CN114656636B - Polyester imide and preparation method thereof - Google Patents
Polyester imide and preparation method thereof Download PDFInfo
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- CN114656636B CN114656636B CN202210457217.XA CN202210457217A CN114656636B CN 114656636 B CN114656636 B CN 114656636B CN 202210457217 A CN202210457217 A CN 202210457217A CN 114656636 B CN114656636 B CN 114656636B
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- 229920003055 poly(ester-imide) Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 56
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
- 238000006068 polycondensation reaction Methods 0.000 claims description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 15
- 229940117969 neopentyl glycol Drugs 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 13
- 229940093476 ethylene glycol Drugs 0.000 claims description 13
- 150000004982 aromatic amines Chemical class 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- -1 alicyclic amine Chemical class 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 9
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229960004063 propylene glycol Drugs 0.000 claims description 5
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 229940015975 1,2-hexanediol Drugs 0.000 claims description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 230000032050 esterification Effects 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- KVMMOSKKPJEDNG-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,5-diamine Chemical compound C1C2C(N)CC1C(N)C2 KVMMOSKKPJEDNG-UHFFFAOYSA-N 0.000 description 4
- VMQNOUCSRQVOKM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,5-diamine Chemical compound C1C(N)C2C(N)CC1C2 VMQNOUCSRQVOKM-UHFFFAOYSA-N 0.000 description 4
- JGVWEAITTSGNGJ-UHFFFAOYSA-N bicyclo[2.2.1]heptane;n-methylmethanamine Chemical compound CNC.C1CC2CCC1C2 JGVWEAITTSGNGJ-UHFFFAOYSA-N 0.000 description 4
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- SUJGVCQADPBTOJ-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,4-diamine Chemical compound C1CC2C(N)CC1(N)C2 SUJGVCQADPBTOJ-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003028 elevating effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- SCMJJGWRVSLYLK-UHFFFAOYSA-N 4-phenoxycarbonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)OC1=CC=CC=C1 SCMJJGWRVSLYLK-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a polyester imide and a preparation method thereof, wherein the preparation method comprises the following steps: mixing acid monomers, alcohol monomers, anhydride monomers and amine monomers in a protective atmosphere, adjusting the molar ratio of the alcohol monomers to the acid monomers to be (2.5-4.0): 1, and reacting under the action of a catalyst to obtain the polyester imide; no solvent is added in the preparation method. In the preparation method, no solvent is added, the reaction monomer is fed by a one-step method, the types of amine monomers are not required to be limited, the process is simple, and the prepared polyester imide has good color phase, good high temperature resistance and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of copolyester preparation, in particular to a polyester imide and a preparation method thereof.
Background
Polyesters, polymers obtained by polycondensation of polyols and polyacids are collectively referred to. The application field of the polyester is greatly expanded due to the changeable raw materials, but the polyester also has the defects of high temperature difference resistance, low mechanical strength and the like, so that the application is limited. Polyimide is a generic name for polymers containing imide ring repeat units, and has good thermal oxidation stability, unique electrical properties, high radiation resistance and solvent resistance, and high mechanical strength. The polyimide structure is introduced into the polyester, so that the rigidity can be improved, and the aim of improving the glass transition temperature of the polyester is fulfilled.
CN113845764a discloses a heat-resistant modified polylactic acid material and a preparation method thereof, the disclosed polylactic acid material comprises the following components in parts by weight: 50-80 parts of lactide, 2-4 parts of catalyst, 10-30 parts of chitosan, 10-26 parts of single-walled carbon nanotube, 10-20 parts of polyimide, 3-9 parts of flame retardant and 0.5-1 part of toughening agent. The disclosed material introduces polyimide and other auxiliary agents into a polylactic acid system, so that the heat resistance of the material is greatly improved; has excellent mechanical properties; is convenient for processing. However, the melt blending method cannot ensure the blending uniformity and is easy to cause component migration in the later use process.
CN105085912a discloses a transparent polyester imide resin and a preparation method thereof by polycondensation reaction of a bis (3, 4-dimethyl anhydride) phenyl terephthalate monomer and a primary diamine monomer. In the design of the dianhydride, the formation of charge transfer complexes in and among the polyester imide molecules is inhibited by reducing the electron affinity of the dianhydride, thereby improving the transparency. The glass transition temperature of the obtained polyester imide resin is 200-350 ℃, the light transmittance at 400nm is 70-90%, the water absorption rate of the film is less than 0.5%, and the polyester imide resin has good application prospects in the fields of flexible substrate materials of solar cells, flexible transparent conductive film substrate materials, liquid crystal display materials and the like. The method takes N, N-dimethylacetamide as a solvent, adds primary amine monomers and anhydride to synthesize a polyesteramide acid solution, and prepares transparent polyesterimide resin through a thermal imidization method or a chemical imidization method, but the method needs a large amount of solvent, and has complex overall procedures such as filtering, washing and the like.
CN109054008A discloses a polyester resin for anti-yellowing HAA system powder coating, a preparation method and application, which uses pyromellitic dianhydride, 1, 6-hexamethylenediamine and the like as raw materials to synthesize polyester imide polyester; CN113563587a also synthesizes a polyester imide by using trimellitic anhydride and ethanolamine as raw materials. However, the processes in both patents have larger limitations on amine monomers, and can only be simpler aliphatic amine monomers such as hexamethylenediamine and ethanolamine, and for more complicated alicyclic amine and aromatic amine, the reaction is more difficult under the condition of no solvent due to steric hindrance of raw materials and existence of benzene ring P-pi conjugation, the reaction temperature is relatively higher, the amine is easy to lose and damage the amine-acid ratio, the overall reaction time is longer, and the sample performance is poorer.
CN109385204a discloses a water-soluble polyester imide insulating varnish and a preparation method thereof, which adopts a two-step feeding method, synthesizes water-soluble polyester imide resin with good hydrolytic stability through melt polycondensation reaction, but has less amine monomer content, so that the mechanical strength is insufficient; in addition, the temperature is increased and reduced for a plurality of times in the synthesis process, the process is complex, and the side reaction is promoted to occur due to the halfway feeding, so that the hue of the product is influenced; meanwhile, the reaction time is long and the energy consumption is high.
In view of the above, it is important to develop a method for synthesizing polyesterimide which is not limited to amine monomers and has a simple process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the polyester imide and the preparation method thereof, in the preparation method, the solvent is not added, the reaction monomer is fed by a one-step method, the types of amine monomers are not required to be limited, the process is simple, and the prepared polyester imide has good color phase, good high temperature resistance and excellent mechanical property.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a polyesterimide, the method comprising the steps of:
mixing acid monomers, alcohol monomers, anhydride monomers and amine monomers in a protective atmosphere, adjusting the molar ratio of the alcohol monomers to the acid monomers to be (2.5-4.0) 1 (wherein, 2.5-4.0 can be 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8 and the like), and reacting under the action of a catalyst to obtain the polyester imide;
no solvent is added in the preparation method.
In the preparation method of the polyester imide, under the condition of high alkyd ratio, an alcohol monomer is used as a synthetic raw material of polyester, and amine monomers can be well dispersed in a system; the preparation process does not add solvent, and the reaction monomer adopts a one-step feeding method, so that amidation can be performed at a lower temperature, amine loss is reduced, the types of amine monomers are not required to be limited, simple straight-chain aliphatic amines, more complex alicyclic amines and aromatic amines can be used, the raw materials have universality, and the application range of the product is widened; in addition, the invention has simple process, can directly adopt a polyester reaction kettle for production, and does not need to additionally modify equipment.
The polyester imide prepared by the method has good color phase and meets the application requirements; the glass transition temperature and the softening point are higher, and the high-temperature resistance is better; the mechanical properties of the prepared sample strip are excellent.
Preferably, the molar ratio of the acid anhydride-based monomer to the amine-based monomer is (0.5-1.05): 1, wherein 1-1.05 may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.01, 1.02, 1.03, 1.04, etc.
Preferably, the molar ratio of the anhydride-based monomer to the acid-based monomer is (1-2.5): 1, wherein 1-2.5 may be 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, etc.
Preferably, the acid monomer comprises a dibasic acid.
Preferably, the dibasic acid comprises any one or a combination of at least two of terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, dodecanedioic acid, adipic acid, or dimer acid, wherein typical but non-limiting combinations include: combinations of terephthalic acid and isophthalic acid, combinations of sebacic acid, azelaic acid and dodecanedioic acid, combinations of terephthalic acid, isophthalic acid, sebacic acid, azelaic acid and dodecanedioic acid, and the like.
Preferably, the alcohol monomer comprises a glycol.
Preferably, the glycol comprises any one or a combination of at least two of ethylene glycol, neopentyl glycol, 1, 2-propanediol, hexylene glycol, or 2-methyl-1, 3-propanediol, wherein typical but non-limiting combinations include: ethylene glycol, a combination of neopentyl glycol and 1, 2-propanediol, a combination of 1, 2-propanediol, hexanediol and 2-methyl-1, 3-propanediol, a combination of ethylene glycol, neopentyl glycol, 1, 2-propanediol, hexanediol and 2-methyl-1, 3-propanediol, and the like.
Preferably, the anhydride-based monomer comprises any one or a combination of at least two of pyromellitic anhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, bisphenol a-type diether dianhydride, or 3,3', 4' -biphenyl tetracarboxylic dianhydride, wherein typical but non-limiting combinations include: combinations of pyromellitic anhydride and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, combinations of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, bisphenol A-type diether dianhydride and 3,3', 4' -biphenyl tetracarboxylic dianhydride, combinations of pyromellitic anhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, bisphenol A-type diether dianhydride and 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the like.
Preferably, the catalyst comprises any one or a combination of at least two of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride, or stannous octoate, wherein typical but non-limiting combinations include: a combination of tetrabutyl titanate and tetraethyl titanate, a combination of tetraethyl titanate, dibutyltin oxide, tin chloride and stannous octoate, a combination of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride and stannous octoate, and the like.
Preferably, the amine monomer comprises any one or a combination of at least two of an aliphatic amine, an aromatic amine, or a cycloaliphatic amine, wherein typical but non-limiting combinations include: a combination of an aliphatic amine and an aromatic amine, a combination of an aromatic amine and an alicyclic amine, a combination of an aliphatic amine, an aromatic amine and an alicyclic amine, and the like.
In the present invention, the amine monomer is not particularly limited, and may be selected from aliphatic amine, aromatic amine or alicyclic amine, or a mixture of aliphatic amine, aromatic amine or alicyclic amine, thereby widening the range of application.
Preferably, the aliphatic amine comprises ethanolamine and/or hexamethylenediamine.
Preferably, the aromatic amine includes p-xylylenediamine and/or m-xylylenediamine.
Preferably, the cycloaliphatic amine comprises any one or a combination of at least two of bicyclo [2.2.1] heptane dimethylamine, bicyclo [2.2.1] heptane-2, 5-diamine, bicyclo [2.2.1] heptane-2, 6-diamine, or bicyclo [2.2.1] heptane-1, 3-diamine, wherein typical but non-limiting combinations include: a combination of bicyclo [2.2.1] heptane dimethylamine and bicyclo [2.2.1] heptane-2, 5-diamine, a combination of bicyclo [2.2.1] heptane-2, 5-diamine, bicyclo [2.2.1] heptane-2, 6-diamine and bicyclo [2.2.1] heptane-1, 3-diamine, a combination of bicyclo [2.2.1] heptane dimethylamine, bicyclo [2.2.1] heptane-2, 5-diamine, bicyclo [2.2.1] heptane-2, 6-diamine and bicyclo [2.2.1] heptane-1, 3-diamine, and the like.
Preferably, the reaction includes a first temperature-rising reaction, a second temperature-rising reaction, and a polycondensation reaction.
Preferably, the first and second warming reactions each independently have a warming rate of 0.1-1.5 ℃/min, e.g., 0.2 ℃/min, 0.4 ℃/min, 0.6 ℃/min, 0.8 ℃/min, 1.0 ℃/min, 1.2 ℃/min, 1.4 ℃/min, etc.
Preferably, the pressure of the first temperature elevating reaction and the second temperature elevating reaction is each independently 0.05 to 0.15MPa, for example, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa, 0.10MPa, 0.11MPa, 0.12MPa, 0.13MPa, 0.14MPa, etc., and more preferably 0.1MPa.
In the invention, in the first temperature rising reaction and the second temperature rising reaction, under the protective atmosphere (such as nitrogen), after materials are added, the pressure in the reaction kettle is pressurized and maintained to be constant to 0.05-0.15MPa, and the reaction is finished and the normal pressure is recovered.
Preferably, the temperature of the first temperature-rising reaction is 100 to 140 ℃, for example 110 ℃, 120 ℃, 130 ℃, 140 ℃, etc.
In the invention, under the condition of high alkyd ratio, the alcohol monomer is used as a synthetic raw material of polyester, the amine raw material can be uniformly dispersed, the amidation reaction can be carried out at a lower temperature in the first heating reaction, and the loss of the amine monomer is small.
Preferably, the temperature is raised to 100-140℃for the first time (e.g., 110 ℃, 120 ℃, 130 ℃, 140 ℃, etc.), and the reaction is maintained for a period of 0.5-1.5 hours, e.g., 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, etc.
Preferably, the temperature of the second warming reaction is 220-240 ℃, e.g., 222 ℃, 224 ℃, 226 ℃, 228 ℃, 230 ℃, 232 ℃, 234 ℃, 236 ℃, 238 ℃, etc.
Preferably, the first and second warming reactions are carried out with agitation at rates of 60-100r/min, e.g., 65r/min, 70r/min, 75r/min, 80r/min, 85r/min, 90r/min, 95r/min, etc., each independently.
Preferably, the temperature of the polycondensation reaction is 220 to 300 ℃, for example 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, etc.
Preferably, the polycondensation reaction is carried out with stirring at a rate of 40-100r/min, such as 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, etc.
Preferably, the vacuum degree of the polycondensation reaction is < 100Pa, for example 90Pa, 80Pa, 70Pa, etc.
Preferably, after the second temperature rising reaction, an auxiliary agent is added into the system.
Preferably, the auxiliary comprises trimethyl phosphate and/or triethyl phosphate.
The auxiliary agent is mainly used for reducing the side reaction of thermal oxidation in the polycondensation process.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Under the protective atmosphere, mixing the acid monomer, the alcohol monomer, the anhydride monomer and the amine monomer, and adjusting the mole ratio of the alcohol monomer to the acid monomer to be (2.5-4.0) 1, the mole ratio of the anhydride monomer to the amine monomer to be (0.5-1.05) 1, and the mole ratio of the anhydride monomer to the acid monomer to be (1-2.5) 1;
(2) Pressurizing and maintaining the pressure in the reaction kettle to be constant to 0.05-0.15MPa, stirring the system at the speed of 60-100r/min, heating to 100-140 ℃ according to the speed of 0.1-1.5 ℃/min, maintaining the reaction for 0.5-1.5h, and heating to 220-240 ℃ according to the speed of 0.1-1.5 ℃/min to complete the imide reaction and the esterification reaction;
(3) Stirring the system at the speed of 40-100r/min, and carrying out polycondensation reaction at 220-300 ℃ and the vacuum degree of less than 100Pa to obtain the polyester imide.
In a second aspect, the present invention provides a polyester imide prepared by the process of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation method of the polyesterimide, the types of amine monomers are not required to be limited, and simple straight-chain aliphatic amines, more complex alicyclic amines and aromatic amines can be used, so that the raw materials have universality and the application range of the product is enlarged;
(2) The invention has simple process, can directly adopt a polyester reaction kettle for production, and does not need to additionally modify equipment;
(3) The polyester imide prepared by the method has good color phase and meets the application requirements; the glass transition temperature and the softening point are higher, and the high-temperature resistance is better; the mechanical properties of the prepared sample strip are excellent.
(4) The polyester imide prepared by the method has the intrinsic viscosity of 0.51-0.68dL/g, the glass transition temperature of 117-178 ℃, the softening point of 209 ℃ or above, the hue of yellow, the tensile strength of 50.1MPa or above and the elongation at break of 9.6 percent or above.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 132.5g of terephthalic acid, 132.5g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 363g of pyromellitic anhydride and 256.7g of bicyclo [2.2.1] heptane dimethylamine into the reaction kettle, and simultaneously adding 0.15g of tetrabutyl titanate into the reaction kettle;
(2) Setting the stirring speed at 60r/min, controlling the temperature rise at 110 ℃, maintaining the pressure of a reaction system at 0.1MPa for 1h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature at 230 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.08g of trimethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 80r/min, the polycondensation temperature is controlled at 270 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 2
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 119.7g of terephthalic acid, 119.7g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 470.4g of pyromellitic anhydride and 268g of bicyclo [2.2.1] heptane-2, 6-diamine into the reaction kettle, and simultaneously adding 0.15g of dibutyl tin oxide into the reaction kettle;
(2) Setting the stirring speed at 80r/min, controlling the temperature rise at 140 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1.5h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature at 220 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.08g of triethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 60r/min, the polycondensation temperature is controlled at 260 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 3
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 106.4g of terephthalic acid, 106.4g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 557.5g of pyromellitic anhydride and 339.4g of p-xylylenediamine into the reaction kettle, and simultaneously adding 0.15g of stannous octoate into the reaction kettle;
(2) Setting the stirring speed to 100r/min, controlling the temperature rise in the first stage to 120 ℃, maintaining the pressure of a reaction system to 0.1MPa, maintaining the pressure for 1h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature to 230 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.05g of trimethyl phosphate and 0.05g of triethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 60r/min, the polycondensation temperature is controlled at 290 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 4
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 92.4g of terephthalic acid, 92.4g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 740.2g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 475.6g of 3,3' -methylenedianiline into the reaction kettle, and simultaneously adding 0.1g of tetrabutyl titanate and 0.1g of dibutyl tin oxide into the reaction kettle;
(2) Setting the stirring speed to 100r/min, controlling the temperature rise in the first stage to 140 ℃, maintaining the pressure of a reaction system to 0.1MPa, maintaining the pressure for 1.5h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature to 230 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.06g of trimethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 80r/min, the polycondensation temperature is controlled at 300 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 5
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, nitrogen is introduced to protect, 86.5g of terephthalic acid, 86.5g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 763.9g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 317.2g of ethanolamine are added into the reaction kettle, 0.04g of tetrabutyl titanate and 0.04g of stannous octoate are simultaneously added into the reaction kettle;
(2) Setting the stirring speed at 60r/min, controlling the temperature rise at the first stage at 100 ℃, maintaining the pressure of a reaction system at 0.1MPa for 0.5h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature at 240 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.04g of trimethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 40r/min, the polycondensation temperature is controlled at 300 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 6
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 83.5g of terephthalic acid, 83.5g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 518.2g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 202.7g of hexamethylenediamine into the reaction kettle, 0.05g of dibutyl tin oxide and 0.05g of stannous octoate into the reaction kettle at the same time;
(2) Setting the stirring speed to 100r/min, controlling the temperature rise in the first stage to 140 ℃, maintaining the pressure of a reaction system to 0.1MPa, maintaining the pressure for 1.5h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature to 240 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.08g of triethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 40r/min, the polycondensation temperature is controlled at 290 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 7
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 106g of terephthalic acid, 106g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 525g of pyromellitic anhydride, 475.6g of 3,3' -methylenedianiline into the reaction kettle, simultaneously adding 0.03g of tetrabutyl titanate, 0.03g of dibutyl tin oxide and 0.03g of stannous octoate into the reaction kettle,
(2) Setting the stirring speed at 80r/min, controlling the temperature rise in the first stage at 130 ℃, maintaining the pressure of a reaction system at 0.1MPa for 1h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature at 240 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.04g of triethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 60r/min, the polycondensation temperature is controlled at 280 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Example 8
This example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, and adding 95.4g of terephthalic acid, 95.4g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 590g of pyromellitic anhydride, 317.2g of ethanolamine into the reaction kettle, and simultaneously adding 0.02g of tetrabutyl titanate, 0.02g of dibutyl tin oxide and 0.02g of stannous octoate into the reaction kettle;
(2) Setting the stirring speed to 100r/min, controlling the temperature rise in the first stage to 140 ℃, maintaining the pressure of a reaction system to 0.1MPa, maintaining the pressure for 1.5h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature to 220 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.03g of trimethyl phosphate and 0.03g of triethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 40r/min, the polycondensation temperature is controlled at 270 ℃, the vacuum degree is less than 100Pa, and discharging when the reaction is carried out until the viscosity is 0.5-0.7dL/g, thereby obtaining the polyesterimide.
Comparative example 1
This comparative example provides a polyester imide prepared by a process comprising the steps of:
(1) In a 2L reaction kettle, introducing nitrogen for protection, adding 132.5g of terephthalic acid, 132.5g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol into the reaction kettle, and simultaneously adding 0.15g of stannous octoate into the reaction kettle;
(2) Setting the stirring speed to 100r/min, controlling the temperature rise in the first stage to 120 ℃, maintaining the pressure of a reaction system to 0.1MPa, maintaining the pressure for 1h, then continuously heating and esterifying at the speed of 0.5 ℃/min, maintaining the temperature to 230 ℃, and controlling the esterification rate to be more than 90%, namely, controlling the normal pressure;
(3) Under the protection of nitrogen, adding 0.05g of trimethyl phosphate and 0.05g of triethyl phosphate into a reaction kettle for polycondensation reaction, wherein the stirring speed is 60r/min, the polycondensation temperature is controlled at 270 ℃, the vacuum degree is less than 100Pa, when the reaction is carried out until the viscosity is 0.5-0.7dL/g, adding 700g of polyimide (purchased from Mitsui chemical under the brand PL 450A) under the protection of nitrogen, maintaining the temperature and stirring for 15min, and discharging to obtain the polyesterimide.
Comparative example 2
This comparative example was different from example 1 in that the mass of neopentyl glycol was adjusted to 90g, the molar ratio of the alcohol monomer to the acid monomer was 2.42, and the remainder was the same as in example 1.
Comparative example 3
This comparative example was different from example 1 in that the mass of neopentyl glycol was adjusted to 393.5g, the molar ratio of the alcohol monomer to the acid monomer was 4.25, and the remainder was the same as in example 1.
Physicochemical testing
The polyesterimides described in examples 1 to 8 and comparative examples 1 to 3 were tested as follows:
(1) Intrinsic viscosity: using an Ubbelohde viscometer, adopting o-chlorophenol as a solvent, and measuring at the temperature of 35 ℃, wherein the calculation formula of the intrinsic viscosity is as follows:
wherein: η: intrinsic viscosity, mL/g; ηsp: increasing specific viscosity; ηr: viscosity ratio; c: polymer concentration, mol/L; t: sample outflow time s; t0: blank run-out time, s.
(2) Glass transition temperature: the TA Q20 differential scanning calorimeter is adopted, and the flow rate under the nitrogen atmosphere is 20 mL.min during the test -1 5mg of the sample was placed on an alumina sample tray and tested as follows: sample at 10 ℃ min -1 Is heated from-30 ℃ to 180 ℃ and kept in this state for 2min to eliminate heat history, and the sample is heated at 10 ℃ for min -1 Is cooled to-30 ℃. Subsequently, the sample was subjected to a second temperature increase from-30℃for 10℃min -1 Is increased at a rate of temperature riseTo 150℃and glass transition temperature (T) g ) Obtained by secondary temperature rise.
(3) Softening point: the softening point of the sample was determined using GB/T4507-2014 asphalt softening point assay-the ring and ball method.
Performance testing
The polyesterimides described in examples 1 to 8 and comparative examples 1 to 3 were tested as follows:
mechanical properties: and (3) carrying out injection molding on the sample by adopting a miniature injection molding machine, adjusting parameters, preparing a spline of 80mm multiplied by 10mm multiplied by 4mm, and testing the tensile strength and the elongation at break of the spline according to the GB/T1040.1-2018 standard.
The test results are summarized in table 1.
TABLE 1
As can be seen from the data in Table 1, the polyester imide prepared by the method has an intrinsic viscosity of 0.51-0.68dL/g, a glass transition temperature of 117-178 ℃, a softening point of 209 ℃ or higher, a hue of yellow, a tensile strength of 50.1MPa or higher and an elongation at break of 9.6% or higher. The method does not need to limit the types of amine monomers, and the prepared polyester imide has good color phase and meets the application requirements; the glass transition temperature and the softening point are higher, and the high-temperature resistance is better; the mechanical properties of the prepared sample strip are excellent.
Analysis of comparative example 1 and example 1 shows that comparative example 1 has less performance than example 1, demonstrating that the polyester imide prepared by the method of the present invention has better performance.
As can be seen from the analysis of comparative examples 2 to 3 and example 1, comparative examples 2 to 3 are inferior in performance to example 1, and it is proved that the polyester imide formed in the present invention is better in performance by adjusting the molar ratio of the alcohol monomer to the acid monomer to 1 (2.5 to 4.0). The reason is that: the alcohol acid ratio is too small, so that the amine loss is caused, the softening point of the product is lower, and the tensile strength is slightly poor; the alkyd is too large in ratio, and ether bonds are easy to be produced as byproducts, so that the softening point and the tensile strength of the product are reduced.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (16)
1. A method for preparing a polyester imide, comprising the steps of:
mixing acid monomers, alcohol monomers, anhydride monomers and amine monomers in a protective atmosphere, adjusting the molar ratio of the alcohol monomers to the acid monomers to be (2.8-4.0): 1, and reacting under the action of a catalyst to obtain the polyester imide;
no solvent is added in the preparation method;
the molar ratio of the anhydride monomer to the amine monomer is (0.5-1.05): 1;
the molar ratio of the anhydride monomer to the acid monomer is (1-2.5): 1;
the acid monomer comprises any one or a combination of at least two of terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, dodecanedioic acid, adipic acid or dimer acid;
the alcohol monomer comprises any one or a combination of at least two of ethylene glycol, neopentyl glycol, 1, 2-propylene glycol, hexanediol or 2-methyl-1, 3-propylene glycol;
the anhydride monomer comprises any one or a combination of at least two of pyromellitic anhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, bisphenol A type diether dianhydride or 3,3', 4' -biphenyl tetracarboxylic dianhydride;
the amine monomer comprises any one or a combination of at least two of aliphatic amine, aromatic amine or alicyclic amine.
2. The method of claim 1, wherein the catalyst comprises any one or a combination of at least two of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride, or stannous octoate.
3. The production method according to claim 1, wherein the reaction comprises a first temperature-rising reaction, a second temperature-rising reaction, and a polycondensation reaction.
4. The method according to claim 3, wherein the first temperature-rising reaction and the second temperature-rising reaction each independently have a temperature-rising rate of 0.1 to 1.5 ℃/min.
5. The method according to claim 3, wherein the pressure of the first temperature-elevating reaction and the second temperature-elevating reaction is each independently 0.05 to 0.15MPa.
6. A process according to claim 3, wherein the first temperature-increasing reaction is carried out at a temperature of 100-140 ℃.
7. A process according to claim 3, wherein the temperature is raised to 100-140 ℃ for the first time and the reaction is maintained for 0.5-1.5 hours.
8. A method of preparing according to claim 3, wherein the temperature of the second elevated temperature reaction is 220-240 ℃.
9. The method according to claim 3, wherein the first temperature-raising reaction and the second temperature-raising reaction are carried out under stirring at a rate of 60 to 100r/min each independently.
10. A process according to claim 3, wherein the polycondensation reaction is carried out at a temperature of 220 to 300 ℃.
11. The process according to claim 3, wherein the polycondensation is carried out with stirring at a rate of 40 to 100r/min.
12. The process according to claim 3, wherein the polycondensation reaction has a vacuum of < 100Pa.
13. The method according to claim 3, further comprising adding an auxiliary agent to the system after the second temperature-raising reaction.
14. The method of claim 13, wherein the auxiliary comprises trimethyl phosphate and/or triethyl phosphate.
15. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Under the protective atmosphere, mixing the acid monomer, the alcohol monomer, the anhydride monomer and the amine monomer, and adjusting the mole ratio of the alcohol monomer to the acid monomer to be (2.8-4.0) 1, the mole ratio of the anhydride monomer to the amine monomer to be (0.5-1.05) 1, and the mole ratio of the anhydride monomer to the acid monomer to be (1-2.5) 1;
(2) Pressurizing and maintaining the system constant to 0.05-0.15MPa, stirring the system at the speed of 60-100r/min, heating to 100-140 ℃ according to the speed of 0.1-1.5 ℃/min, maintaining the reaction for 0.5-1.5h, and heating to 220-240 ℃ according to the speed of 0.1-1.5 ℃/min to complete the imide reaction and the esterification reaction;
(3) Stirring the system at the speed of 40-100r/min, and carrying out polycondensation reaction at 220-300 ℃ and the vacuum degree of less than 100Pa to obtain the polyester imide.
16. A polyesterimide prepared by the method of any one of claims 1 to 15.
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| CN202210457217.XA Active CN114656636B (en) | 2022-04-27 | 2022-04-27 | Polyester imide and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075179A (en) * | 1975-12-24 | 1978-02-21 | Essex International, Inc. | Polyesterimides and processes for preparing same |
| KR19980075997A (en) * | 1997-03-31 | 1998-11-16 | 허완수 | Organic Ti-P catalyst, preparation method thereof and preparation method of polyester imide using same |
| JP2010106140A (en) * | 2008-10-30 | 2010-05-13 | Sumitomo Electric Wintec Inc | Method for synthesizing ester imide resin |
| JP2012164424A (en) * | 2011-02-03 | 2012-08-30 | Sumitomo Electric Ind Ltd | Polyester imide resin based varnish for low dielectric constant coating film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012026438A1 (en) * | 2010-08-24 | 2012-03-01 | 住友電気工業株式会社 | Polyester imide resin based varnish for low-permittivity coating |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075179A (en) * | 1975-12-24 | 1978-02-21 | Essex International, Inc. | Polyesterimides and processes for preparing same |
| KR19980075997A (en) * | 1997-03-31 | 1998-11-16 | 허완수 | Organic Ti-P catalyst, preparation method thereof and preparation method of polyester imide using same |
| JP2010106140A (en) * | 2008-10-30 | 2010-05-13 | Sumitomo Electric Wintec Inc | Method for synthesizing ester imide resin |
| JP2012164424A (en) * | 2011-02-03 | 2012-08-30 | Sumitomo Electric Ind Ltd | Polyester imide resin based varnish for low dielectric constant coating film |
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