CN114656636A - Polyester imide and preparation method thereof - Google Patents
Polyester imide and preparation method thereof Download PDFInfo
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- CN114656636A CN114656636A CN202210457217.XA CN202210457217A CN114656636A CN 114656636 A CN114656636 A CN 114656636A CN 202210457217 A CN202210457217 A CN 202210457217A CN 114656636 A CN114656636 A CN 114656636A
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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 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- 239000000178 monomer Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 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 41
- 238000006068 polycondensation reaction Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- 238000005886 esterification reaction Methods 0.000 claims description 20
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 15
- -1 alicyclic amine Chemical class 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 150000004982 aromatic amines Chemical class 0.000 claims description 11
- 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
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 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
- 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 7
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 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
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 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 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-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
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 3
- 229940093476 ethylene glycol Drugs 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229940117969 neopentyl glycol Drugs 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 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
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 230000032050 esterification Effects 0.000 description 18
- 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
- 230000009477 glass transition Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 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
- 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 238000004458 analytical method Methods 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
- 238000007599 discharging Methods 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
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229940015975 1,2-hexanediol Drugs 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
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 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
- ABPUBUORTRHHDZ-UHFFFAOYSA-N [4-(aminomethyl)-3-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1CC2(CN)C(CN)CC1C2 ABPUBUORTRHHDZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 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
- JGVWEAITTSGNGJ-UHFFFAOYSA-N bicyclo[2.2.1]heptane;n-methylmethanamine Chemical compound CNC.C1CC2CCC1C2 JGVWEAITTSGNGJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000013098 chemical test 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
- 238000001816 cooling Methods 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
- 239000003063 flame retardant Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 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
- 238000000520 microinjection Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding 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
- 238000013031 physical testing Methods 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
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000000843 powder Substances 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 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
- 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: under the protection atmosphere, mixing an acid monomer, an alcohol monomer, an anhydride monomer and an amine monomer, adjusting the molar ratio of the alcohol monomer to the acid monomer to be (2.5-4.0):1, and reacting under the action of a catalyst to obtain the polyesterimide; the preparation method does not add solvent. In the preparation method, no solvent is added, the reaction monomer is fed by a one-step method, the type of the amine monomer is not particularly limited, the process is simple, and the prepared polyesterimide has good hue, good high temperature resistance and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of copolyester preparation, in particular to polyesterimide and a preparation method thereof.
Background
The polyester is a general term for a polymer obtained by polycondensation of a polyhydric alcohol and a polybasic acid. The application field of the polyester is greatly expanded due to the changeful 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, which is a generic name for polymers containing imide ring repeating units, has good thermal oxidation stability, unique electrical properties, high radiation resistance and solvent resistance, and high mechanical strength. The introduction of the polyimide structure into the polyester can improve the rigidity so as to achieve the purpose of improving the glass transition temperature of the polyester.
CN113845764A discloses a heat-resistant modified polylactic acid material and a preparation method thereof, wherein 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 material disclosed by the invention introduces polyimide and other additives 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 polyesterimide resin and a preparation method thereof by polycondensation reaction of a terephthalic acid di (3, 4-diformyl anhydride) phenyl ester monomer and a binary primary amine monomer. In the design of dianhydride, the electron affinity of the dianhydride is reduced, the formation of a charge transfer complex in a polyester imide molecule and between molecules is inhibited, and the transparency is improved. The obtained polyester imide resin has the glass transition temperature of 200-350 ℃, the light transmittance at 400nm of 70-90 percent, the water absorption of the film is less than 0.5 percent, and the polyester imide resin has good application prospect 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, primary amine monomers and acid anhydride are added to synthesize polyesteramide acid solution, and transparent polyesterimide resin is prepared by a thermal imidization method or a chemical imidization method.
CN109054008A discloses a polyester resin for an anti-yellowing HAA system powder coating, a preparation method and application thereof, wherein pyromellitic dianhydride, 1, 6-hexanediamine and the like are used as raw materials to synthesize polyester imide polyester; CN113563587A adopts trimellitic anhydride and ethanolamine as raw materials to synthesize polyesterimide. However, the processes in the two patents have great limitation on amine monomers, and only can be simpler aliphatic amine monomers such as hexamethylene diamine and ethanolamine, and for more complex alicyclic amine and aromatic amine, because of steric hindrance of raw materials and P-pi conjugation of benzene rings, the reaction is difficult under the condition of no solvent, the reaction temperature is relatively high, amine loss is easy to cause, the amine-acid ratio is damaged, the overall reaction time is long, and the sample performance is poor.
CN109385204A discloses a water-soluble polyester imide insulating varnish and a preparation method thereof, wherein a two-step feeding method is adopted, a melt polycondensation reaction is carried out to synthesize a water-soluble polyester imide resin with good hydrolytic stability, but the content of amine monomers is low, so that the mechanical strength is not enough; in addition, the temperature is raised and lowered for many times in the synthesis process, the process is complex, and the side reaction is promoted to occur due to midway feeding, so that the hue of the product is influenced; meanwhile, the reaction time is long, and the energy consumption is high.
In conclusion, it is important to develop a method for synthesizing polyesterimide which has no limitation on amine monomers and 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 order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing polyesterimide, comprising the steps of:
under the protection atmosphere, acid monomers, alcohol monomers, anhydride monomers and amine monomers are mixed, the molar ratio of the alcohol monomers to the acid monomers is adjusted 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 the mixture is reacted under the action of a catalyst to obtain the polyesterimide;
the preparation method does not add solvent.
In the preparation method of the polyesterimide, the alcohol monomer is used under the condition of high alcohol-acid ratio, and not only is used as a synthetic raw material of polyester, but also the amine monomer can be well dispersed in a system; the preparation process does not add a solvent, the reaction monomer is fed by a one-step method, so that amidation can be carried out at a lower temperature, the loss of amines is reduced, the types of amine monomers are not required to be particularly limited, simple straight-chain aliphatic amines can be used, more complex alicyclic amines and aromatic amines can be used, the raw materials have universality, and the application range of the product is expanded; in addition, the method has simple process, can directly adopt the polyester reaction kettle for production, and does not need to additionally transform equipment.
The polyester imide prepared by the method has good color phase and meets the application requirement; the glass transition temperature and the softening point are higher, and the better high temperature resistance is embodied; the prepared sample strip has excellent mechanical property.
Preferably, the molar ratio of the acid anhydride monomer to the amine monomer is (0.5-1.05):1, wherein 1-1.05 can 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 anhydride monomer to acid monomer is (1-2.5):1, where 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 of terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, dodecanedioic acid, adipic acid, or dimer acid, or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of terephthalic acid and isophthalic acid, 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 includes a diol.
Preferably, the glycol comprises any one of ethylene glycol, neopentyl glycol, 1, 2-propylene glycol, hexylene glycol, or 2-methyl-1, 3-propanediol, or a combination of at least two thereof, 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 includes any one of or a combination of at least two of pyromellitic anhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, bisphenol a type diether dianhydride, or 3,3',4,4' -biphenyltetracarboxylic dianhydride, wherein typical but non-limiting combinations include: a combination of pyromellitic anhydride and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, a combination of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, bisphenol a type diether dianhydride and 3,3',4,4' -biphenyltetracarboxylic dianhydride, a combination of pyromellitic anhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, bisphenol a type diether dianhydride and 3,3',4,4' -biphenyltetracarboxylic dianhydride, and the like.
Preferably, the catalyst comprises any one of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride, or stannous octoate, or a combination of at least two, wherein typical but non-limiting combinations include: combinations of tetrabutyl titanate and tetraethyl titanate, combinations of tetraethyl titanate, dibutyltin oxide, tin chloride, and stannous octoate, combinations of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride, and stannous octoate, and the like.
Preferably, the amine-based monomer comprises any one of an aliphatic amine, an aromatic amine, or a cycloaliphatic amine, or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of aliphatic amines and aromatic amines, combinations of aromatic amines and alicyclic amines, combinations of aliphatic amines, aromatic amines, and alicyclic amines, and the like.
In the invention, the amine monomer is not specifically limited, and can be selected from aliphatic amine, aromatic amine or alicyclic amine, or from a mixture of aliphatic amine, aromatic amine or alicyclic amine, so that the application range is widened.
Preferably, the aliphatic amine comprises ethanolamine and/or hexamethylenediamine.
Preferably, the aromatic amine comprises p-xylylenediamine and/or m-xylylenediamine.
Preferably, the cycloaliphatic amine comprises any one of, or a combination of at least two of, bicyclo [2.2.1] heptanediamine, 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, with typical but non-limiting combinations including: a combination of bicyclo [2.2.1] heptanediamine 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 temperature rise rates of the first temperature rise reaction and the second temperature rise reaction are each independently 0.1-1.5 ℃/min, such as 0.2 ℃/min, 0.4 ℃/min, 0.6 ℃/min, 0.8 ℃/min, 1.0 ℃/min, 1.2 ℃/min, 1.4 ℃/min, and the like.
Preferably, the pressure of the first temperature-raising reaction and the pressure of the second temperature-raising reaction are 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 0.1 MPa.
In the invention, in the processes of the first heating reaction and the second heating reaction, under the protective atmosphere (such as nitrogen), after materials are added, the pressure is increased and the pressure in the reaction kettle is kept constant to 0.05-0.15MPa, and the normal pressure is recovered after the reaction is finished.
Preferably, the temperature of the first temperature-raising reaction is 100-140 ℃, such as 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like.
In the invention, under the condition of high alcohol-acid ratio, the alcohol monomer is used as a synthetic raw material of polyester, and the amine raw material can be uniformly dispersed, and in the first heating reaction, the amidation reaction can be carried out at a lower temperature, so that the loss of the amine monomer is small.
Preferably, the temperature is raised to 140 ℃ for 100-.
Preferably, the temperature of the second temperature-raising reaction is 220-240 ℃, such as 222 ℃, 224 ℃, 226 ℃, 228 ℃, 230 ℃, 232 ℃, 234 ℃, 236 ℃, 238 ℃ and the like.
Preferably, the first temperature-raising reaction and the second temperature-raising reaction are carried out under stirring, and the stirring rate is 60 to 100r/min, such as 65r/min, 70r/min, 75r/min, 80r/min, 85r/min, 90r/min, 95r/min and the like, independently.
Preferably, the polycondensation reaction temperature is 220-.
Preferably, the polycondensation is carried out under stirring at a rate of from 40 to 100r/min, such as 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, and the like.
Preferably, the degree of vacuum 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 agent comprises trimethyl phosphate and/or triethyl phosphate.
The auxiliary agent of the invention 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) mixing an acid monomer, an alcohol monomer, an anhydride monomer and an amine monomer under a protective atmosphere, and adjusting the molar ratio of the alcohol monomer to the acid monomer to be (2.5-4.0):1, the molar ratio of the anhydride monomer to the amine monomer to be (0.5-1.05):1, and the molar 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 constant to 0.05-0.15MPa, stirring the system at the speed of 60-100r/min, heating to 100-140 ℃ at the speed of 0.1-1.5 ℃/min, maintaining the reaction for 0.5-1.5h, heating to 220-240 ℃ at the speed of 0.1-1.5 ℃/min, and completing the imide reaction and the esterification reaction;
(3) stirring the system at the speed of 40-100r/min, and carrying out polycondensation reaction at the temperature of 220-300 ℃ and the vacuum degree of less than 100Pa to obtain the polyesterimide.
In a second aspect, the present invention provides a polyesterimide prepared by the method 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 particularly limited, simple straight-chain aliphatic amines can be used, more complex alicyclic amines and aromatic amines can be used, the raw materials have universality, and the application range of the product is expanded;
(2) the method has simple process, can directly adopt the polyester reaction kettle for production, and does not need to additionally transform equipment;
(3) the polyester imide prepared by the method has good color phase and meets the application requirement; the glass transition temperature and the softening point are higher, and the better high temperature resistance is embodied; the prepared sample strips have excellent mechanical properties.
(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 more than 209 ℃, the color phase of yellow, the tensile strength of more than 50.1MPa and the elongation at break of more than 9.6 percent.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into 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 dianhydride 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 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 230 ℃, and controlling the esterification rate to be more than 90%, namely introducing normal pressure;
(3) under the protection of nitrogen, 0.08g of trimethyl phosphate is added into a reaction kettle for polycondensation reaction, the stirring speed is 80r/min, the polycondensation temperature is controlled at 270 ℃, the vacuum degree is less than 100Pa, and the polyester imide is obtained after the reaction is carried out until the viscosity is 0.5-0.7 dL/g.
Example 2
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into a 2L reaction kettle, introducing 119.7g of terephthalic acid, 119.7g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 470.4g of pyromellitic dianhydride, 268g of bicyclo [2.2.1] heptane-2, 6-diamine into the reaction kettle, and simultaneously adding 0.15g of dibutyltin 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, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 220 ℃, and controlling the esterification rate to be more than 90%, namely introducing normal pressure;
(3) under the protection of nitrogen, 0.08g of triethyl phosphate is added into a reaction kettle for polycondensation reaction, the stirring speed is 60r/min, the polycondensation temperature is controlled at 260 ℃, the vacuum degree is less than 100Pa, and the polyester imide is obtained after the reaction is carried out until the viscosity is 0.5-0.7 dL/g.
Example 3
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into a 2L reaction kettle 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 dianhydride 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 at 100r/min, controlling the temperature rise at 120 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 230 ℃, and controlling the esterification rate to be more than 90 percent, namely introducing normal pressure;
(3) under the protection of nitrogen, 0.05g of trimethyl phosphate and 0.05g of triethyl phosphate are added into a reaction kettle for polycondensation reaction, the stirring speed is 60r/min, the polycondensation temperature is controlled at 290 ℃, the vacuum degree is less than 100Pa, and the materials are discharged when the reaction reaches the viscosity of 0.5-0.7dL/g, so as to obtain the polyesterimide.
Example 4
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into 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',4,4' -biphenyltetracarboxylic dianhydride and 475.6g of 3,3' -methylene dianiline into the reaction kettle, and simultaneously adding 0.1g of tetrabutyl titanate and 0.1g of dibutyltin oxide into the reaction kettle;
(2) setting the stirring speed at 100r/min, controlling the temperature rise at 140 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1.5h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 230 ℃, and controlling the esterification rate to be more than 90%, namely introducing normal pressure;
(3) under the protection of nitrogen, 0.06g of trimethyl phosphate is added into a reaction kettle for polycondensation reaction, the stirring speed is 80r/min, the polycondensation temperature is controlled at 300 ℃, the vacuum degree is less than 100Pa, and the polyester imide is obtained after the reaction is carried out until the viscosity is 0.5-0.7 dL/g.
Example 5
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into a 2L reaction kettle, introducing nitrogen for protection, adding 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',4,4' -biphenyltetracarboxylic dianhydride and 317.2g of ethanolamine into the reaction kettle, and simultaneously adding 0.04g of tetrabutyl titanate and 0.04g of stannous octoate into the reaction kettle;
(2) setting the stirring speed at 60r/min, controlling the temperature rise at 100 ℃ in the first stage, maintaining the pressure of the reaction system at 0.1MPa for 0.5h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 240 ℃, and controlling the esterification rate to be more than 90 percent, namely introducing normal pressure;
(3) under the protection of nitrogen, adding 0.04g of trimethyl phosphate into a reaction kettle for polycondensation reaction, controlling the stirring speed to be 40r/min, the polycondensation temperature to be 300 ℃, controlling the vacuum degree to be less than 100Pa, discharging when the viscosity is 0.5-0.7dL/g, and obtaining the polyesterimide.
Example 6
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into 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',4,4' -biphenyltetracarboxylic dianhydride and 202.7g of hexamethylene diamine into the reaction kettle, and simultaneously adding 0.05g of dibutyltin oxide and 0.05g of stannous octoate into the reaction kettle;
(2) setting the stirring speed at 100r/min, controlling the temperature rise at 140 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1.5h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 240 ℃, and controlling the esterification rate to be more than 90 percent, namely introducing normal pressure;
(3) under the protection of nitrogen, 0.08g of triethyl phosphate is added into a reaction kettle for polycondensation reaction, the stirring speed is 40r/min, the polycondensation temperature is controlled at 290 ℃, the vacuum degree is less than 100Pa, and the polyester imide is obtained after the reaction is carried out until the viscosity is 0.5-0.7 dL/g.
Example 7
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into a 2L reaction kettle for protection, adding 106g of terephthalic acid, 106g of isophthalic acid, 186.2g of ethylene glycol, 104.1g of neopentyl glycol, 525g of pyromellitic dianhydride and 475.6g of 3,3' -methylene dianiline into the reaction kettle, simultaneously adding 0.03g of tetrabutyl titanate, 0.03g of dibutyltin oxide and 0.03g of stannous octoate into the reaction kettle,
(2) setting the stirring speed at 80r/min, controlling the temperature rise at 130 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 240 ℃, and controlling the esterification rate to be more than 90 percent, namely introducing normal pressure;
(3) under the protection of nitrogen, 0.04g of triethyl phosphate is added into a reaction kettle for polycondensation reaction, the stirring speed is 60r/min, the polycondensation temperature is controlled at 280 ℃, the vacuum degree is less than 100Pa, and the polyester imide is obtained after the reaction is carried out until the viscosity is 0.5-0.7 dL/g.
Example 8
This example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into a 2L reaction kettle for protection, 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 dibutyltin oxide and 0.02g of stannous octoate into the reaction kettle;
(2) setting the stirring speed at 100r/min, controlling the temperature rise at 140 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1.5h, continuously carrying out temperature rise esterification at the speed of 0.5 ℃/min, maintaining the temperature at 220 ℃, and controlling the esterification rate to be more than 90%, namely introducing normal pressure;
(3) under the protection of nitrogen, adding 0.03g of trimethyl phosphate and 0.03g of triethyl phosphate into a reaction kettle to carry out 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 is carried out when the reaction reaches the viscosity of 0.5-0.7dL/g, so as to obtain the polyesterimide.
Comparative example 1
This comparative example provides a polyesterimide prepared by a process comprising the steps of:
(1) introducing nitrogen into a 2L reaction kettle for protection, adding 132.5g of terephthalic acid, 132.5g of isophthalic acid, 186.2g of ethylene glycol and 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 at 100r/min, controlling the temperature rise at 120 ℃ in the first stage, maintaining the pressure of a reaction system at 0.1MPa for 1h, continuously heating for esterification at the speed of 0.5 ℃/min, maintaining the temperature at 230 ℃, and controlling the esterification rate to be more than 90 percent, namely introducing 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, under the protection of nitrogen, 700g of polyimide (purchased from Mitsui chemical, and the trade name is PL450A) is added, the temperature is maintained, the stirring is carried out for 15min, and the polyesterimide is obtained after discharging.
Comparative example 2
This comparative example is 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 adjusted to 2.42, and the rest was the same as example 1.
Comparative example 3
This comparative example is 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 adjusted to 4.25, and the rest is the same as example 1.
Physical and chemical testing
The polyesterimides described in examples 1-8 and comparative examples 1-3 were tested as follows:
(1) intrinsic viscosity: measured by using an Ubbelohde viscometer and adopting o-chlorophenol as a solvent at the temperature of 35 ℃, the calculation formula of the intrinsic viscosity is as follows:
in the formula: eta: intrinsic viscosity, mL/g; η sp: increasing the specific viscosity; η r: a viscosity ratio; c: polymer concentration, mol/L; t: sample flow time, s; t 0: blank efflux 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-1The 5mg sample was placed in an alumina sample pan and tested as follows: the sample temperature is 10 ℃ min-1Is heated from-30 ℃ to 180 ℃, and is kept for 2min in the state to eliminate the heat history, and the temperature of the sample is 10 ℃ min-1The cooling rate of (2) is cooled to-30 ℃. Subsequently, the sample was subjected to a second heating process from-30 ℃ at 10 ℃ min-1The temperature rise rate of (A) to 150 ℃ and the glass transition temperature (T) of the sampleg) Obtained by secondary heating.
(3) Softening point: the softening point of the sample is determined by a GB/T4507-2014 asphalt softening point determination method-ring and ball method.
Performance testing
The polyesterimides described in examples 1-8 and comparative examples 1-3 were tested as follows:
mechanical properties: and (3) carrying out injection molding on the sample by using a micro injection molding machine, adjusting parameters, preparing a sample strip with the thickness of 80mm multiplied by 10mm multiplied by 4mm, and testing the tensile strength and the elongation at break of the sample strip according to the GB/T1040.1-2018 standard.
The test results are summarized in table 1.
TABLE 1
As can be seen from the analysis of the data in Table 1, the polyesterimide 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 more than 209 ℃, the hue of yellow color, the tensile strength of more than 50.1MPa and the elongation at break of more than 9.6 percent. The method does not need to limit the types of amine monomers, and the prepared polyesterimide has good hue and meets the application requirements; the glass transition temperature and the softening point are higher, and the better high temperature resistance is embodied; the prepared sample strips have excellent mechanical properties.
As can be seen from the analysis of comparative example 1 and example 1, the performance of comparative example 1 is inferior to that of example 1, and the polyester imide prepared by the method of the present invention is proved to have 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 to example 1 in performance, and it is confirmed that the polyesterimide of the present invention is more excellent in performance by adjusting the molar ratio of the alcohol monomer to the acid monomer to (2.5 to 4.0): 1. The reason is that: when the alcohol-acid ratio is too low, amine loss is caused, so that the softening point of a product is lower, and the tensile strength is slightly poor; when the ratio of the alkyd is too large, ether bonds are easily formed as by-products, so that the softening point and the tensile strength of the product are reduced.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of polyesterimide is characterized by comprising the following steps:
under the protection atmosphere, mixing an acid monomer, an alcohol monomer, an anhydride monomer and an amine monomer, adjusting the molar ratio of the alcohol monomer to the acid monomer to be (2.5-4.0):1, and reacting under the action of a catalyst to obtain the polyesterimide;
no solvent is added in the preparation method.
2. The method according to claim 1, wherein the molar ratio of the acid anhydride monomer to the amine monomer is (0.5-1.05): 1.
3. The production method according to claim 1 or 2, wherein the molar ratio of the acid anhydride monomer to the acid monomer is (1-2.5): 1.
4. The production method according to any one of claims 1 to 3, wherein the acid-based monomer comprises a dibasic acid;
preferably, the dibasic acid comprises any one of terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, dodecanedioic acid, adipic acid, or dimer acid, or a combination of at least two thereof;
preferably, the alcohol monomer includes a diol;
preferably, the diol comprises any one of ethylene glycol, neopentyl glycol, 1, 2-propylene glycol, hexylene glycol or 2-methyl-1, 3-propylene glycol or a combination of at least two thereof;
preferably, the acid 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',4,4' -biphenyl tetracarboxylic dianhydride;
preferably, the catalyst comprises any one of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride or stannous octoate or a combination of at least two of the foregoing.
5. The method according to any one of claims 1 to 4, wherein the amine monomer comprises any one of an aliphatic amine, an aromatic amine, or an alicyclic amine, or a combination of at least two thereof.
6. The production method according to any one of claims 1 to 5, wherein the reaction includes a first temperature-raising reaction, a second temperature-raising reaction, and a polycondensation reaction;
preferably, the heating rates of the first heating reaction and the second heating reaction are respectively and independently 0.1-1.5 ℃/min;
preferably, the pressure of the first temperature-rising reaction and the pressure of the second temperature-rising reaction are respectively and independently 0.05-0.15 MPa;
preferably, the temperature of the first temperature-raising reaction is 100-140 ℃;
preferably, the temperature is raised to 100-140 ℃ for the first time, and the reaction time is maintained to be 0.5-1.5 h;
preferably, the temperature of the second temperature-raising reaction is 220-240 ℃;
preferably, the first temperature-rising reaction and the second temperature-rising reaction are carried out under stirring, and the stirring speed is 60-100r/min independently.
7. The method as claimed in claim 6, wherein the temperature of the polycondensation reaction is 220-300 ℃;
preferably, the polycondensation reaction is carried out under stirring, the stirring speed being 40-100 r/min;
preferably, the degree of vacuum of the polycondensation reaction is < 100 Pa.
8. The preparation method according to claim 6 or 7, characterized in that after the second temperature-rising reaction, an auxiliary agent is added into the system;
preferably, the auxiliary agent comprises trimethyl phosphate and/or triethyl phosphate.
9. The production method according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) mixing an acid monomer, an alcohol monomer, an anhydride monomer and an amine monomer under a protective atmosphere, and adjusting the molar ratio of the alcohol monomer to the acid monomer to be (2.5-4.0):1, the molar ratio of the anhydride monomer to the amine monomer to be (0.5-1.05):1, and the molar 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 140 ℃ at the speed of 0.1-1.5 ℃/min, maintaining the reaction for 0.5-1.5h, heating to 240 ℃ at the speed of 0.1-1.5 ℃/min, and completing the imide reaction and the esterification reaction;
(3) stirring the system at the speed of 40-100r/min, and carrying out polycondensation reaction at the temperature of 220-300 ℃ and the vacuum degree of less than 100Pa to obtain the polyesterimide.
10. A polyesterimide, wherein said polyesterimide is prepared by the process of any of claims 1 to 9.
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| US20130153262A1 (en) * | 2010-08-24 | 2013-06-20 | Sumitomo Electric Industries, Ltd. | Polyester imide resin based varnish for low-permittivity coating film |
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| 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 |
| US20130153262A1 (en) * | 2010-08-24 | 2013-06-20 | Sumitomo Electric Industries, Ltd. | Polyester imide resin based varnish for low-permittivity coating film |
| 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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