CN107383300A - The phenolic Hyperbranched polyphenylene of diamines three and oxazine and preparation method thereof - Google Patents
The phenolic Hyperbranched polyphenylene of diamines three and oxazine and preparation method thereof Download PDFInfo
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- CN107383300A CN107383300A CN201710725346.1A CN201710725346A CN107383300A CN 107383300 A CN107383300 A CN 107383300A CN 201710725346 A CN201710725346 A CN 201710725346A CN 107383300 A CN107383300 A CN 107383300A
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- hyperbranched polyphenylene
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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Abstract
The present invention is to provide a kind of phenolic Hyperbranched polyphenylene of diamines three and oxazine and preparation method thereof.Diamine compound, three phenolic compounds, paraformaldehyde and organic solvent are added into container, wherein, the amount ratio of the material of diamine compound, three phenolic compounds and paraformaldehyde is 3:2:12, it is warming up to 60~110 DEG C, after 10~75h of isothermal reaction, by NaOH solution alkali cleaning, washing, rotary evaporation, vacuum drying of the reaction solution through 0.2mol/L, obtain the phenolic Hyperbranched polyphenylene of diamines three and oxazine, the weight average molecular weight of product is 6000~55000, and molecular weight distributing index is 1.7~3.5.The present invention phenolic Hyperbranched polyphenylene of diamines three and oxazine using three phenolic compounds and diamine compounds as Material synthesis.Duo oxazine ring make it that its cured product crosslink density is high, molecular weight is big, has excellent hot property and mechanical property, available for manufacture high performance structures material, electronic package material etc., can be widely used in the fields such as electronics, aviation and machine-building.
Description
Technical field
The present invention relates to a kind of high-molecular organic material, and the present invention also relates to a kind of preparation of high-molecular organic material
Method.The specifically a kind of phenolic of diamines-three Hyperbranched polyphenylene and oxazine and preparation method thereof.
Background technology
Benzoxazine is to be reacted to contract through Mannich by phenolic compound, primary amine compound and formaldehyde (or paraformaldehyde)
Close the 6-membered heterocyclic compound of the atom containing O and N formed.In the presence of heating or catalyst, benzoxazine energy ring-opening polymerisation
Cross-linked network structure of the generation similar to phenolic resin.Compared with traditional phenolic resin, the performance of benzoxazine is more superior,
It is in the curing process catalyst without using strong acid or alkali with flexible MOLECULE DESIGN, no small molecule by-product generation,
Volume approximation zero shrink even microdilatancy, polymer have higher heat resistance and heat endurance, relatively low water absorption rate and surface energy,
Good insulating properties and UV resistance etc..But benzoxazine is present, and crosslink density is relatively low, solidification temperature is higher, poor toughness etc.
Deficiency, it is therefore necessary to be modified to it.
Dissaving polymer is similar to tree shaped polymer, possess a large amount of terminal groups, the centronucleus of polyfunctionality, viscosity it is low,
The good advantage of dissolubility, therefore toughening modifying is carried out to thermosetting resin using dissaving polymer.Ratna et al. utilizes hydroxyl end
Base study on hyperbranched polymer modified epoxy resins system, in the case that research adds dissaving polymer content difference, solidify power
Learning parameter, the toughness of phenomenon of phase separation and material can be by being influenceed (D Ratna, GP Simon.Thermomechanical
properties and morphology of blends of a hydroxy-functionalized hyperbranched
polymer and epoxy resin.Polymer,2001,42(21):8833-8839；D Ratna,R Varley,RKS
Raman,et al.Studies on blends of epoxy-functionalized hyperbranched polymer
and epoxy resin.Journal of Materials Science,2003,38(1):147-154).As a result understand, surpass
Substantial amounts of hydroxyl causes the solidification rate of epoxy-resin systems to significantly improve in branched polymer structure, when addition is 10%
When, impact strength improves the most notable.
The content of the invention
It is an object of the invention to provide a kind of phenolic hyperbranched poly of diamines-three with good thermal and mechanical property
Benzoxazine.The present invention also aims to provide the preparation method of a kind of phenolic of diamines-three Hyperbranched polyphenylene and oxazine.
The phenolic of diamines-three Hyperbranched polyphenylene and oxazine of the present invention has following structural formula：
The phenolic of diamines-three Hyperbranched polyphenylene and the preparation method of oxazine of the present invention be：
Diamine compound, three phenolic compounds, paraformaldehyde and organic solvent are added into container, wherein, diamine compound,
The amount ratio of the material of three phenolic compounds and paraformaldehyde is 3:2:12, it is warming up to 60~110 DEG C, will after 10~75h of isothermal reaction
NaOH solution alkali cleaning, washing, rotary evaporation, vacuum drying of the reaction solution through 0.2mol/L, obtain the phenolic hyperbranched poly of diamines-three
Benzoxazine, the weight average molecular weight of product is 6000~55000, and molecular weight distributing index (PDI) is 1.7~3.5.
The phenolic of diamines-three Hyperbranched polyphenylene and the preparation method of oxazine of the present invention can also include：
1st, three described phenolic compounds are one kind in triphenol methylmethane or 1,1,1- tri- (4- hydroxy phenyls) ethane.
2nd, described diamine compound is polyetheramine D-230, polyetheramine D-400, aliphatic diamine (H2N-(CH2)n-NH2, n
=2~8), double (3- the aminopropyls) -1,1,3,3- tetramethyl disiloxanes of 1,3- or aminopropyl end-blocking dimethyl silicone polymer
(molecular weight：1070) one kind in.
3rd, described organic solvent is one kind in benzene, toluene, chloroform or dioxane.
The present invention, using commercialized three phenolic compound and diamine compounds as raw material, passes through control by MOLECULE DESIGN
The conditions such as the ratio in reaction time processed, monomer concentration and two kinds of monomers have synthesized a series of phenolic of diamines-three Hyperbranched polyphenylenes
Bing oxazines and preparation method thereof.Many on the market be present and can be directly used for A2+B3The monomer of polymerisation, in not only reducing
Between monomer synthesis step, improve production efficiency, and production cost can be reduced, realize quick and cheap preparation and surpass
Branched polymer.
The phenolic of diamines-three Hyperbranched polyphenylene and the structural characterization of oxazine of the present invention utilizes infrared spectrum (Spotlight
100, PE companies of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker), examination of infrared spectrum use KBr pressure
Piece method, Sample Scan 4 times, resolution ratio 4cm-1, scanning range to 4000~500cm-1；Proton nmr spectra is with tetramethylsilane
Alkane (TMS) makees internal standard, deuterated dimethyl sulfoxide (DMSO-d6) make solvent；Polymer performance test using thermogravimetric analyzer (TGA,
TA companies of the U.S.) and dynamic thermomechanical analysis apparatus (DMA, TA companies of the U.S.).Wherein TGA uses nitrogen atmosphere, and heating rate is
20℃/min；DMA uses air atmosphere, single-cantilever pattern, and heating rate is 3 DEG C/min.
The present invention is by MOLECULE DESIGN, diamines-triphenol using three phenolic compounds and diamine compounds as Material synthesis
Type hyperbranched poly benzo oxazine.Duo oxazine ring make it that its cured product crosslink density is high, molecular weight is big, has excellent hot
Energy and mechanical property, available for manufacture high performance structures material, electronic package material etc., electronics, aviation and machine can be widely used in
The fields such as tool manufacture.
Brief description of the drawings
The proton nmr spectra of Fig. 1 polyetheramine D-230- triphenol methylmethane base hyperbranched poly benzo oxazines.
The infrared spectrum of Fig. 2 polyetheramine D-230- triphenol methylmethane base hyperbranched poly benzo oxazines.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that, the embodiment of the present invention is only
It is used to further illustrate the present invention, but it is not intended that limiting the scope of the invention, the technology in the field are ripe
Practice personnel and some nonessential modifications and adaptations are made according to the content of the invention described above.
Embodiment 1
In the three-necked flask equipped with magnetic agitation rotor, thermometer and condenser pipe, addition triphenol methylmethane (0.78g,
2mmol), polyetheramine D-230 (0.69g, 3mmol), paraformaldehyde (0.36g, 12mmol) and 50mL Isosorbide-5-Nitraes-dioxane are molten
Agent, is warming up to 100 DEG C, after isothermal reaction 72h, by NaOH solution alkali cleaning of the reaction solution through 0.2mol/L, washing, rotary evaporation,
Vacuum drying, obtains polyetheramine D-230- triphenol methylmethane base hyperbranched poly benzo oxazine powder, yield 83%, the weight of polymer
Average molecular weight is 36000, PDI 3.2.
Proton nmr spectra test result (500M, DMSO-d6, ppm)：6.65~7.28ppm is proton hydrogen on phenyl ring
Chemical shift；It is respectively O-CH in oxazine ring at 5.34ppm and 4.88ppm2- N and Ar-CH2- N characteristic peak；3.74ppm place is
The chemical shift of amide proton hydrogen；It is the characteristic peak of methine protons hydrogen at 2.71ppm；Peak near 0.99~1.05ppm is
The chemical shift of methyl proton hydrogen (see Fig. 1)；Examination of infrared spectrum result (KBr, cm-1)：3277cm-1The absworption peak ownership at place
The O-H stretching vibrations in phenolic hydroxyl group, 2976cm-1And 2868cm-1The absworption peak at place belongs to the stretching vibration of saturation c h bond,
1665cm-1And 1613cm-1The absworption peak at place belongs to phenyl ring skeleton stretching vibration, 1512cm-1And 823cm-1Locate as on phenyl ring 1,
2,4- tri- substitution absworption peaks, 1256cm-1The absworption peak at place be C-O-C asymmetric stretching vibration, 1101cm-1The absworption peak at place
Belong to C-N-C asymmetric stretching vibration, 746cm-1And 702cm-1Locate the out-of-plane bending vibration for c h bond, 921cm-1Place
Absworption peak is the characteristic absorption peak of Dai You oxazine rings on phenyl ring (see Fig. 2).Institute is confirmed with reference to proton nmr spectra and infrared spectrum
It is target product to obtain product.
A certain amount of hyperbranched benzoxazine is added in a mold, is subsequently placed in air dry oven, according to program
The mode of heating carries out heat cure, and specific curing cycle is：160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h, utilize
DMA and TGA is tested final solidfied material.The ether amines D-230- triphenol methylmethane base hyperbranched poly benzo oxazines finally given
The glass transition temperature of resin (is abbreviated as Tg) for 193 DEG C, weightlessness 5% and 10% corresponding to heat decomposition temperature (be abbreviated as T5
And T10) it is respectively that carbon yield at 358 and 383 DEG C, 800 DEG C (is abbreviated as Yc) it is 46.5%.
Embodiment 2
Except polyetheramine D-230 is replaced with into ethylenediamine (0.18g, 3mmol) outside, other conditions finally give with embodiment 1
Ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazine, yield 87%, the weight average molecular weight of polymer are for 24500, PDI
2.7。
Proton nmr spectra test result (500M, DMSO-d6, ppm)：6.64~7.27,5.32,4.77,3.83,
2.76th, 0.98~1.03；Examination of infrared spectrum result (KBr, cm-1)：3433、2944、2852、1671、1613、1496、820、
1330、1231、1118、921、872、748、701.Confirm that products therefrom produces for target with reference to proton nmr spectra and infrared spectrum
Thing.
Solidification and test condition finally give ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazine tree with embodiment 1
The T of fatg、T5、T10And YcValue is respectively 231 DEG C, 374 DEG C, 398 DEG C and 43.6%.
Embodiment 3
In addition to the reaction time is changed to 48h by 72h, other conditions finally give ethylenediamine-triphenol methylmethane with embodiment 2
Base hyperbranched poly benzo oxazine, yield 85%, the weight average molecular weight of polymer is 19700, PDI 2.3.
Solidification and test condition finally give ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazine tree with embodiment 1
The T of fatg、T5、T10And YcValue is respectively 227 DEG C, 367 DEG C, 382 DEG C and 39.8%.
Embodiment 4
In addition to temperature is changed outside 70 DEG C, other conditions finally give ethylenediamine-triphenol methylmethane base over-expense with embodiment 3
Change Polybenzoxazine, yield 81%, the weight average molecular weight of polymer is 17300, PDI 1.9.
Solidification and test condition finally give ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazine tree with embodiment 1
The T of fatg、T5、T10And YcValue is respectively 227 DEG C, 367 DEG C, 382 DEG C and 39.8%.
Embodiment 5
In addition to organic solvent is changed into chloroform, other conditions finally give ethylenediamine-triphenol methylmethane base with embodiment 4
Hyperbranched poly benzo oxazine, yield 82%, the weight average molecular weight of polymer is 16800, PDI 1.8.
Solidification and test condition finally give ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazine tree with embodiment 1
The T of fatg、T5、T10And YcValue is respectively 225 DEG C, 368 DEG C, 384 DEG C and 40.1%.
Embodiment 6
Except triphenol methylmethane is changed into 1,1,1- tri- (4- hydroxy phenyls) ethane (0.52g, 2mmol) outside, other conditions are same
Embodiment 1, finally give polyetheramine D-230-1,1,1- tri- (4- hydroxy phenyls) ethyl group hyperbranched poly benzo oxazine, yield
84%, the weight average molecular weight of polymer is 20800, PDI 2.1.
Proton nmr spectra test result (500M, DMSO-d6, ppm)：6.67~7.32,5.41,4.83,3.82,
2.70th, 0.98~1.03；Examination of infrared spectrum result (KBr, cm-1)：3434、2947、2854、1669、1613、1495、820、
1330、1232、1116、921、870、751、701.Confirm that products therefrom produces for target with reference to proton nmr spectra and infrared spectrum
Thing.
Solidification and test condition finally give polyetheramine D-230-1,1,1- tri- (4- hydroxy phenyls) ethane with embodiment 1
The T of base hyperbranched poly benzo oxazine resing、T5、T10And YcValue is respectively 208 DEG C, 362 DEG C, 389 DEG C and 44.1%.
Embodiment 7
In addition to temperature is changed into 70 DEG C, solvent is changed to outside chloroform, and other conditions finally give polyetheramine D- with embodiment 6
230-1,1,1- tri- (4- hydroxy phenyls) ethyl group hyperbranched poly benzo oxazine, yield 82%, the weight average molecular weight of polymer are
21900, PDI 2.2.
Solidification and test condition finally give polyetheramine D-230-1,1,1- tri- (4- hydroxy phenyls) ethane with embodiment 1
The T of base hyperbranched poly benzo oxazine resing、T5、T10And YcValue is respectively 201 DEG C, 355 DEG C, 379 DEG C and 42.8%.
Simultaneously oxazine resin shows excellent heat resistance to the prepared phenolic of diamines-three Hyperbranched polyphenylene in the present invention,
Available for manufacture high performance structures material, electronic package material, high-temperature Resistance Adhesives, ablation resistant material, resistant material etc.,
The fields such as electronics, Aero-Space, machine-building are with a wide range of applications.
Claims (6)
1. a kind of phenolic of diamines-three Hyperbranched polyphenylene and oxazine, it is characterized in that having following structural formula：
2. the preparation method of the phenolic of diamines-three Hyperbranched polyphenylene and oxazine described in a kind of claim 1, it is characterized in that：Xiang Rong
Diamine compound, three phenolic compounds, paraformaldehyde and organic solvent are added in device, wherein, diamine compound, three phenolic compounds with
The amount ratio of the material of paraformaldehyde is 3:2:12, it is warming up to 60~110 DEG C, after 10~75h of isothermal reaction, reaction solution is passed through
0.2mol/L NaOH solution alkali cleaning, washing, rotary evaporation, vacuum drying, obtain the phenolic of diamines-three Hyperbranched polyphenylene and Evil
Piperazine, the weight average molecular weight of product is 6000~55000, and molecular weight distributing index is 1.7~3.5.
3. the preparation method of the phenolic of diamines-three Hyperbranched polyphenylene according to claim 2 and oxazine, it is characterized in that：It is described
Three phenolic compounds be one kind in triphenol methylmethane or 1,1,1- tri- (4- hydroxy phenyls) ethane.
4. the preparation method of the phenolic of diamines-three Hyperbranched polyphenylene and oxazine according to Claims 2 or 3, it is characterized in that：Institute
The diamine compound stated is polyetheramine D-230, polyetheramine D-400, aliphatic diamine, double (3- the aminopropyls) -1,1,3,3- of 1,3-
One kind in tetramethyl disiloxane or aminopropyl end-blocking dimethyl silicone polymer.
5. the preparation method of the phenolic of diamines-three Hyperbranched polyphenylene and oxazine according to Claims 2 or 3, it is characterized in that：Institute
The organic solvent stated is one kind in benzene, toluene, chloroform or dioxane.
6. the preparation method of the phenolic of diamines-three Hyperbranched polyphenylene according to claim 4 and oxazine, it is characterized in that：It is described
Organic solvent be benzene, toluene, chloroform or dioxane in one kind.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030023007A1 (en) * | 2001-07-27 | 2003-01-30 | Hycomp, Inc. | Enhancement of thermal properties of benzoxazine polymers by use of aromatic polyamines to incorporate internal benzoxazine groups within the monomer |
| CN101883807A (en) * | 2007-12-06 | 2010-11-10 | 汉高两合股份公司 | Curable benzoxazine macromonomers, their preparation and cured product thereof |
| CN107074789A (en) * | 2014-10-27 | 2017-08-18 | 塞特工业公司 | Method for preparing benzoxazine |
-
2017
- 2017-08-22 CN CN201710725346.1A patent/CN107383300B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030023007A1 (en) * | 2001-07-27 | 2003-01-30 | Hycomp, Inc. | Enhancement of thermal properties of benzoxazine polymers by use of aromatic polyamines to incorporate internal benzoxazine groups within the monomer |
| CN101883807A (en) * | 2007-12-06 | 2010-11-10 | 汉高两合股份公司 | Curable benzoxazine macromonomers, their preparation and cured product thereof |
| CN107074789A (en) * | 2014-10-27 | 2017-08-18 | 塞特工业公司 | Method for preparing benzoxazine |
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