CN114656633A - Dihydropyridine polymer and preparation method thereof - Google Patents
Dihydropyridine polymer and preparation method thereof Download PDFInfo
- Publication number
- CN114656633A CN114656633A CN202210334077.7A CN202210334077A CN114656633A CN 114656633 A CN114656633 A CN 114656633A CN 202210334077 A CN202210334077 A CN 202210334077A CN 114656633 A CN114656633 A CN 114656633A
- Authority
- CN
- China
- Prior art keywords
- substituent
- polymer
- dihydropyridine
- hydrogen
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000001424 substituent group Chemical group 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- -1 ester compound Chemical class 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229940078552 o-xylene Drugs 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 claims description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 2
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000003445 Hantzsch reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 125000004925 dihydropyridyl group Chemical group N1(CC=CC=C1)* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a dihydropyridine polymer, the structural formula of which is shown as follows;
wherein, the substituent R1、R4Independently selected from hydrogen, aryl, benzyl, alkyl; substituent R2、R6Independently selected from COOR, COR, CONR, SO3R; the substituent R is selected from hydrogen or alkyl; substituent R3、R5Independently selected from aryl, alkyl. The preparation method comprises the following steps: (1) putting an ester compound and a bifunctional compound into a solvent, and carrying out esterification reaction under the catalytic action of a supported catalyst to prepare a polymer monomer; (2) and (3) placing a polymer monomer, an amine source and aldehyde in a solvent to perform Hantzsch polymerization reaction to prepare the dihydropyridine polymer. The dihydropyridine polymer disclosed by the invention is applied to increasing the thermal stability and lubricity of a polyvinyl chloride material as an additive. The preparation method has the advantages of easily obtained raw materials, simple and convenient operation and mild reaction conditionsGreen and environment-friendly, and low production cost.
Description
Technical Field
The invention relates to a dihydropyridine polymer and a preparation method thereof, belonging to the technical field of polymer preparation.
Background
1,4-dihydropyridines (1,4-dihydropyridines,1,4-DHPs) nitrogen-containing heterocyclic compounds mostly have physiological activity and are widely researched in the fields of medicine synthesis, application and the like. Dihydropyridine calcium ion antagonists are the most widely used drugs for treating cardiovascular and cerebrovascular diseases clinically in recent years. The synthesis of low molecular dihydropyridine structure has been studied, but the synthesis of dihydropyridine polymers and their application in PVC materials have not been reported.
Disclosure of Invention
In view of the above prior art, the present invention provides a dihydropyridine polymer, and a method for preparing the same. The invention has the advantages that various bifunctional ester and amide compounds are synthesized by ester exchange reaction under the action of a supported catalyst, and different substituted dihydropyridine compounds are realized by Hantzsch reaction with aldehyde and ammonia compounds, so that the reaction operation is simple and convenient, the environment is friendly, no additive is required to be added, and the reaction time is short.
The invention is realized by the following technical scheme:
the dihydropyridine polymer has a structural formula shown as the following formula;
wherein, the substituent R1、R4Independently selected from hydrogen, aryl, benzyl, alkyl; substituent R2、R6Independently selected from COOR, COR, CONR, SO3R; the substituent R is selected from hydrogen or alkyl; substituent R3、R5Independently selected from aryl, alkyl; n is a positive integer of 2-10000.
Preferably, the substituent R1、R4Independently selected from hydrogen, phenyl; the substituent R2、R6Independently selected from COOCH2、COO(CH2)5CH2、CONCH2、CON(CH2)5CH2(ii) a The substituent R3、R5Independently selected from methyl, propyl.
More preferably, the dihydropyridine polymer is one of the following:
(ii) the substituent R1、R4Selected from hydrogen; the substituent R2、R6Is selected from COOCH2(ii) a The substituent R3、R5Selected from methyl.
② the substituent R1、R4Selected from hydrogen; the substituent R2、R6Selected from COO (CH)2)5CH2(ii) a The substituent R3、R5Selected from methyl.
③ said substituent R1、R4Selected from hydrogen; the substituent R2、R6Selected from CONCH2(ii) a The substituent R3、R5Selected from methyl.
Fourthly, the substituent R1Selected from hydrogen, said substituents R4Is selected from phenyl; the substituent R2、R6Selected from CONCH2(ii) a The substituent R3、R5Selected from propyl groups.
Pentakis said substituent R1Selected from hydrogen, said substituent R4Is selected from phenyl; the substituent R2、R6Selected from CON (CH)2)5CH2(ii) a The substituent R3、R5Selected from methyl.
Sixthly, the substituent R1、R4Selected from hydrogen; the substituent R2Selected from CONCH2The substituent R6Is selected from COOCH2(ii) a The substituent R3、R5Selected from methyl and propyl.
The dihydropyridine polymer is synthesized by the following synthetic route;
further, the preparation method of the dihydropyridine polymer comprises the following steps:
(1) putting an ester compound and a bifunctional compound into a solvent, carrying out esterification reaction under the catalytic action of a supported catalyst, and filtering to prepare a polymer monomer;
the ester compound is selected from one or more than two of methyl acetoacetate, ethyl acetoacetate and methyl n-butyrylacetate;
the bifunctional compound is selected from any one or more than two of ethylene glycol, dodecanediol, ethylenediamine and 2-aminoethanol;
(2) putting a polymer monomer, an amine source and aldehyde into a solvent, carrying out Hantzsch polymerization reaction, and centrifuging to prepare a dihydropyridine polymer;
the amine source is selected from one or more than two of ammonia gas, ammonia water, ammonium acetate, ammonium bromide, methylammonium and aromatic ammonium;
the aldehyde is selected from one or more than two of alkyl aldehyde, aryl aldehyde, urotropine, trioxymethylene and paraformaldehyde.
Further, in the step (1), the molar ratio of the ester compound to the bifunctional compound is 1: 2-5.
Further, in the step (1), the solvent is any one or more of benzene, o-xylene, chlorobenzene, toluene and 1, 4-dioxane.
Further, in the step (1), the supported catalyst is selected from Co/AIPO and Al2O3/SiO2An acidic supported catalyst such as Pt/CeO-CN, Ca/SBA-15, Mg/SBA-15 and the like; the dosage of the catalyst is 1-25% of the total weight of the reaction raw materials.
Further, in the step (1), the esterification reaction conditions are as follows: the reaction temperature is 20-180 ℃, and the reaction time is 8-24 hours.
Further, in the step (2), the molar ratio relationship among the polymer monomer, the amine source and the aldehyde is 2: 1-15.
Further, in the step (2), the solvent is one or more selected from the group consisting of propylene glycol, tripropylene glycol, acetone, ethanol, methanol, isopropanol, n-butanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 2-t-butoxyethanol, ethylene glycol, tetrapropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.
Further, in the step (2), the mass percentage of the solvent is 50% -80%, and an initiator and an emulsifier are not needed in the polycondensation reaction.
Further, in the step (2), the conditions of the Hantzsch polymerization reaction are as follows: the temperature is 20-80 ℃, and the reaction time is 8-24 hours.
Use of the dihydropyridine polymer as an additive to increase the thermal stability and/or lubricity of a polyvinyl chloride (PVC) material.
The invention has the advantages that various bifunctional ester and amide compounds are synthesized by ester exchange reaction under the action of a supported catalyst, and different substituted dihydropyridine compounds are realized by Hantzsch reaction with aldehyde and ammonia compounds, so that the reaction operation is simple and convenient, the environment is friendly, no additive is required to be added, and the reaction time is short. The preparation method disclosed by the invention has the advantages of easiness in obtaining raw materials, simplicity and convenience in operation, mild reaction conditions, greenness, environmental friendliness and low production cost. The dihydropyridine polymer disclosed by the invention can be used as an additive for preparing a polyvinyl chloride material, and can be used for increasing the thermal stability and lubricity of the polyvinyl chloride material.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
EXAMPLE 1 preparation of Hydropyridine Polymer
The synthetic route is shown below.
The preparation method comprises the following steps: at normal temperature and in an air atmosphere, methyl acetoacetate (11.5g, 0.1mol), ethylene glycol (13.03g, 0.21mol), a supported catalyst (5%) (Co/AIPO acidic supported catalyst) and 10mL of o-xylene are sequentially added into a reaction bottle, and a polymerization monomer is obtained by refluxing for 12h and suction filtration. Then, liquid ammonia (11.28g,0.66mol), formaldehyde (19.8g,0.66mol) and 10mL of methanol were added thereto, refluxed at room temperature for 8 hours, and centrifuged to obtain a yellow solid.
EXAMPLE 2 preparation of Hydropyridine Polymer
The synthetic route is shown below.
The preparation method comprises the following steps: at normal temperature and in an air atmosphere, ethyl acetoacetate (13.01g, 0.1mol), dodecanediol (50.58g, 0.25mol), a supported catalyst (5%) Co/AIPO acidic supported catalyst) and 10mL o-xylene are sequentially added into a reaction bottle, reflux is carried out for 12h, and a polymerization monomer is obtained by suction filtration. Then, liquid ammonia (18.7g, 1.1mol), formaldehyde (1.1mol) and methanol (10 mL) were added, and the mixture was refluxed at 50 ℃ for 8 hours, and the dissolved solution was homogenized by emulsification and centrifuged to obtain a yellow solid.
EXAMPLE 3 preparation of Hydropyridine Polymer
The synthetic route is shown below.
The preparation method comprises the following steps: ethyl acetoacetate (13.01g, 0.1mol), ethylenediamine (12.62g, 0.21mol), a supported catalyst (5%) Co/AIPO acidic supported catalyst) and 10mL of toluene were sequentially added to a reaction flask at normal temperature in an air atmosphere, refluxed for 12 hours, and suction-filtered to obtain a polymerization monomer. Then, liquid ammonia (11.28g,0.66mol), formaldehyde (19.8g,0.66mol), 10mL of ethanol was added, refluxed at 80 ℃ for 8h, and centrifuged to obtain a yellow solid.
EXAMPLE 4 preparation of Hydropyridine Polymer
The synthetic route is shown below.
The preparation method comprises the following steps: methyl n-butyrylacetate (13.01g, 0.1mol), ethylene glycol (13.03g, 0.21mol), a supported catalyst (5%) Co/AIPO acidic supported catalyst) and 10mL of o-xylene are sequentially added into a reaction bottle at normal temperature and in an air atmosphere, refluxed for 12 hours, and filtered to obtain a polymerization monomer. Aniline (93.13g,1.0mol), formaldehyde (30.03g,1.0mol), ethanol 10mL, reflux at 30 ℃ for 8h, and centrifugation gave a yellow solid.
EXAMPLE 5 preparation of Hydropyridine Polymer
The synthetic route is shown below.
The preparation method comprises the following steps: methyl acetoacetate (11.5g, 0.1mol), dodecadiamine (46.08g, 0.23mol), supported catalyst (5%) Co/AIPO acidic supported catalyst) and o-xylene (10 mL) are sequentially added into a reaction bottle at normal temperature and in an air atmosphere, and then the mixture is refluxed for 12 hours and filtered to obtain a polymerization monomer. Aniline (74.50g, 0.8mol), urotropin (112.15g,0.8mol), methanol 10mL, reflux at 40 ℃ for 8h, and centrifugation gave a yellow solid.
EXAMPLE 6 preparation of Hydropyridine Polymer
The synthetic route is shown below.
The preparation method comprises the following steps: methyl acetoacetate (11.61g, 0.1mol), 2-aminoethanol (12.83g, 0.21mol), a supported catalyst (5%) Co/AIPO acidic supported catalyst) and 10mL of o-xylene are sequentially added into a reaction bottle at normal temperature in an air atmosphere, refluxed for 12h and filtered to obtain a polymerization monomer. Ammonium acetate (50.88g,0.66mol), urotropin (42.057g,0.3mol), diethyl ether 10mL, reflux at 60 ℃ for 8h, and centrifugation gave a yellow solid.
The above examples are provided to enable those skilled in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. The dihydropyridine polymer has a structural formula shown as the following formula;
wherein, the substituent R1、R4Independently selected from hydrogen, aryl, benzyl, alkyl; substituent R2、R6Independently selected from COOR, COR, CONR, SO3R; the substituent R is selected from hydrogen or alkyl; substituent R3、R5Independently selected from aryl, alkyl; n is a positive integer of 2-10000.
2. The dihydropyridine polymer of claim 1, characterized in that: the substituent R1、R4Independently selected from hydrogen, phenyl; the substituent R2、R6Independently selected from COOCH2、COO(CH2)5CH2、CONCH2、CON(CH2)5CH2(ii) a The substituent R3、R5Independently selected from methyl, propyl.
3. The dihydropyridine polymer of claim 1, characterized in that: the dihydropyridine polymer is one of the following;
(ii) the substituent R1、R4Selected from hydrogen; the substituent R2、R6Is selected from COOCH2(ii) a The substituent R3、R5Is selected from methyl;
② the substituent R1、R4Selected from hydrogen; the substituent R2、R6Selected from COO (CH)2)5CH2(ii) a The substituent R3、R5Is selected from methyl;
③ said substituent R1、R4Selected from hydrogen; the substituent R2、R6Selected from CONCH2(ii) a The substituent R3、R5Is selected from methyl;
fourthly, the substituent R1Selected from hydrogen, said substituent R4Is selected from phenyl; the substituent R2、R6Selected from CONCH2(ii) a The substituent R3、R5Is selected from propyl;
pentakis said substituent R1Selected from hydrogen, said substituent R4Is selected from phenyl; the substituent R2、R6Selected from CON (CH)2)5CH2(ii) a The substituent R3、R5Is selected from methyl;
sixthly, the substituent R1、R4Selected from hydrogen; the substituent R2Selected from CONCH2The substituent R6Is selected from COOCH2(ii) a The substituent R3、R5Selected from methyl and propyl.
4. The preparation method of the dihydropyridine polymer is characterized by comprising the following steps of:
(1) putting an ester compound and a bifunctional compound into a solvent, and carrying out esterification reaction under the catalytic action of a supported catalyst to prepare a polymer monomer;
the ester compound is selected from one or more than two of methyl acetoacetate, ethyl acetoacetate and methyl n-butyrylacetate;
the bifunctional compound is selected from any one or more than two of ethylene glycol, dodecanediol, ethylenediamine and 2-aminoethanol;
(2) putting a polymer monomer, an amine source and aldehyde into a solvent, and carrying out Hantzsch polymerization reaction to prepare a dihydropyridine polymer;
the amine source is selected from one or more than two of ammonia gas, ammonia water, ammonium acetate, ammonium bromide, methylammonium and aromatic ammonium;
the aldehyde is selected from one or more than two of alkyl aldehyde, aryl aldehyde, urotropine, trioxymethylene and paraformaldehyde.
5. The method of claim 4, wherein: in the step (1), the molar ratio of the ester compound to the bifunctional compound is 1: 2-5;
the solvent is selected from any one or more than two of benzene, o-xylene, chlorobenzene, toluene and 1, 4-dioxane;
the supported catalyst is selected from Co/AIPO and Al2O3/SiO2An acidic supported catalyst such as Pt/CeO-CN, Ca/SBA-15, Mg/SBA-15 and the like; the dosage of the catalyst is 1-25% of the total weight of the reaction raw materials.
6. The method of claim 4, wherein: in the step (1), the esterification reaction conditions are as follows: the reaction temperature is 20-180 ℃, and the reaction time is 8-24 hours.
7. The method of claim 4, wherein: in the step (2), the molar ratio of the polymer monomer, the amine source and the aldehyde is 2: 1-15;
the solvent is selected from one or more of propylene glycol, tripropylene glycol, acetone, ethanol, methanol, isopropanol, n-butanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 2-tert-butoxyethanol, ethylene glycol, tetrapropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and tripropylene glycol monomethyl ether.
8. The method of claim 4, wherein: in the step (2), the conditions of the Hantzsch polymerization reaction are as follows: the temperature is 20-80 ℃, and the reaction time is 8-24 hours.
9. A dihydropyridine polymer produced by the production method according to any one of claims 4 to 8.
10. Use of a dihydropyridine polymer as claimed in any one of claims 1, 2, 3, 9 as an additive to increase the thermal stability and/or lubricity of a polyvinyl chloride material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210334077.7A CN114656633A (en) | 2022-03-31 | 2022-03-31 | Dihydropyridine polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210334077.7A CN114656633A (en) | 2022-03-31 | 2022-03-31 | Dihydropyridine polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114656633A true CN114656633A (en) | 2022-06-24 |
Family
ID=82034171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210334077.7A Pending CN114656633A (en) | 2022-03-31 | 2022-03-31 | Dihydropyridine polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114656633A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286887A1 (en) * | 1987-04-15 | 1988-10-19 | Lagor Spa | Poly 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylesters useful as thermal stabilizers for synthetic polymers |
| CN101942088A (en) * | 2010-08-24 | 2011-01-12 | 中山大学 | Method for synthesizing acetoacetate ester compound |
| CN111440260A (en) * | 2019-01-16 | 2020-07-24 | 清华大学 | 1, 4-dihydropyridine polymer and high-flux preparation method and application thereof |
-
2022
- 2022-03-31 CN CN202210334077.7A patent/CN114656633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286887A1 (en) * | 1987-04-15 | 1988-10-19 | Lagor Spa | Poly 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylesters useful as thermal stabilizers for synthetic polymers |
| CN101942088A (en) * | 2010-08-24 | 2011-01-12 | 中山大学 | Method for synthesizing acetoacetate ester compound |
| CN111440260A (en) * | 2019-01-16 | 2020-07-24 | 清华大学 | 1, 4-dihydropyridine polymer and high-flux preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2010110460A1 (en) | METHOD FOR PRODUCING LACTIDE/ε-CAPROLACTONE COPOLYMER | |
| US8039618B2 (en) | Method for producing bicyclic guanidines by use of a cyclic urea | |
| KR20020057949A (en) | New phenylpiperazines | |
| JP2016525083A (en) | 2-oxo-1,3-dioxolane-4-acyl halide, its preparation and use | |
| US3832362A (en) | Epoxidized alkylidene and arylidene indandiones | |
| CN114656633A (en) | Dihydropyridine polymer and preparation method thereof | |
| CN104311582A (en) | Schiff base zinc compound, preparation method of schiff base zinc compound, and preparation method of polylactic acid | |
| WO2020088119A1 (en) | Catalyst for silylation reaction of aromatic amine | |
| CN104557874A (en) | Quinoline amido indolyl zinc, magnesium and calcium compound as well as preparation method and application thereof | |
| CN101921258B (en) | Preparation method of 5-( arylmethylene) meldrum's acid | |
| WO2022116463A1 (en) | Polythiocarbamate compound, preparation method therefor and application thereof | |
| JP6021818B2 (en) | Method for preparing enamine | |
| JPS6026154B2 (en) | Production method of basic oxazine dye | |
| CN108503576B (en) | Asymmetric ligand containing o-phenylenediamine group, preparation method and application thereof | |
| CN108003087B (en) | Chiral asymmetric nitrogen-oxygen ligand containing salicylaldehyde group and preparation method and application thereof | |
| Wei et al. | Catalyst‐Free Multicomponent Tandem Polymerizations of Aliphatic Amines, Activated Alkyne, and Formaldehyde toward Poly (tetrahydropyrimidine) s | |
| JPH0321620A (en) | New polyacetal copolymers of trioxane and glycidyl ester derivatives | |
| JP6022472B2 (en) | Method for preparing enamine | |
| Cammack et al. | Synthesis of ketobemidone precursors via phase‐transfer catalysis | |
| CN102516273B (en) | Compound containing zinc core and preparation and application thereof | |
| CN108558705A (en) | A kind of carbamic acid aromatic ester monomer of phenolic hydroxy group amino acid, preparation method and application | |
| CN113943281B (en) | Synthetic method and application of isoxazole pyrimidine derivative | |
| CN107383010A (en) | A kind of compound and preparation method thereof | |
| JPS63501082A (en) | Poly(1-oxy-3-lactam vinylene) | |
| CA2215837C (en) | Dimethylamine benzoate or p-anisate catalysed process for the preparation of 4-(nitrophenyl)-dihydropyridines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220624 |
|
| RJ01 | Rejection of invention patent application after publication |