylate, which comprises the following steps: in the presence of a catalyst, 3 (4-hydroxyphenyl) isobenzopyrrolidone, a diacyl chloride monomer and a dihydroxyl monomer are subjected to an interfacial polymerization method to obtain the hyperbranched polyarylate with the structure shown in the formula (I). The product with good processability, high mechanical strength and other comprehensive properties can be obtained by regulating and controlling the structure and the branching degree of the hyperbranched polyarylester, and the hyperbranched polyarylester can be applied to reinforcing polyurethane/polycaprolactone low-temperature thermoplastic plates.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to hyperbranched polyarylate and a preparation method thereof.
Background
The polyarylate is a typical special engineering plastic and has the characteristics of high strength, high modulus, high temperature resistance and the like. Because the rigid skeleton of the polyarylate contains aromatic or heterocyclic repeating units, the processing temperature is high, the melt viscosity is high, and the requirements on processing equipment and molding technology are very strict, which is a technical bottleneck restricting the application of the polyarylate.
The hyperbranched polymer is a high-branching-degree macromolecule with a three-dimensional structure, is approximately spherical in molecular scale, is relatively linear, has the characteristics of central nuclear functional groups, high branching degree, a large number of end groups, cavities and the like, and can improve the processability of the rigid-structure polymer and the compatibility of a blend. Meanwhile, the hyperbranched polymer has relatively simple synthesis conditions, can be synthesized in one step, is easy to industrialize, and shows excellent performance in the fields of biomedicine, aerospace, composite materials, nuclear industry and the like in recent years. The main chain of the hyperbranched polyarylate, which is composed of aromatic rings and ester groups, has high rigidity and can provide higher mechanical strength; the polymer with good processability, high mechanical property and other comprehensive properties is hopefully obtained by regulating and controlling the structure and the branching degree.
The hyperbranched polyarylates reported at present mostly have planar branch point structures, and the structures close to the branch points extend outwards in a plane. And the stereo branching points provide a stereo three-dimensional direction chain growth space, and new structures and properties are endowed to the hyperbranched polyarylate. Therefore, the preparation of the polyarylate containing the three-dimensional branch point structure has profound significance for researching the relationship between the structure and the performance and for matrix reinforcing mechanism.
Disclosure of Invention
The invention aims to provide hyperbranched polyarylate, and the hyperbranched polyarylate provided by the application has the comprehensive properties of good processability, high mechanical strength and the like.
In view of the above, the present application provides a hyperbranched polyarylate having the structure (I),
wherein Ar is formed 1 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
formation of Ar 2 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A,1, 5-dihydroxynaphthalene, bisphenol fluorene, 4 '-dihydroxydiphenyl ether, 4' -dihydroxybiphenyl and isosorbide.
Preferably, the degree of branching DB of the hyperbranched polyarylate is from 0.1 to 0.8.
The application also provides a preparation method of the hyperbranched polyarylate, which comprises the following steps:
carrying out interfacial polymerization on 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a structure shown in a formula (II), a diacyl chloride monomer and a dihydroxyl monomer to obtain hyperbranched polyarylate;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 1, 5-dihydroxynaphthalene, 4 '-dihydroxydiphenyl ether, 4' -dihydroxybiphenyl and isosorbide;
preferably, the preparation of the hyperbranched polyarylate is specifically as follows:
reacting 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a dihydroxy monomer under the action of a catalyst and a phase transfer catalyst to obtain an initial reactant;
and dropwise adding the bisacyl chloride monomer solution into the initial reactant for reaction to obtain the hyperbranched polyarylate.
Preferably, the molar ratio of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the bis-acid chloride monomer and the bis-hydroxyl monomer is (0.5-1): (2-6): (2-6).
Preferably, the catalyst for interfacial polymerization is selected from NaOH and K 2 CO 3 And Na 2 CO 3 The phase transfer catalyst for interfacial polymerization is selected from one or more of benzyltriethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide.
Preferably, the molar amount of the catalyst to the dihydroxy monomer is 2 to 10:1, the phase transfer catalyst is 0.2 to 10 weight percent of the total amount of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the bis-acyl chloride monomer and the bis-hydroxyl monomer.
Preferably, the dropping rate is 0.01 to 30ml/min.
Preferably, the solvent of the bis-acid chloride monomer solution is selected from chloroform, dichloromethane or dichloroethane, and the amount of the solvent in the bis-acid chloride monomer solution is 10 to 70wt%.
Preferably, the temperature of the interfacial polymerization is-10 to 25 ℃ and the time is 0.5 to 10 hours.
The application provides hyperbranched polyarylate, which is prepared from 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, diacyl chloride monomer and dihydroxyl monomer; the structure of the hyperbranched polyarylate can endow the polymer with good processing performance and mechanical performance, and meanwhile, the hyperbranched polyarylate with various novel structures and high performance can be obtained by adjusting the structures of the diacid chloride monomer and the bisphenol monomer.
Drawings
FIG. 1 is an IR spectrum of a hyperbranched polyarylate prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a hyperbranched polyarylate prepared in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the current development of hyperbranched polymers and the demand for stereo-branched polyarylate in the prior art, the embodiment of the invention discloses a hyperbranched polyarylate with the structure (I),
wherein Ar is formed 1 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
formation of Ar 2 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 1, 5-dihydroxynaphthalene, 4 '-dihydroxydiphenyl ether, 4' -dihydroxybiphenyl and isosorbide.
In the context of the present application, it is,
represent with Ar 2 Radical attached according to Ar 1 、Ar 2 Are connected in sequence.
In the present application, the degree of branching DB of the hyperbranched polyarylate is from 0.1 to 0.8.
According to the invention, ar is formed in 1 The monomer of the unit is selected from terephthaloyl chloride to form Ar 2 When the monomer of the unit is selected from hydroquinone, the structural formula of the hyperbranched polyarylate is specifically as follows:
the application also provides a preparation method of the hyperbranched polyarylate, which comprises the following steps:
carrying out interfacial polymerization on 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a structure shown in a formula (II), a diacyl chloride monomer and a dihydroxyl monomer to obtain hyperbranched polyarylate;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 1, 5-dihydroxynaphthalene, 4 '-dihydroxydiphenyl ether, 4' -dihydroxydiphenyl and isosorbide;
in the above preparation process, in order to obtain the hyperbranched polyarylate with the structure described in the present application, the preparation process of the hyperbranched polyarylate specifically comprises:
reacting 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a dihydroxy monomer under the action of a catalyst and a phase transfer catalyst to obtain an initial reactant;
and dropwise adding the bisacyl chloride monomer solution into the initial reactant for reaction to obtain the hyperbranched polyarylate.
In the process, firstly, the dihydroxy monomer is activated by the catalyst, and then the dropwise added diacyl chloride monomer is added, so that on one hand, the dihydroxy monomer is used for adjusting the molecular weight and the structure, the addition amount is relatively small, and on the other hand, the solubility is relatively poor compared with that of the trifunctional monomer, and therefore, the conversion rate of the acyl chloride terminated trifunctional product obtained by reacting the dihydroxy monomer with the trifunctional monomer is high; and then, carrying out condensation reaction on the acyl chloride-terminated trifunctional product and a dihydroxy monomer to finally obtain the structure shown in the formula (I).
The bis-acid chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, and in particular embodiments, from one or two of terephthaloyl chloride and isophthaloyl chloride, and more preferably from one of terephthaloyl chloride and isophthaloyl chloride; the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol a,1, 5-dihydroxynaphthalene, bisphenol fluorene, 4 '-dihydroxydiphenyl ether, 4' -dihydroxydiphenyl and isosorbide, preferably one or more of phenolphthalein, bisphenol a, bisphenol fluorene, 4 '-dihydroxydiphenyl ether and isosorbide, and in the embodiment, is specifically selected from one of phenolphthalein, bisphenol a, bisphenol fluorene, 4' -dihydroxydiphenyl ether and isosorbide; the molar ratio of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone to the bis-acyl chloride monomer to the bis-hydroxyl monomer is 0.5-1: 2 to 6:2 to 6, in specific embodiments, the molar ratio is from 0.5 to 0.8:2 to 5:2 to 5, more particularly 0.5 to 0.7:2 to 5:2 to 5.
Under the action of catalyst, the monomer is made into hyperbranched polyarylate by interfacial polymerization, wherein the catalyst is selected from NaOH and K 2 CO 3 And Na 2 CO 3 Preferably NaOH and Na 2 CO 3 One or two, more preferably NaOH; the phase transfer catalyst is selected from one or more of benzyltriethylammonium chloride (TEBAC), tetrabutylammonium chloride (TBAC) and tetrabutylammonium bromide (TBAB), preferably one or two of benzyltriethylammonium chloride (TEBAC) and tetrabutylammonium chloride (TBAC), more preferably one of benzyltriethylammonium chloride (TEBAC) and tetrabutylammonium chloride (TBAC).
The molar weight of the catalyst and the dihydroxy monomer is 2-10: 1, preferably 2 to 8:1, more particularly 2 to 6:1. the addition amount of the phase transfer catalyst is 0.2 to 10%, preferably 0.2 to 7%, more preferably 0.2 to 5% of the total amount of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the bisacyl chloride monomer and the bishydroxy monomer.
In the present application, the organic solvent of the diacyl chloride monomer solution in the interfacial polymerization is chloroform, dichloromethane or dichloroethane, preferably chloroform or dichloromethane, more preferably dichloromethane; the content of the solvent is 10 to 70 percent, preferably 35 to 65 percent, and more preferably 45 to 65 percent
The feeding method of the invention for the diacyl chloride monomer is a dropping method, the feeding rate is 0.01-30 ml/min, preferably 0.01-20 ml/min, in the embodiment, the accelerating rate is 0.01-5 ml/min; the interfacial polymerization temperature is-10 to 25 ℃, preferably-5 to 15 ℃, and in the embodiment, the interfacial polymerization temperature is specifically 0 to 10 ℃; the reaction time is 0.5 to 10 hours, preferably 2 to 8 hours, and in the examples, the reaction time is specifically 2.5 to 5 hours.
After the interfacial polymerization was stopped, the solution was precipitated in acetone under vigorous stirring, filtered, repeatedly boiled with deionized water and dried to give a white polymer product, which was analyzed by infrared spectroscopy. The thermal decomposition performance of the product was determined using a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer. Experiments show that the invention can prepare hyperbranched polyarylate with different structures, has good thermal stability and widens the application range of polyarylate.
In addition, the preparation method provided by the invention has the advantages of mild conditions and easiness in implementation, and the monomer has higher cost performance, is popularized and applied and has obvious economic and social benefits.
For further understanding of the present invention, the following examples are given to illustrate the hyperbranched polyarylate of the present invention and the preparation method thereof, and the scope of the present invention is not limited by the following examples.
Example 1
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 5.7g of phenolphthalein, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h at the temperature of 10 ℃; dripping 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution for 10 minutes, setting the temperature to 10 ℃, and stirring for 5 hours; the solution was placed in a beaker containing 50ml of acetone with vigorous stirring, precipitated for 2h, filtered, repeatedly washed with deionized water to remove residual inorganic salts, and dried to give a white product with a yield of >90% and a structure as shown in the infrared spectrum (fig. 1) giving a degree of branching of 0.46.
The thermal decomposition performance of the product is measured by a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer, and the measurement conditions are as follows: under the protection of nitrogen, the temperature rise speed is 10 ℃/min and 0-700 ℃. The results show that: the temperature of 5% weight loss of the hyperbranched polyarylate is 370 ℃, and the temperature of 10% weight loss of the hyperbranched polyarylate is 450 ℃.
Example 2
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 5.7g of phenolphthalein, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h, wherein the temperature is set to be 10 ℃; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropwise manner within 20 minutes, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of more than 90%.
According to the test method in the example 1, the test result is as follows: the weight loss 5% temperature is: 388 ℃, 10% weight loss temperature: 465 ℃.
Example 3
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 5.7g of phenolphthalein, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h at the temperature of 10 ℃; and (2) dropwise adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a 30-minute dripping mode, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product, wherein the yield is over 90 percent, and the branching degree is 0.36.
The white product was subjected to infrared spectroscopic analysis, and the results were shown in FIG. 2, 3311cm -1 Is located at 3178cm and is N-H vibration peak -1 Is at C-H stretching vibration peak on benzene ring, 1776cm -1 Is located at 1651cm of carbonyl stretching vibration peak on phenolphthalein structural unit lactone -1 Is located at 1511cm and is the vibration peak of carbonyl stretching -1 The equivalent is a benzene ring skeleton stretching vibration peak of 1243cm -1 Is represented by C-O-C stretching vibration peak 1167cm on the aromatic ether -1 Is positioned as C-O stretching vibration peak in phenolphthalein lactone。
According to the test method in example 1, the test results are: the weight loss 5% temperature is: 392 ℃, 10% weight loss temperature: 467 deg.C.
Example 4
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 4.08g of bisphenol A,1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water in a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h at the temperature of 10 ℃; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropping mode within 30 minutes, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of more than 90%.
According to the test method in the example 1, the test result is as follows: the weight loss 5% temperature is: 390 ℃, 10% weight loss temperature: 479 deg.C.
Example 5
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 6.27g of bisphenol fluorene, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and setting the temperature to be 10 ℃ for reacting for 1 hour; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropwise manner within 30 minutes, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of more than 90%.
According to the test method in example 1, the test results are: the weight loss 5% temperature is: 406 ℃ and 10% weight loss temperature: 489 deg.C.
The hyperbranched polyarylates prepared herein can be processed by solution methods (solution cast films) and thus, solubility can reveal their processing properties as shown in table 1:
TABLE 1 solubility data of hyperbranched polyarylates in common organic solvents
++: completely dissolved at room temperature
The hyperbranched polyarylates prepared in examples 1 and 3 in table 1 are soluble in the above-mentioned organic solvents at room temperature, which indicates that the solution process is feasible, and the product is not crosslinked and has a branched structure.
Comparative example 1 (KOH was used as a catalyst)
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 5.7g of phenolphthalein, 1.9g of KOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water in a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h at the temperature of 10 ℃; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropping mode within 30 minutes, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of 30%.
The thermal decomposition performance of the product is measured by a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer, and the measurement conditions are as follows: under the protection of nitrogen, the temperature rise speed is 10 ℃/min and is 0-700 ℃. The test results are as follows: the temperature of 5 percent weight loss of the hyperbranched polyarylate is 140 ℃, and the temperature of 243 percent weight loss of 10 percent is 243 ℃.
Comparative example 2 (feeding mode of one-time whole feeding of acyl chloride solution)
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 5.7g of phenolphthalein, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h, wherein the temperature is set to be 10 ℃; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a one-step feeding mode, setting the temperature at 10 ℃, stirring for 5h, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of 59%.
The thermal decomposition performance of the product is measured by a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer, and the measurement conditions are as follows: under the protection of nitrogen, the temperature rise speed is 10 ℃/min and is 0-700 ℃. The test results are: the weight loss 5% temperature is: 180 ℃, 10% weight loss temperature: 275 ℃.
Comparative example 3 (polymerization temperature 30 ℃ C.)
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 5.7g of phenolphthalein, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h at the temperature of 10 ℃; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropping mode within 30 minutes, setting the temperature at 30 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of 60%.
The thermal decomposition performance of the product is measured by a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer, and the measurement conditions are as follows: under the protection of nitrogen, the temperature rise speed is 10 ℃/min and is 0-700 ℃. The test results are as follows: the weight loss 5% temperature is: 174 ℃, 10% weight loss temperature: 266 ℃ C.
Comparative example 4 (phase transfer catalyst addition 0.1%)
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 4.08g of bisphenol A,1.44g of NaOH,0.02g of benzyltriethylammonium chloride and 50ml of deionized water in a three-mouth bottle with a thermometer, introducing nitrogen and mechanically stirring, and reacting for 1h at the temperature of 10 ℃; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropwise manner within 30 minutes, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of 58%.
The thermal decomposition performance of the product is measured by a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer, and the measurement conditions are as follows: under the protection of nitrogen, the temperature rise speed is 10 ℃/min and 0-700 ℃. The test results are: the weight loss 5% temperature is: 190 ℃, 10% weight loss temperature: 281 ℃.
Comparative example 5 (hydroxyl monomer used 1, 5-dihydroxynaphthalene)
Placing 1.9g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 2.68g of 1, 5-dihydroxynaphthalene, 1.44g of NaOH,0.272g of benzyltriethylammonium chloride and 50ml of deionized water into a three-necked flask with a thermometer, introducing nitrogen and mechanically stirring, setting the temperature to be 10 ℃, and reacting for 1h; adding 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride into the aqueous phase solution in a dropwise manner within 30 minutes, setting the temperature at 10 ℃, stirring for 5 hours, placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product with the yield of 40%.
The thermal decomposition performance of the product is measured by a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer, and the measurement conditions are as follows: under the protection of nitrogen, the temperature rise speed is 10 ℃/min and 0-700 ℃. The test results are: the weight loss 5% temperature is: 176 ℃, 10% weight loss temperature: 267 ℃.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A hyperbranched polyarylate having the structure of (I),
wherein Ar is formed 1 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
formation of Ar 2 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4 '-dihydroxy diphenyl ether, 4' -dihydroxy biphenyl and isosorbide.
2. Hyperbranched polyarylate according to claim 1, wherein the degree of branching DB of the hyperbranched polyarylate is from 0.1 to 0.8.
3. The method of preparing the hyperbranched polyarylate as claimed in claim 1, comprising:
carrying out interfacial polymerization on 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a structure shown in a formula (II), a diacyl chloride monomer and a dihydroxyl monomer to obtain hyperbranched polyarylate;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4 '-dihydroxy diphenyl ether, 4' -dihydroxy biphenyl and isosorbide;
4. the preparation method according to claim 3, wherein the hyperbranched polyarylate is prepared by:
reacting 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a dihydroxy monomer under the action of a catalyst and a phase transfer catalyst to obtain an initial reactant;
and dropwise adding the bisacyl chloride monomer solution into the initial reactant for reaction to obtain the hyperbranched polyarylate.
5. The production method according to claim 3 or 4, wherein the molar ratio of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the bisacyl chloride monomer and the bishydroxy monomer is (0.5 to 1): (2-6): (2-6).
6. The method of claim 3 or 4, wherein the interfacial polymerization catalyst is selected from NaOH and K 2 CO 3 And Na 2 CO 3 The phase transfer catalyst for interfacial polymerization is selected from one or more of benzyltriethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide.
7. The method according to claim 6, wherein the molar amount of the catalyst to the bishydroxy monomer is 2 to 10:1, the phase transfer catalyst is 0.2 to 10 weight percent of the total amount of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the diacyl chloride monomer and the dihydroxy monomer.
8. The production method according to claim 4, wherein the dropping rate is 0.01 to 30ml/min.
9. The method according to claim 4, wherein the solvent of the bisacyl chloride monomer solution is selected from chloroform, dichloromethane or dichloroethane, and the amount of the solvent in the bisacyl chloride monomer solution is 10 to 70wt%.
10. The method according to claim 3 or 4, wherein the interfacial polymerization is carried out at a temperature of-10 to 25 ℃ for a time of 0.5 to 10 hours.
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