CN101659721A - Method for forming highly branched polymer and formula - Google Patents
Method for forming highly branched polymer and formula Download PDFInfo
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- CN101659721A CN101659721A CN200810146910A CN200810146910A CN101659721A CN 101659721 A CN101659721 A CN 101659721A CN 200810146910 A CN200810146910 A CN 200810146910A CN 200810146910 A CN200810146910 A CN 200810146910A CN 101659721 A CN101659721 A CN 101659721A
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- bismaleimide
- hyperbranched polymer
- bta
- monomer
- dmf
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 title description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 105
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 51
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims abstract description 26
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012670 alkaline solution Substances 0.000 claims abstract 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 172
- 239000000463 material Substances 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- -1 coatings Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- SEBFKVKRAREXAK-UHFFFAOYSA-N 1-[(2,5-dioxopyrrol-1-yl)disulfanyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1SSN1C(=O)C=CC1=O SEBFKVKRAREXAK-UHFFFAOYSA-N 0.000 claims description 2
- OIZOXAITXCKQIN-UHFFFAOYSA-N 3-[4-[[4-(2,5-dioxopyrrol-3-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC(CC=3C=CC(=CC=3)C=3C(NC(=O)C=3)=O)=CC=2)=C1 OIZOXAITXCKQIN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 4
- 238000009472 formulation Methods 0.000 claims 4
- ZLMARZJGISXEOG-UHFFFAOYSA-N 1-[(2,5-dioxopyrrol-1-yl)methyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CN1C(=O)C=CC1=O ZLMARZJGISXEOG-UHFFFAOYSA-N 0.000 claims 2
- FJKKJQRXSPFNPM-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(N2C(C=CC2=O)=O)C=C1N1C(=O)C=CC1=O FJKKJQRXSPFNPM-UHFFFAOYSA-N 0.000 claims 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims 2
- OJCNHTCSMRAQJZ-UHFFFAOYSA-N 1-(2,5-dioxopyrrol-1-yl)sulfanylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1SN1C(=O)C=CC1=O OJCNHTCSMRAQJZ-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 239000002000 Electrolyte additive Substances 0.000 claims 1
- 239000012620 biological material Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 239000005518 polymer electrolyte Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 98
- 238000006243 chemical reaction Methods 0.000 description 87
- 239000000243 solution Substances 0.000 description 58
- 238000003756 stirring Methods 0.000 description 48
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 22
- 239000000376 reactant Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 19
- 230000009471 action Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000005352 clarification Methods 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 230000002950 deficient Effects 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 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 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 101100058550 Mus musculus Bmi1 gene Proteins 0.000 description 4
- 239000003637 basic solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 description 2
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- NAKOELLGRBLZOF-UHFFFAOYSA-N phenoxybenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NAKOELLGRBLZOF-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229940032159 propylene carbonate Drugs 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ZLLQQGWNYVJPAS-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound C1(CCCCC1)N1C(C=CC1=O)=O.C1(CCCCC1)N1C(C=CC1=O)=O ZLLQQGWNYVJPAS-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a method for forming a hyperbranched polymer and a formula thereof, which comprises the steps of adding bismaleimide and barbituric acid into a Bronsted alkaline solution, and reacting at the temperature of 20-100 ℃ to form the hyperbranched polymer. The above formula can further add mono-maleimide monomer and/or polymaleimide monomer to adjust the properties of the hyperbranched polymer.
Description
Technical field
The present invention relates to a kind of hyper branched polymer (hyper branched polymers), more relates to prescription of hyper branched polymer and forming method thereof.
Background technology
Generally speaking, three-D branch-shape polymer (dendritech polymer) is for having the polymkeric substance of high branching or dendritic structure, its solvability can be higher than the linear polymer of analog structure, its reason is the structure of polymkeric substance branching, cause packing of molecules loose, free volume is also bigger, and reduces tangling between the molecular chain.Polymkeric substance can be divided into two kinds of forms according to the structure of its branching:
(1) tree-shaped polymkeric substance (dendrimers): synthetic method can be divided for by the in layer synthetic outward expansion in core, is called Divergent approaches; Other method is an earlier synthetic branch part, and then symmetric receiving on the core position, is called Convergent approaches.The tree-shaped polymer architecture of this kind is symmetry and intimate circular quite, and (degree of branch is 1 DB) to its degree of branching of the tree-shaped polymkeric substance of ideal; And because its specific molecule structure makes it have unique physics and chemical property, such as good solubleness, low viscosity, amorphousness and a large amount of terminal functional groups etc.Yet in building-up process, often must add protecting group, go protecting group, and the complex steps of purifying etc. repeatedly, make synthetic difficulty relatively, and productive rate is also low excessively, cost of manufacture is difficult to effectively reduce, therefore can't scale operation.
(2) hyper branched polymer (hyper branched polymers): normally with AB
xThe monomer of form (wherein x is 2 or bigger), a step aggregates into high molecular weight polymers, so compared to tree-shaped polymkeric substance, the molecular structure of hyper branched polymer is more irregular, degree of branching (DB) is about 0.5, formula 1 is AB
2The structural representation of the synthetic hyper branched polymer of type monomer.In the formula 1, A, B are reactive functional group, and ab is that A and B carry out the segment that condensation reaction produces.Contain a large amount of terminal functional groups in the structure of hyper branched polymer, can be used to material is carried out modification, character such as the many materializations of gain material, some unique character that also have tree-shaped polymkeric substance (dendrimers), and owing to can simplify suitable synthesis step, molecular structure controlled preferable again, more tree-shaped polymkeric substance is more easy in the preparation, and also there is sizable lifting the solvability aspect of polymkeric substance, therefore quite be subjected to academic research and development industry and industry to use the favor on boundary, the research and development of numerous and confused actively input, its development potentiality is very abundant.
(Tsueyuki Sato) that the Japan Tokushima honorary professor of university helps rattan perseverance in the function material, and vol.26, No.8,44-52 (2006) is delivered " Nanosize Hyperbranched Polymers " mention the high polymkeric substance that props up usually with AB in the paper
2The monomer polymerization of type forms, and that is to say to utilize the synthesis mode of one kettle way (one-pot) to make synthetic hyper branched polymer, and this technology is called IFIRP (initiator-fregmentincorporation radical polymerization).Yet IFIRP is owing to need to use the initiator (initiator) of combining and the combo architectures of monomer (monomer) (to be called trigger monomer, inimer) carry out the synthetic of hyper branched polymer, the kind of its utilization and pattern all are subjected to suitable restriction, and it does not have effectively controlled to molecular structure and molecular weight yet, and the productive rate of the hyper branched polymer that is synthesized is not high yet, and the scope field of application will be limited to.If want to promote effectively the building-up reactions of hyper branched polymer and controlled, then must add and kind chain mobile agent and coincidence inhibitor with combining equals in the reaction of trigger monomer, this rule more increases preparation technology's step and complexity.
Summary of the invention
The object of the present invention is to provide a kind of formation method of hyper branched polymer, comprise with bismaleimides and malonylurea add cloth bear this special basic solution (
Base solution) in, under 20-100 ℃, reacts, form hyper branched polymer.
The present invention also aims to provide a kind of prescription of hyper branched polymer, comprise bismaleimides; Malonylurea; And cloth is born this special basic solution.
The present invention discloses a kind of synthetic method of hyper branched polymer of novelty and constituent thereof, bear in this special basic solution in cloth via malonylurea for a kind of, mixture with bismaleimides, under in 20 to 100 ℃, or even the hyper branched polymer (hyper branched polymers) of room temperature institute polymerization formation.Malonylurea of the present invention, itself and its reaction intermediates are when carrying out response procedures, promptly with monomer (monomer), initiator (initiator), chain propagation agent (propagator), stopper (inhibitor) and chain terminator multiple identities such as (terminator), and interactive between various status and pin down with transferance in polymerization process, can do variation according to the reaction operating environment, such as reactant concn and ratio, solvent effect, the temperature and time gradient, and the control of atmosphere etc., carry out from causing (self-initiating), from chainpropagation (self-propagating), and autotermination reaction mechanisms such as (self-terminating).Snappiness Molecular Structure Design and the good polymerization reaction engineering means of control by hyper branched polymer, the composition that can prepare the hyper branched polymer (multifunctional hyper branched polymer) of providing the multi-functional type makes the aspect of its utilization can be more broad.
The structure of above-mentioned malonylurea series is suc as formula 2:
R wherein
1, R
2Independent separately, comprising:
-H，-CH
3，
-CH(CH
3)
2，-CH
2CH(CH
3)
2，-CH
2CH
2CH(CH
3)
2
Or
The structure of malonylurea series is special, substituted radical displacement that can be different is at the structural hydrogen of ketone group, form enantiomer (enantiomers), the molecule that its structure energy and mirror image overlap is called achiral molecule (achiral molecules), as malonylurea (barbiture acid), chiral centre (chiral center) is arranged and can't then be chiral molecules (chiral molecules) with the mirror image molecule overlaps.Contain many nitrogen, oxygen and hydrogen in the structure of malonylurea, be easy to form intermolecular hydrogen bond configuration, building structure is molecular clustering (cluster), and itself is not only reaction terminating agent, the person's that has the radical-scavenging simultaneously function.Malonylurea is not by providing free radical with reaction terminating, grab the free radical that causes successive reaction but catch, it is subtracted fall or lose reactive activity, so as to reaching the purpose of reaction terminating, and then prevent the coacervation that produced because of excessive polymerization, with molecular structure and the molecular weight thereof of stablizing hyper branched polymer.In an embodiment of the present invention, the mol ratio of bismaleimides and malonylurea is approximately between 40: 1 to 0.9: 1.
It should be noted that the solvent that the present invention adopts is solvent such as N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyrrolidone, N-dodecyl pyrrolidone or the above-mentioned combination that cloth is born this special alkalescence.Above-mentioned basic solvent can add other cloth and bear this special neutral solvent such as γ-butyl lactone, in order to control solvent pH-value.Compare with the polymeric reaction temperature (＞100 ℃) of general using malonylurea and bismaleimides, temperature of reaction of the present invention is between 20 ℃ to 100 ℃, and even need not heat (room temperature reaction) can react.Via experiment showed, that the present invention can be that cloth bears this special basic solution in the key that low temperature forms down hyper branched polymer.
In an embodiment of the present invention, except bismaleimides, in addition can with the single maleimide monomer and/or the More Malay dant monomer of its copolymerization, in order to adjust the rerum natura of high branched copolymers.Above-mentioned single maleimide monomer is to comprise N-phenylmaleimide (N-phenyl-maleimide, be called for short PMI), N-cyclohexyl maleimide (N-cyclohexyl-maleimide) or other suitable single maleimide, its structure is as shown in Equation 3.And the More Malay dant monomer comprises three (4-phenyl maleimide base) amine (Tris (4-phenymaleimide) amine), polyphenyl methyl maleimide (polyphenylmethane maleimide) or other suitable More Malay imide, and its structure is suc as formula shown in the 4-6.In an embodiment of the present invention, bismaleimides: the mol ratio of More Malay imide and/or single maleimide is approximately between 99: 1 to 1: 1.
(formula 3) (formula 4) (formula 5)
(formula 6)
In formula 3-5, R
3Be to select from phenyl, C
1-8Alkyl or C
5-8Cycloalkyl.In formula 6, n is 5 to 1000 integer.
Above-mentioned bismaleimides can be formula 7 or formula 8:
R wherein
4Be select from-R-,-R-NH
2-R-,-C (O)-,-R-C (O)-R-,-R-C (O)-,-O-,-O-O-,-S-,-S-S-,-S (O)-,-R-S (O)-R-,-SO
2-,-(C
6H
5)-,-R-(C
6H
5)-R-or-R-(C
6H
5)-O-,-(C
6H
5)-(C
6H
5)-,-R-(C
6H
5)-(C
6H
5)-R-or-R-(C
6H
5)-(C
6H
5)-O-; Above-mentioned R is C
1-8Alkyl, above-mentioned (C
6H
5) be phenyl, and above-mentioned (C
6H
5)-(C
6H
5) be xenyl; Y be select from-R-,-C (O)-,-O-,-O-O-,-S-,-S-S-,-S (O)-or-SO
2-; And X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8Independent separately, be to select from halogen, hydrogen, C
1-8Alkyl, C
1-8Cycloalkyl or C
1-8Silylation.
In an embodiment of the present invention, bismaleimides can be N, N '-bismaleimides-4; 4 '-phenylbenzene is for methane; 1; 1 '-(methylene-bis-4,1-phenylene) bismaleimides; N, N '-(1; 1 '-phenylbenzene-4; 4 '-dimethylene) bismaleimides; N, N '-(4-methyl isophthalic acid, 3-phenylene) bismaleimides; 1; 1 '-(3; 3 '-dimethyl-1,1 '-phenylbenzene-4,4 '-dimethylene) bismaleimides; N; N '-ethanoyl dimaleimide; N; N '-(1, the 2-phenylene) dimaleimide; N, N '-(1; the 3-phenylene) dimaleimide; N; N '-sulfenyl bismaleimides; N, N '-dithiobis maleimide; N, N '-bismaleimides ketone; N; N '-methylene-bis maleimide; dimaleoyl imino ether; 1; 2-dimaleoyl imino-1; N, N '-4; 4 '-phenyl ether-bismaleimides; or 4,4 '-bismaleimides-sulfobenzide.
It should be noted that malonylurea of the present invention is that segmentation adds in the reaction, be not to be about to all malonylurea and other reactants at the beginning to put one pot altogether.This kind practice cooperates parameter controls such as concentration rate, temperature of reaction, action time and ambiance can change and control degree of branching, the polymerization degree and the structural configuration of high branched-chain polymer.
The invention has the advantages that: the few compound of the highly purified multifunctional type bismaleimides of this kind has a high branched structure (hyper branch architecture) and many pairs of key reactive functional group group of planes (multi double bondreactive functional groups), can promote solubleness and seizure (trap) ability to solvent, and compatible and reactive with resin, the processing characteristics excellence, do not need additionally to carry out the modification operation of resin, and can improve the fragility of material yet because of the solubleness of solvent with to the problem of the compatibility of resin; Can be that action-reaction such as resin (acrylate) or other resin material form molecular level matrix material (molecular composites) with Resins, epoxy (epoxies), polyimide (polyimides), acryl easily more, can improve thermostability, pliability, the solvent moisture retention of integral material effectively, and gain other physical properties, electrical properties, chemical property and mechanical properties etc., have advantages such as simplifying preparation technology and reduction cost of manufacture simultaneously concurrently.Hyper branched polymer of the present invention can solid or solution or colloidal state or liquid crystal kenel, is applied to stage construction fields such as electronic packaging, indicating meter, solar cell, transmitter, photoelectric material, functional type material, additive agent electrolyte, liquid state/colloidal state/solid state polyelectrolyte, barrier film, ion/proton exchange membrane, plate material, catalyst material, functional type matrix material, functional paint and biotechnology apply materials.
Description of drawings
Fig. 1 is the hydrogen spectrum of BTA;
Fig. 2 is the hydrogen spectrum of BMI;
Fig. 3 is in the embodiment of the invention, the hydrogen spectrum of STOBA (1: 1);
Fig. 4 is in the embodiment of the invention, the hydrogen spectrum of STOBA (2: 1);
Fig. 5 is the DSC collection of illustrative plates of the embodiment of the invention 1;
Fig. 6 is the DSC collection of illustrative plates of the embodiment of the invention 4;
Fig. 7 is the DSC collection of illustrative plates of the embodiment of the invention 2;
Fig. 8 is the gpc chromatogram of BMI in DMF solution;
Fig. 9 is the gpc chromatogram of the embodiment of the invention 6; And
Figure 10 is the gpc chromatogram of the embodiment of the invention 7.
Embodiment
For above and other objects of the present invention, feature and advantage can be become apparent, several embodiment cited below particularly are described in detail below:
The material source that the embodiment of the invention adopted is as follows:
The bismaleimide amine monomers is available from Homide company, its NMR (Nuclear Magnetic Resonance) spectrum as shown in Figure 1, it is as follows to have a chemical shift: 1H NMR (500MHz, d
6-DMSO): δ 3.997 (m, 2H), 7.124 (s, 4H), 7.211-7.232 (d, 4H), 7.320-7.341 (d, 4H).
Malonylurea is available from Alfa Aesar company, its NMR (Nuclear Magnetic Resonance) spectrum as shown in Figure 2, it is as follows to have a chemical shift: 1H NMR (500MHz, d
6-DMSO): δ 3.352 (m, 2H), 11.103 (m, 2H).
γ-Ding Suan lactone (γ-Butyrolactone, abbreviation GBL), propylene carbonate (PropyleneCarbonate, PC), methyl-2-pyrrolidone (N-methyl pyrollidone, NMP), dimethyl formamide (Dimethylformamide, DMF), N,N-DIMETHYLACETAMIDE, pyrrolidone, N-dodecyl pyrrolidone equal solvent be available from the Tokyo chemical industry (Tokyo Chemical Industry Co., LTD.).
Single maleimide (N-phenyl-maleimide, PMI) then available from the Tokyo chemical industry (Tokyo ChemicalIndustry Co., LTD.).
Dihydroxyphenyl propane phenyl ether bismaleimides (Bisphenol A diphenyl ether bismaleimide) and polyphenyl methyl maleimide (Polyphenylmethane maleimide) then available from big and change into industry (DaiwakaseiIndustry Co., Ltd).The experiment materials that respond all need dewater earlier or dewatering operation, with the side effect reaction of avoiding moisture to produce.Bismaleimides is monomeric to dewater or dewatering operation is to put into vacuum drying oven, is warming up to 70 ℃ and vacuumize and remove the remaining and absorption moisture on it.Active easy greatly reaction of malonylurea, also comparatively responsive to temperature, remove remnants and the moisture that adsorbs on it so only at room temperature vacuumize.In addition, solvent partly also must add dewatering agent or molecular sieve, is contained in moisture in it in order to removal.
Comparative example 1:BMI-GBL-20wt%-90 ℃-6H
BMI-GBL-20wt%-90 ℃-6H was meant that reactant only has BMI, and solid content is about 20wt%, and solvent is the GBL system, 90 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(4,4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle to get about 20 bismaleimidess that restrain.Add about 80 gram GBL solvents, and be heated to 90 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the GBL solvent fully.Continue to stir after 6 hours, leave standstill to room temperature.From gpc chromatogram, can know by inference and reactionless generation.
Comparative example 2:BMI-NMP-20wt%-40 ℃-6H
BMI-NMP-20wt%-40 ℃-6H was meant that reactant only has BMI, and solid content is about 20wt%, and solvent is the NMP system, 40 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(4,4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle to get about 20 bismaleimidess that restrain.Add about 80 gram nmp solvents, and be heated to 40 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the nmp solvent fully.Continue to stir after 6 hours, leave standstill to room temperature.From gpc chromatogram, can know by inference and reactionless generation.
Comparative example 3:BMI-NMP-20wt%-70 ℃-6H
BMI-NMP-20wt%-70 ℃-6H was meant that reactant only has BMI, and solid content is about 20wt%, and solvent is the NMP system, 70 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(4,4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle to get about 20 bismaleimidess that restrain.Add about 80 gram nmp solvents, and be heated to 70 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the nmp solvent fully.Continue to stir after 6 hours, leave standstill to room temperature.From gpc chromatogram, can know by inference and reactionless generation.
Comparative example 4:BTA-GBL-1wt%-40 ℃-6H
BTA-GBL-1wt%-40 ℃-6H was meant that reactant only has BTA, and solid content is about 1wt%, and solvent is the GBL system, 40 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(Barbituric Acid BTA) inserts in the 250ml round bottom three-necked bottle to get about 0.5 malonylurea that restrains.Add about 50 gram GBL solvents, and be heated to 40 ℃ and fully stir after 6 hours, leave standstill, adularescent BTA powder precipitation still under the bottle to room temperature BTA and can't dissolving fully as a result.
Comparative example 5:BTA-NMP-1wt%-70 ℃-6H
BTA-NMP-1wt%-70 ℃-6H was meant that reactant only has BTA, and solid content is about 1wt%, and solvent is the NMP system, 70 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(Barbituric Acid BTA) inserts in the 250ml round bottom three-necked bottle to get about 0.5 malonylurea that restrains.Add about 50 gram nmp solvents, and be heated to 70 ℃ of abundant stirrings after 6 hours, leave standstill to room temperature, BTA can dissolve fully, and solution is yellowish-orange.
Comparative example 6:BTA-DMF-1wt%-40 ℃-6H
BTA-DMF-10wt%-40 ℃-6H was meant that reactant only has BTA, and solid content is about 1wt%, and solvent is the DMF system, 40 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(Barbituric Acid BTA) inserts in the 250ml round bottom three-necked bottle to get about 0.5 malonylurea that restrains.Add about 50 gram DMF solvents, and be heated to 40 ℃ of abundant stirrings after 6 hours, leave standstill to room temperature, BTA can dissolve fully, and solution is yellowish-orange.
Embodiment 1:STOBA (1: 1)-GBL-20wt%-90 ℃-6H
STOBA (self-terminated oligomer with hyper-branched architecture) refers to the high branching oligomer of terminate self.STOBA (1: 1)-GBL-20wt%-90 ℃-6H was meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 20wt.%, and solvent is the GBL system, 90 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 18 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram GBL solvents, and be heated to 90 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the GBL solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram GBL solvents, and fully stir, BTA can be dispersed in the GBL solvent with magnetite.
(3) BTA-GBL milky solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 90 ℃ the BMI-GBL solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that the BTA-GBL milky solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (1: 1)-GBL-20wt%-90 ℃-6H solution, presents pale brown look clarification.
Embodiment 2:STOBA (1: 1)-NMP-20wt%-70 ℃-6H
STOBA (1: 1)-NMP-20wt%-70 ℃-6H was meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 20wt.%, and solvent is the NMP system, 70 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 18 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram nmp solvents, and be heated to 70 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the nmp solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram nmp solvents, and fully stir, BTA can be dispersed in the nmp solvent with magnetite.
(3) BTA-NMP milky solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 70 ℃ the BMI-NMP solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that the BTA-NMP milky solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (1: 1)-NMP-20wt%-70 ℃-6H solution, presents brown clarification.
Embodiment 3:STOBA (1: 1)-DMF-20wt%-40 ℃-20H
STOBA (1: 1)-NMP-20wt%-40 ℃-6H was meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 20wt.%, and solvent is the DMF system, 40 ℃ of reactions 20 hours; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 18 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram DMF solvents, and be heated to 40 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the DMF solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram DMF solvents, and fully stir, BTA can be dispersed in the DMF solvent with magnetite.
(3) BTA-DMF milky solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 40 ℃ the BMI-DMF solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that the BTA-DMF milky solution has added fully after, continuous action reaction is 18 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (1: 1)-DMF-20wt%-40 ℃-20H solution, presents the yellowish brown clarification.
Embodiment 4:STOBA (1: 1)-NMP/GBL-20wt%-70 ℃-6H
STOBA (1: 1)-NMP/GBL-20wt%-70 ℃-6H is meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 20wt.%, and solvent is a NMP/GBL system (1: 1w/w), reacted 6 hours at 70 ℃; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 18 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram NMP/GBL solvents, and be heated to 70 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the NMP-GBL solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram NMP/GBL solvents, and fully stir, BTA can be dispersed in the NMP/GBL solvent with magnetite.
(3) BTA-NMP/GBL solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 70 ℃ the BMI-NMP/GBL solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that BTA-NMP/GBL solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (1: 1)-NMP/GBL-20wt%-70 ℃-6H solution, presents brown clarification.
Embodiment 5:STOBA (1: 1)-DMF/GBL-20wt%-85 ℃-6H
STOBA (1: 1)-DMF/GBL-20wt%-85 ℃-6H is meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 20wt.%, and solvent is a DMF/GBL system (1: 1w/w), reacted 6 hours at 85 ℃; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 18 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram DMF/GBL solvents, and be heated to 85 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the DMF-GBL solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram DMF/GBL solvents, and fully stir, BTA can be dispersed in the DMF/GBL solvent with magnetite.
(3) BTA-DMF/GBL solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 85 ℃ the BMI-DMF/GBL solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that BTA-DMF/GBL solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (1: 1)-DMF/GBL-20wt%-85 ℃-6H solution, presents brown clarification.
Embodiment 6:STOBA (1: 1)-DMF-10wt%-90 ℃-6H
STOBA (1: 1)-DMF-10wt%-90 ℃-6H was meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 10wt.%, and solvent is the DMF system, 90 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 9 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram DMF solvents, and be heated to 90 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the DMF solvent fully.
(2) claim about 3.5 gram BTA powder, add in about 40 gram DMF solvents, and fully stir, BTA can be dispersed in the DMF solvent with magnetite.
(3) BTA-DMF milky solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 90 ℃ the BMI-DMF solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that the BTA-DMF milky solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (1: 1)-DMF-10wt%-90 ℃-6H solution, presents the yellowish brown clarification.Gel permeation chromatography instrument (Gel PermeationChromatography with the DMF solution of BMI, abbreviation GPC) collection of illustrative plates (Fig. 8) is compared, the Rf value of the product S TOBA of embodiment 6 is about 26.6 minutes, and does not have the signal of BMI and BTA, shows that BMI and BTA fully react.In addition, the product S TOBA of embodiment 6 is approximate unimodal, and its purity is also quite high.
Embodiment 7:STOBA (2: 1)-NMP/GBL-20wt%-70 ℃-6H
STOBA (2: 1)-NMP/GBL-20wt%-70 ℃-6H is meant that the mol ratio of reactant B MI and BTA is 2: 1, and solid content is about 20wt.%, and solvent is a NMP/GBL system (1: 1w/w), reacted 6 hours at 70 ℃; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 21 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram NMP/GBL solvents, and be heated to 70 ℃ of fully stirrings, the bismaleimide amine monomers can be dissolved in the NMP-GBL solvent fully.
(2) claim about 4 gram BTA powder, add in about 40 gram NMP/GBL solvents, and fully stir, BTA can be dispersed in the NMP/GBL solvent with magnetite.
(3) BTA-NMP/GBL solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 70 ℃ the BMI-NMP/GBL solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that BTA-NMP/GBL solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is STOBA (2: 1)-NMP/GBL-20wt%-70 ℃-6H solution, presents brown clarification.
In embodiment 6, except reacting 4 hours product, more increase reaction times to 8 hour and 12 hours, and measure product such as Figure 10 with GPC.As shown in Figure 10, its Rf value of STOBA product of 4,8 or 12 hours of reaction is all near 26.6 minutes.
Embodiment 8:PMI/BTA (1: 1)-NMP-20wt%-70 ℃-6H
PMI-BTA (1: 1)-NMP-20wt%-70 ℃-6H was meant that the mol ratio of reactant PMI and BTA is 1: 1, and solid content is about 20wt.%, and solvent is NMP, 70 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(1) N-phenyl-maleimide (PMI) monomer of getting about 18 grams is inserted in the 250ml round bottom three-necked bottle, adds about 60 gram nmp solvents, and is heated to 70 ℃ of fully stirrings, and maleimide monomer can be dissolved in the nmp solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram nmp solvents, and fully stir, BTA can be dispersed in the nmp solvent with magnetite.
(3) BTA-NMP solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 70 ℃ the PMI-NMP solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that BTA-NMP solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is PMI/BTA (1: 1)-NMP-20wt%-70 ℃-6H solution, presents glistening yellow look clarification.
Embodiment 9:PPMI/BTA (1: 1)-NMP-20wt%-70 ℃-6H
PPMI-BTA (1: 1)-NMP-20wt%-70 ℃-6H is meant reactant polyphenylene methylene radical maleimide (polyphenylmethane maleimide, abbreviation PPMI) mol ratio with BTA is 1: 1, solid content was about 20wt.%, and solvent is the NMP system, 70 ℃ of reactions 6 hours; The programstep of its preparation and reaction conditions list as follows:
(1) PPMI that gets about 18 grams inserts in the 250ml round bottom three-necked bottle, adds about 60 gram nmp solvents, and is heated to 70 ℃ of fully stirrings, and maleimide monomer can be dissolved in the nmp solvent fully.
(2) claim about 7 gram BTA powder, add in about 40 gram nmp solvents, and fully stir, BTA can be dispersed in the nmp solvent with magnetite.
(3) BTA-NMP solution branch is made 8 addition materials such as branch such as grade, to add a defective material in per 15 minutes, segmented mode progressively is incorporated in 70 ℃ the polyphenylmethane maleimide-NMP solution in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that BTA-NMP solution has added fully after, continuous action reaction is 4 hours again.
(5) reaction is finished and is cooled off the back and take out, and promptly is PPMI/BTA (1: 1)-NMP-20wt%-70 ℃-6H solution, presents glistening yellow look clarification.
Embodiment 10:STOBA (1: 1)-DMF-10wt%-RT-8day
STOBA (1: 1)-DMF-10wt%-RT-8day was meant that the mol ratio of reactant B MI and BTA is 1: 1, and solid content is about 10wt.%, and solvent is the DMF system, room temperature (about 24 ℃) reaction 8 days; The programstep of its preparation and reaction conditions list as follows:
(1) gets about 9 bismaleimidess (4 that restrain, 4 '-Bismaleimidodi-phenylmethane) monomer is inserted in the 250ml round bottom three-necked bottle, add about 60 gram DMF solvents, and at room temperature fully stir, the bismaleimide amine monomers can be dissolved in the DMF solvent fully.
(2) claim about 3.5 gram BTA powder, add in about 40 gram DMF solvents, and, BTA can be dissolved in the DMF solvent with the abundant stir about of magnetite 2 hours.
(3) BTA-DMF solution branch is made 8 addition materials such as branch such as grade, added a defective material with per 15 minutes, segmented mode progressively is incorporated in the BMI-DMF solution of room temperature in batches, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat that BTA-DMF solution has added fully after, continuous action reaction is 8 days again.
(5) after reaction is finished, promptly be STOBA (1: 1)-DMF-10wt%-RT-8day solution, present the yellowish brown clarification.
Embodiment 11:BMI 2/BTA (1: 1)-DMF-10wt%-90C-4H
(1) dihydroxyphenyl propane phenyl ether bismaleimides (the Bisphenol A diphenyl etherbismaleimide) monomer of getting about 9 grams is inserted in the 250ml round bottom three-necked bottle, add about 60 gram DMF solvents, and at room temperature fully stir, the bismaleimide amine monomers can be dissolved in the DMF solvent fully.
(2) claim about 3.5 gram BTA powder, add in about 40 gram DMF solvents, and, BTA can be dissolved in the DMF solvent with the abundant stir about of magnetite 2 hours.
(3) BTA-DMF solution directly is incorporated in 90 ℃ the BMI2-DMF solution, fully stirs the heat polymerization that carries out the two keys of bismaleimides.
(4) treat BTA-DMF and BMI2-DMF solution mix after, continuous action reaction is 4 hours again.
(5) after reaction is finished, promptly be BMI2/BTA (1: 1)-DMF-10wt%-90C-4H, present the yellowish brown clarification.
Gel permeation chromatography instrument (Gel Permeation Chromatography with the DMF solution of BMI, abbreviation GPC) collection of illustrative plates (Fig. 8) is compared, the Rf value of the product S TOBA of embodiment 11 is about 26.7 minutes, and does not have the signal of BMI and BTA, shows that BMI and BTA fully react.In addition, the product S TOBA of embodiment 11 is approximate unimodal, and its purity is also quite high.
Embodiment 12:BMI 1-PMI/BTA (9: 1: 10)-DMF-10wt%-90C-4H
BMI 1-PMI/BTA (9: 1: 10)-DMF-10wt%-90C-4H is meant reactant bismaleimides (4,4 '-Bismaleimidodi-phenylmethane), N-phenyl-maleimide (PMI) is about 9: 1: 10 with the mol ratio of BTA, solid content is about 10wt.%, solvent was the DMF system, 90 ℃ of reactions 4 hours; The programstep of its preparation and reaction conditions list as follows:
(1) gets 4 of about 8.8 grams, 4 '-Bismaleimidodi-phenylmethane and about 0.47 gram N-phenyl-maleimide monomer are inserted in the 250ml round bottom three-necked bottle, add about 60 gram DMF solvents, and at room temperature fully stir, the bismaleimide amine monomers can be dissolved in the DMF solvent fully.
(2) claim about 3.5 gram BTA powder, add in about 40 gram DMF solvents, and, BTA can be dissolved in the DMF solvent with the abundant stir about of magnetite 2 hours.
(3) BTA-DMF solution directly is incorporated in 90 ℃ the BMI 1/PMI-DMF solution, fully stirs the heat polymerization that carries out bismaleimides and the two keys of single maleimide.
(4) treat BTA-DMF and BMI 1/PMI-DMF solution mix after, continuous action reaction is 4 hours again.
(5) after reaction is finished, promptly be BMI 1-PMI/BTA (9: 1: 10)-DMF-10wt%-90C-4H, present the yellowish brown clarification.
Embodiment 13:BMI 1-PPMI/BTA (9: 1: 10)-DMF-10wt%-90C-4H
BMI 1-PPMI/BTA (9: 1: 10)-DMF-10wt%-90C-4H is meant reactant bismaleimides (4,4 '-Bismaleimidodi-phenylmethane, abbreviation BMI), the mol ratio of PPMI and BTA is about 9: 1: 10, solid content is about 10wt.%, solvent was the DMF system, 90 ℃ of reactions 4 hours; The programstep of its preparation and reaction conditions list as follows:
(1) BMI and the about 0.5 gram PPMI monomer of getting about 8.8 grams inserted in the 250ml round bottom three-necked bottle, adds about 60 gram DMF solvents, and at room temperature fully stirs, and bismaleimide amine monomers and PPMI monomer can be dissolved in the DMF solvent fully.
(2) claim about 3.5 gram BTA powder, add in about 40 gram DMF solvents, and, BTA can be dissolved in the DMF solvent with the abundant stir about of magnetite 2 hours.
(3) BTA-DMF solution directly is incorporated in 90 ℃ the BMI 1/PPMI-DMF solution, fully stirs the heat polymerization that carries out bismaleimides and the two keys of single maleimide.
(4) treat BTA-DMF and BMI 1/PPMI-DMF solution mix after, continuous action reaction is 4 hours again.
(5) after reaction is finished, promptly be BMI 1-PPMI/BTA (9: 1: 10)-DMF-10wt%-90C-4H, present the yellowish brown clarification.
(chromatography tubing string group is KD-G, KD-801, KD-802, KD-802, KD-802.5 for above-mentioned each reactant and solvent systems, comparative example (1～6) and embodiment (1～13) utilization gel chromatography instrument, flow velocity: 0.8ml/min) examine and analyse, tomographic results is converged peak value bigger in the collection of illustrative plates and is made into table, and is as shown in table 1.Can find out that from table bismaleimides (BMI) and malonylurea (BTA) under different concns ratio, solvent, temperature of reaction and time, all can be reacted into the similar hyper branched polymer of scantlings of the structure (Hyper-branchedPolymer).The separation main peak value of gpc chromatogram shows that about 26.4～26.7 reaction structurally has the effect that the oneself stops (self-terminating).If reaction continues to carry out, then solution can produce the phenomenon of gel, and this moment, gpc chromatogram had the peak value of disengaging time to occur between 19～23 minutes, as embodiment 11.The spectrum peak of disengaging time can appear in the embodiment of possible gelation between 19～23 minutes of GPC spectrogram; Yet if form gel, be insoluble in the solvent dimethylformamide (DMF), also can't carry out GPC and detect.Therefore the GPC of embodiment detects and is the formula solution that dissolves in solvent dimethylformamide (DMF), does not also form gel.But when more of a specified duration as if the reaction times, the spectral strength value that occurs between 19～23 minutes of GPC spectrogram can increase, and after this peak value reached certain intensity, promptly moment produced gel state, and promptly can't carry out the detection of GPC this moment.
(STOBA2: product 1) is dissolved in DMSO-d with embodiment 7 to get embodiment 1-6 (STOBA 1: 1)
6After, measure the proton nmr spectra of those products.Hydrogen by embodiment 1-6 is composed as can be known, and no matter solvent is GBL, PC, NMP or DMF,
1The corresponding chemical shift of each feature hydrogen that the H-NMR wave spectrogram occurs is quite similar.On the other hand, no matter the ratio of BMI and BTA is 1: 1 (as shown in Figure 3) or 2: 1 (as shown in Figure 4),
1The corresponding chemical shift of each feature hydrogen that the H-NMR wave spectrogram occurs is quite similar.In Fig. 3 and Fig. 4, the chemical shift of hydrogen spectrum has following feature: the hydrogen wave spectrum between δ 11.2-12.4 for BTA in the STOBA structure-NH; And δ 7.155 is the hydrogenation displacement study on two keys in the BMI structure.δ 7.2-7.5 then is the hydrogenation displacement study on the phenyl in the BMI structure.Fig. 3-4 is compared with the hydrogen spectrum (Fig. 1-2) of releaser BTA and BMI, and the BMI of embodiment 1-7 forms STOBA with the abundant action-reaction of BTA as can be known, and residual BMI and BTA monomer are quite few.
The present invention analyzes embodiment 1,2, reaches 4 temperature of reaction, shown in Fig. 5-7 with elementary errors scan-type thermal analyzer (differential scanning calorimetry is called for short DSC).When Fig. 5-7 contains Brewster alkali such as NMP the solvent as can be known, can effectively subtract the temperature of falling action-reaction.As shown in Figure 5, if use GBL as solvent systems such as embodiment 1 merely, its exothermic heat of reaction peak is about 124 ℃.As shown in Figure 6, if heavy NMP such as embodiment 4 such as addings, its exothermic heat of reaction peak subtracts reduces to about 92 ℃.As shown in Figure 7, if use NMP such as embodiment 2 separately, its exothermic heat of reaction peak more can subtract to be reduced to about 83 ℃.
Though the present invention with several preferred embodiments openly as above; right its is not in order to limit the present invention; have in the technical field under any and know the knowledgeable usually; without departing from the spirit and scope of the present invention; when can changing arbitrarily and retouching, so protection scope of the present invention is as the criterion when looking the accompanying Claim book scope person of defining.
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| CN101210073B (en) * | 2006-12-30 | 2010-12-08 | 财团法人工业技术研究院 | Composition containing bismaleimide oligomer and preparation method thereof |
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| JP2016152152A (en) * | 2015-02-18 | 2016-08-22 | 三井化学株式会社 | Separator and manufacturing method therefor, and lithium ion secondary battery |
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