CN117229497A - Hyperbranched polyamide resin and preparation method and application thereof - Google Patents
Hyperbranched polyamide resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN117229497A CN117229497A CN202311278994.9A CN202311278994A CN117229497A CN 117229497 A CN117229497 A CN 117229497A CN 202311278994 A CN202311278994 A CN 202311278994A CN 117229497 A CN117229497 A CN 117229497A
- Authority
- CN
- China
- Prior art keywords
- acid
- polyamide resin
- amino
- substituted
- hyperbranched polyamide
- 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.)
- Granted
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007112 amidation reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 229940126062 Compound A Drugs 0.000 claims description 12
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 carbonyl ethyl Chemical group 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 5
- ODKSFYDXXFIFQN-UHFFFAOYSA-N Arginine Chemical compound OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001555 benzenes Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Chemical compound OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- PKUWKAXTAVNIJR-UHFFFAOYSA-N O,O-diethyl hydrogen thiophosphate Chemical compound CCOP(O)(=S)OCC PKUWKAXTAVNIJR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004984 aromatic diamines Chemical class 0.000 claims description 2
- 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 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The application provides a preparation method of hyperbranched polyamide resin, and a preparation method and application thereof. The preparation method comprises the following steps: the mixed reaction system containing the dibasic acid, diamine and catalyst is heated to 80-130 ℃ to react, then heated to 150-180 ℃ to react, the hyperbranched polyamide resin is obtained, wherein the dibasic acid comprises the dibasic acid containing amino group shown in the formula II,wherein Y is selected from p-benzene or m-benzene, R 1 、R 2 Independently selected from a substituted or unsubstituted straight or branched chain alkyl group or a substituted or unsubstituted aryl group. The hyperbranched polyamide resin provided by the application contains rich terminal amino groups and higher branching degree, and can well improve the mechanical property and heat resistance of epoxy resin when being used as an epoxy resin curing agent.
Description
Technical Field
The application belongs to the technical field of polymer chemistry, and particularly relates to hyperbranched polyamide resin, and a preparation method and application thereof.
Background
The epoxy resin is a chemical product widely applied to a plurality of fields, is a linear polymer material, and needs to be crosslinked with a curing agent to form a net structure with a body shape so as to show excellent performance.
At present, the epoxy curing agent mainly comprises an anhydride curing agent and an amine curing agent, wherein the polyamine curing agent is the most widely applied curing agent, wherein the polyamide curing agent occupies an important position in the polyamine curing agent, the traditional polyamide curing agent is synthesized by polyamine and dimer acid, and the cured product has the defects of low hardness, poor heat resistance, poor solvent resistance and the like due to the mild curing condition and good flexibility.
Disclosure of Invention
In order to solve all or part of the technical problems, the application provides the following technical scheme:
one of the objects of the present application is to provide a hyperbranched polyamide resin comprising a segmented structure represented by formula I:
wherein Y is selected from p-benzene or m-benzene, R 1 And R is 2 Independently selected from substituted or unsubstituted straight or branched chain alkyl or substituted or unsubstituted aryl, R 3 Selected from linear or branched alkyl groups.
In some embodiments, R 3 Selected from hexyl, ethyl, propyl, butyl, nonyl, decyl, octyl or octadecyl.
The second object of the present application is to provide a method for producing a hyperbranched polyamide resin, comprising: the mixed reaction system containing the dibasic acid, diamine and catalyst is heated to 80-130 ℃ to react, then heated to 150-180 ℃ to react, the hyperbranched polyamide resin is obtained, wherein the dibasic acid comprises the dibasic acid containing amino group shown in the formula II,
wherein Y is selected from p-benzene or m-benzene, R 1 、R 2 Independently selected from a substituted or unsubstituted straight or branched chain alkyl group or a substituted or unsubstituted aryl group.
In some embodiments, R 1 、R 2 Independently selected from substituted or unsubstituted C 1 ～C 10 Straight or branched alkyl or substituted or unsubstituted benzene ring.
Further, R 1 、R 2 Independently selected from benzene ring, carbonyl ethyl, carbonyl propyl, pentyl, butyl formamidino or sec-butyl.
In some embodiments, the amino group-containing dibasic acid of formula II comprises at least one of compound 1, compound 2, compound 3, compound 4, and compound 5,
in some embodiments, the amino group-containing diacid is present in an amount of 5 to 100 weight percent of the diacid. The degree of branching of the polyamide resin can be controlled by adjusting the content of the amino dibasic acid, thereby adjusting the solubility and the amino content of the polyamide resin. Preferably, the content of the amino-containing dibasic acid is 10 to 50wt% of the dibasic acid.
In some embodiments, the content of the dibasic acid and diamine in the preparation process of the hyperbranched polyamide resin enables the molar ratio of carboxyl to amino in the mixed reaction system to be 1:1.1-1:2. Preferably 1:1.1 to 1:1.5.
In some embodiments, the diacid further comprises aliphatic diacid and/or aromatic diacid, and the content of the aliphatic diacid and/or the aromatic diacid accounts for 0% -95% of the total amount of the diacid. Further, the dibasic acid preferably includes at least one of terephthalic acid, isophthalic acid, adipic acid, succinic acid, sebacic acid, and azelaic acid.
In some embodiments, the diamine comprises an aliphatic diamine and/or an aromatic diamine. Further, the diamine preferably includes at least one of m-phenylenediamine, p-phenylenediamine, ethylenediamine, dipropylene triamine, propylenediamine, hexamethylenediamine, nonylenediamine, laurylenediamine, octadecyl diamine, and decylenediamine.
In some embodiments, the catalyst comprises at least one of diphenylphosphoryl chloride, diethyl phosphorothioate, dicyclohexylcarbodiimide, and triphenylphosphine.
In some implementations, the catalyst content is 100 to 1000ppm.
In some embodiments, the preparation method specifically includes: and uniformly dispersing the dibasic acid, diamine and catalyst in a first solvent to obtain the mixed reaction system.
Further, the first solvent includes at least one of water, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone.
In some embodiments, the hyperbranched polyamide resin is obtained by heating the mixed reaction system to 80-130 ℃ for 1-5 hours, and then heating the mixed reaction system to 150-180 ℃ for 2-6 hours.
In some embodiments, the method for preparing an amino group-containing dibasic acid comprises: amidation reaction is carried out on benzene ring dicarboxylic acid chloride and a compound A, wherein the compound A contains at least two amino groups and one carboxyl group, and the amidation reaction is carried out on the carboxyl group in the benzene ring dicarboxylic acid and the amino group on the compound A to obtain the amino group-containing dibasic acid.
In some embodiments, the compound A has a structure of formula III,
wherein R is selected from a substituted or unsubstituted straight or branched chain alkyl or a substituted or unsubstituted aryl.
In some embodiments, R is selected fromSubstituted or unsubstituted C 1 ～C 10 Straight or branched alkyl groups, or substituted or unsubstituted benzene rings.
In some embodiments, the compound a is selected from at least one of 3, 5-diaminobenzoic acid, 2-amino-3-carbamoylpropionic acid, 2-amino-4-carboxamidobutyric acid, 2-amino-5-guanidino valeric acid, and 2, 6-diaminohexanoic acid. It may be of the D, L or DL hybrid type.
In some embodiments, the benzene ring dicarboxylic acid dichloride includes at least one of terephthaloyl dichloride and isophthaloyl dichloride.
In some embodiments, the molar ratio of benzene ring dicarboxylic acid dichloride to compound A is 1:2 to 1:10. Preferably 1:2 to 1:4.
In some embodiments, the amidation reaction temperature is between 0 and 50 ℃.
In some embodiments, the amidation reaction time is 60 to 600 minutes.
In some embodiments, the amidation reaction has a pH of 7 to 8.5.
In some embodiments, the preparation method specifically includes: the benzene ring type dicarboxylic acid chloride and the compound a are uniformly dispersed in a second solvent to perform the amidation reaction. Suitable second solvents include, but are not limited to, water or one or more combinations of non-aqueous solvents such as organic solvents, ionic liquids, and the like. The organic solvent may be exemplified by a single alcohol (ethanol), an ether (tetrahydrofuran), a ketone (acetone), a halogenated hydrocarbon (methylene chloride), a nitrogen compound, a sulfur compound (N, N-dimethylformamide, dimethylsulfoxide), and the like. The second solvent preferably includes at least one of water, methylene chloride, ethanol, tetrahydrofuran, acetone, N-dimethylformamide, and dimethyl sulfoxide.
In one embodiment, the amidation reaction may be performed in the presence of an auxiliary agent or the like. Illustratively, the adjuvants may include catalysts and the like.
In the present application, the entire synthesis reaction of the amino dibasic acid may be performed in one reaction vessel, that is, synthesized by a one-pot reaction.
In the present application, after the amidation reaction is completed, the target product, i.e., the amino group-containing diacid compound, may be separated by post-treating the reaction mixture. The post-treatment comprises acidification, salification and recrystallization to obtain the product.
The third object of the present application is to provide a hyperbranched polyamide resin obtained by the above-mentioned production method.
In some embodiments, the hyperbranched polyamide resin has an amino value of 50 to 300mg KOH/g.
The fourth object of the present application is to provide the use of the hyperbranched polyamide resin according to any one of the above-mentioned aspects as a curing agent for epoxy resins.
Compared with the prior art, the application has at least the following technical effects: the hyperbranched polyamide resin prepared by the application has the characteristics of high branching degree, low viscosity, good solubility, low volatility, low toxicity and the like; and the epoxy resin curing agent has high reactivity due to the fact that the epoxy resin curing agent contains a large number of end groups, and the prepared cured product has high temperature resistance and mechanical properties due to high crosslinking degree.
Detailed Description
The following detailed description of the present application is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present application. Specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present application in virtually any appropriately detailed embodiment.
Example 1
50g of terephthaloyl chloride is weighed and dissolved in methylene dichloride to obtain terephthaloyl chloride solution, 110g of 3, 5-diaminobenzoic acid is weighed and dissolved in aqueous solution with pH value of 8-9 to obtain 3, 5-diaminobenzoic acid solution; slowly dripping terephthaloyl chloride solution into 3, 5-diaminobenzoic acid aqueous solution, reacting for 3 hours, controlling pH to 8-9 in the reaction process and the reaction temperature to 10+/-5 ℃, adjusting the pH to about 2.0-3.0 by using hydrochloric acid after the reaction is finished, evaporating water, and recrystallizing by using ethanol to obtain amino-containing dibasic acid, wherein the structural formula is as follows:
30g of the prepared amino diacid, 30g of terephthalic acid, 24.3g of hexamethylenediamine and 0.01g of diphenyl phosphoryl chloride are weighed and dissolved in dimethylformamide to obtain a mixed reaction system, the mixed reaction system is firstly heated to 80 ℃ for reaction for 2 hours, then heated to 160 ℃ for reaction for 2 hours, and the temperature is reduced after the reaction is finished, so that no solid is separated out, and the hyperbranched polyamide resin obtained has good solubility in the dimethylformamide, and is obtained through distilling, recovering the solvent, washing and drying.
The molecular weight of the resulting hyperbranched polyamide resin was 2300Da and the amino value thereof was found to be 168mg KOH/g.
Example 2
The preparation of the amino dibasic acid in this example differs from that in example 1 only in that 3, 5-diaminobenzoic acid is replaced with 2-amino-3-carbamoylpropionic acid to prepare the amino dibasic acid, which has the structural formula:
weighing 10g of the prepared amino diacid, 90g of isophthalic acid, 92.3g of dipropylene triamine and 0.02g of dicyclohexylcarbodiimide, dissolving in dimethyl sulfoxide to obtain a mixed reaction system, firstly heating the mixed reaction system to 100 ℃ for reaction for 1h, then heating to 180 ℃ for reaction for 1h, cooling after the reaction is finished, and no solid precipitation, thus indicating that the obtained hyperbranched polyamide resin has good solubility in dimethyl sulfoxide, distilling to recover solvent, washing with water and drying to obtain the hyperbranched polyamide resin.
The molecular weight of the resulting hyperbranched polyamide resin was 1800Da and the amino value thereof was measured to be 278mg KOH/g.
Example 3
This example differs from example 1 only in that 3, 5-diaminobenzoic acid is replaced with 2-amino-5-guanidinopentic acid and terephthalic acid is replaced with isophthalic acid, and has the structural formula:
weighing 20g of the prepared amino dibasic acid, 80g of adipic acid, 59.2g of ethylenediamine and 0.05g of triphenylphosphine, dissolving in N-methylpyrrolidone to obtain a mixed reaction system, heating the mixed reaction system to 120 ℃ for reaction for 1h, heating to 170 ℃, and reacting for 3h under the vacuum degree of 100Pa to obtain the hyperbranched polyamide resin.
The molecular weight of the resulting hyperbranched polyamide resin was 3500Da and the amino value thereof was measured to be 128mg KOH/g.
Example 4
This example differs from example 1 only in that 3, 5-diaminobenzoic acid was replaced with 2-amino-4-carboxamido-butyric acid and terephthalic acid was replaced with isophthalic acid, and the structural formula is:
weighing 30g of the prepared amino dibasic acid, 50g of succinic acid, 47.8g of propylene diamine and 0.06g of dicyclohexylcarbodiimide, dissolving in N-methylpyrrolidone to obtain a mixed reaction system, firstly heating the mixed reaction system to 110 ℃ for reaction for 1h, then heating to 180 ℃ for reaction for 2h, cooling after the reaction is finished, and no solid is separated out, so that the obtained hyperbranched polyamide resin has good solubility in N-methylpyrrolidone, distilling to recover the solvent, washing with water and drying to obtain the hyperbranched polyamide resin.
The molecular weight of the resulting hyperbranched polyamide resin was 2800Da and the amino value thereof was measured to be 89mg KOH/g.
Example 5
This example differs from example 1 only in that 3, 5-diaminobenzoic acid was replaced with 2, 6-diaminohexanoic acid and terephthalic acid was replaced with isophthalic acid, and the structural formula is:
and (3) weighing 20g of the prepared amino diacid, 40g of azelaic acid, 37.6g of m-xylylenediamine and 0.04g of diethyl phosphate, dissolving in water to obtain a mixed reaction system, heating the mixed reaction system to 100 ℃ to react for 2 hours, distilling to remove water, heating to 180 ℃ and reacting for 4 hours under the condition of 150Pa vacuum degree to obtain the hyperbranched polyamide resin.
The molecular weight of the resulting hyperbranched polyamide resin was 5600Da and the amino value thereof was measured to be 59mg KOH/g.
The hyperbranched polyamide resins of examples 1 to 5 and a commercially available epoxy resin E51 were prepared into floor paints, and after coating, test samples were prepared, and the tensile strength, heat distortion temperature and impact strength of the test samples were measured, and the measurement results are shown in Table 1 below, wherein the curing agent used in the comparative example was polyamide curing agent 650.
Table 1 test sample properties using examples 1 to 5 and comparative example
The application successfully prepares the novel hyperbranched polyamide resin, and when the novel hyperbranched polyamide resin is used as an epoxy resin curing agent, the novel hyperbranched polyamide resin contains a large amount of terminal amino groups due to high branching degree, so that the crosslinking degree of the epoxy resin can be greatly improved, and the mechanical property and heat resistance of the epoxy resin are further improved.
The various aspects, embodiments, features and examples of the application are to be considered in all respects as illustrative and not intended to limit the application, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed application.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the application has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the application. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the application without departing from the scope thereof. Therefore, it is intended that the application not be limited to the particular embodiment disclosed for carrying out this application, but that the application will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A hyperbranched polyamide resin characterized in that: the hyperbranched polyamide resin comprises a chain segment structure shown in a formula I:
wherein Y is selected from p-benzene or m-benzene, R 1 And R is 2 Independently selected from substituted or unsubstituted straight or branched chain alkyl or substituted or unsubstituted aryl, R 3 Selected from linear or branched alkyl groups.
2. A method for preparing hyperbranched polyamide resin, characterized by comprising: the mixed reaction system containing the dibasic acid, diamine and catalyst is heated to 80-130 ℃ to react, then heated to 150-180 ℃ to react, the hyperbranched polyamide resin is obtained, wherein the dibasic acid comprises the dibasic acid containing amino group shown in the formula II,
wherein Y is selected from p-benzene or m-benzene, R 1 、R 2 Independently selected from a substituted or unsubstituted straight or branched chain alkyl group or a substituted or unsubstituted aryl group.
3. The preparation method according to claim 2, characterized in that: r is R 1 、R 2 Independently selected from substituted or unsubstituted C 1 ～C 10 A linear or branched alkyl group or a substituted or unsubstituted benzene ring;
preferably, R 1 、R 2 Independently selected from benzene ring, carbonyl ethyl, carbonyl propyl, pentyl, butyl formamidino or sec-butyl.
4. The preparation method according to claim 2, characterized in that: the content of the amino-containing dibasic acid is 5-100 wt% of the dibasic acid, preferably 10-50 wt%;
and/or the content of the dibasic acid and diamine is such that the molar ratio of carboxyl to amino in the mixed reaction system is 1:1.1-1:2, preferably 1:1.1-1:1.5;
and/or the dibasic acid further comprises an aliphatic diacid and/or an aromatic diacid, preferably at least one of terephthalic acid, isophthalic acid, adipic acid, succinic acid, sebacic acid, and azelaic acid;
and/or the diamine comprises aliphatic diamine and/or aromatic diamine, preferably comprises at least one of m-phenylenediamine, p-phenylenediamine, ethylenediamine, dipropylene triamine, propylenediamine, hexamethylenediamine, nonylenediamine, laurylenediamine, octadecyl diamine and decylenediamine;
and/or the catalyst comprises at least one of diphenyl phosphoryl chloride, diethyl phosphorothioate, dicyclohexylcarbodiimide and triphenylphosphine;
and/or the content of the catalyst is 100-10000 ppm.
5. The preparation method according to claim 2, characterized by comprising the following steps: dispersing the dibasic acid, diamine and catalyst in a first solvent to obtain the mixed reaction system; preferably, the first solvent includes at least one of water, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone;
and/or heating the mixed reaction system to 80-130 ℃ for 1-5 h, and then heating to 150-180 ℃ for 2-6 h to obtain the hyperbranched polyamide resin.
6. The preparation method according to claim 2, characterized in that: the preparation method of the amino-containing dibasic acid comprises the following steps: amidation reaction is carried out on benzene ring dicarboxylic acid chloride and a compound A, wherein the compound A contains at least two amino groups and one carboxyl group, and the amidation reaction is carried out on the carboxyl group in the benzene ring dicarboxylic acid and the amino group on the compound A to obtain the amino group-containing dibasic acid.
7. The method of manufacturing according to claim 6, wherein: the compound A has a structure shown in a formula III,
wherein R is selected from a substituted or unsubstituted straight or branched chain alkyl group or a substituted or unsubstituted aryl group; preferably, R is selected from substituted or unsubstituted C 1 ～C 10 A linear or branched alkyl group or a substituted or unsubstituted benzene ring; more preferably, the compound A is selected from the group consisting of 3, 5-diaminobenzoic acid, 2-amino-3-carbamoylpropionic acid, 2-amino-4-carboxamidobutyric acid, 2-amino-5-guanidino valeric acid and 2, 6-diaminovaleric acidAt least one of caproic acid;
and/or the benzene ring type dicarboxylic acid dichloride comprises at least one of terephthaloyl dichloride and isophthaloyl dichloride.
8. The method of manufacturing according to claim 6, wherein: the molar ratio of the benzene ring type diformyl chloride to the compound A is 1:2-1:10, preferably 1:2-1:4:
and/or, the reaction temperature of the amidation reaction is 0-50 ℃;
and/or the reaction time of the amidation reaction is 60-600 min;
and/or the pH of the amidation reaction is 7-8.5;
and/or, the preparation method specifically comprises the following steps: uniformly dispersing the benzene ring type diformyl chloride and the compound A in a second solvent to perform the amidation reaction; preferably, the second solvent includes at least one of water, dichloromethane, ethanol, tetrahydrofuran, acetone, N-dimethylformamide and dimethyl sulfoxide.
9. Hyperbranched polyamide resin obtained by the preparation method according to any one of claims 2 to 8; preferably, the hyperbranched polyamide resin has an amino value of 50 to 300mg KOH/g.
10. Use of the hyperbranched polyamide resin according to claim 1 or 9 as curing agent for epoxy resins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311278994.9A CN117229497B (en) | 2023-09-28 | 2023-09-28 | Hyperbranched polyamide resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311278994.9A CN117229497B (en) | 2023-09-28 | 2023-09-28 | Hyperbranched polyamide resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117229497A true CN117229497A (en) | 2023-12-15 |
| CN117229497B CN117229497B (en) | 2024-03-29 |
Family
ID=89092745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311278994.9A Active CN117229497B (en) | 2023-09-28 | 2023-09-28 | Hyperbranched polyamide resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117229497B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07258406A (en) * | 1994-03-25 | 1995-10-09 | Chisso Corp | Polyamide resin |
| CN1354767A (en) * | 1999-05-05 | 2002-06-19 | 罗迪亚尼尔公司 | Hyperbranched copolyamide, composition based on said hyperbranched copolyamide, and method for obtaining same |
| CN103113578A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof |
| CN107586384A (en) * | 2017-09-18 | 2018-01-16 | 济南大学 | A kind of synthesis and application of ultrabranching polyamide type TPO modifying agent |
-
2023
- 2023-09-28 CN CN202311278994.9A patent/CN117229497B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07258406A (en) * | 1994-03-25 | 1995-10-09 | Chisso Corp | Polyamide resin |
| CN1354767A (en) * | 1999-05-05 | 2002-06-19 | 罗迪亚尼尔公司 | Hyperbranched copolyamide, composition based on said hyperbranched copolyamide, and method for obtaining same |
| CN103113578A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof |
| CN107586384A (en) * | 2017-09-18 | 2018-01-16 | 济南大学 | A kind of synthesis and application of ultrabranching polyamide type TPO modifying agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117229497B (en) | 2024-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20030055209A1 (en) | Process for manufacture of soluble highly branched polyamides, and at least partially aliphatic highly branched polyamides obtained therefrom | |
| WO2016050910A1 (en) | Copolyamides with alternating repeat units | |
| EP2444387A1 (en) | Cross-linkable end-cappers for primary amino groups | |
| Mondal et al. | Triptycene based organosoluble polyamides: synthesis, characterization and study of the effect of chain flexibility on morphology | |
| US20180194896A1 (en) | Production of a polyamide that contains 2,5-bis(aminomethyl)furan | |
| JP5416829B2 (en) | Method for producing heat-resistant polyamide | |
| CA1073592A (en) | Process of polymerization for the preparation of aromatic polyamides containing ether groups | |
| CN117229497B (en) | Hyperbranched polyamide resin and preparation method and application thereof | |
| US20090247709A1 (en) | Diamine polymer and resin composition thereof | |
| JPS58204021A (en) | Curing agent for epoxy resin | |
| JP3351007B2 (en) | Amorphous polyamide resin and method for producing the same | |
| CN110835412B (en) | Hyperbranched polymer, preparation method thereof and epoxy resin composition | |
| CN117186392B (en) | Polyamide resin and preparation method and application thereof | |
| JP2016166315A (en) | Truxillic acid-based polymer and production intermediate thereof | |
| US4948831A (en) | Process for preparing polyetherimide/epoxyimide resin composition | |
| JPH08302185A (en) | Polymer blend comprising aromatic polyamide and soluble polyamide | |
| Wang et al. | The Synthesis and Solubility of a Wholly Aromatic Polyamide Containing para-and meta-Substituted Phenylene Rings | |
| Kolahdoozan et al. | Synthesis and properties of novel co-poly (amide-ester-imide) s containing a PEG-600 linkage in the main chain | |
| KR102514169B1 (en) | Flow modifier comprising hyperbranched polymer and polymer composition with enhanced flowability by comprising the same | |
| RU2321609C1 (en) | Method for preparing polyamides | |
| WO2001081453A1 (en) | Method for making polyimide | |
| CN108484903B (en) | Polyamide containing 2-alkoxy-isophthalamide structure and preparation method thereof | |
| KR102263527B1 (en) | Semi-aromatic copolyamides based on caprolactam | |
| KR100948137B1 (en) | Polyamideimide resin having improved dimensional stability | |
| RU2544990C2 (en) | Method of producing aromatic polyamides |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |