CN107383300B - - three phenolic Hyperbranched polyphenylene of diamines and oxazines and preparation method thereof - Google Patents
- three phenolic Hyperbranched polyphenylene of diamines and oxazines and preparation method thereof Download PDFInfo
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- CN107383300B CN107383300B CN201710725346.1A CN201710725346A CN107383300B CN 107383300 B CN107383300 B CN 107383300B CN 201710725346 A CN201710725346 A CN 201710725346A CN 107383300 B CN107383300 B CN 107383300B
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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-three phenolic Hyperbranched polyphenylene of diamines and oxazines and preparation method thereof.Diamine compound, three phenolic compounds, paraformaldehyde and organic solvent are added into container, wherein, the mass 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, NaOH solution alkali cleaning, washing, rotary evaporation, vacuum drying by reaction solution through 0.2mol/L obtain-three phenolic Hyperbranched polyphenylene of diamines and oxazines, the weight average molecular weight of product is 6000~55000, and molecular weight distributing index is 1.7~3.5.The present invention is using three phenolic compounds and diamine compounds as-three phenolic Hyperbranched polyphenylene of Material synthesis diamines and oxazines.Multiple oxazines rings make its cured product crosslink density height, molecular weight big, have excellent hot property and mechanical property, can be used for manufacturing 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 materials, and the present invention also relates to a kind of preparations of high-molecular organic material
Method.Specifically a kind of-three phenolic Hyperbranched polyphenylene of diamines and oxazines and preparation method thereof.
Background technique
Benzoxazine is to be reacted to contract through Mannich by phenolic compound, primary amine compound and formaldehyde (or paraformaldehyde)
The 6-membered heterocyclic compound of the atom containing O and N made of conjunction.Under the action of heating or catalyst, benzoxazine energy ring-opening polymerisation
Generate the cross-linked network structure for being 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 generates,
Volume approximation zero shrinks even microdilatancy, polymer have higher heat resistance and thermal stability, lower water absorption rate and surface can,
Good insulation performance and UV resistance etc..But that there are crosslink densities is lower for benzoxazine, solidification temperature is higher, poor toughness etc.
It is insufficient, it is therefore necessary to which that it is modified.
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 solidifies power in the case that dissaving polymer content difference is added in research
Learn influence (D Ratna, the GP Simon.Thermomechanical that the toughness of parameter, phenomenon of phase separation and material will receive
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 it is found that it is super
A large amount of hydroxyl significantly improves the solidification rate of epoxy-resin systems in branched polymer structure, when additional amount is 10%
When, impact strength improves the most significant.
Summary of the invention
The purpose of the present invention is to provide a kind of-three phenolic hyperbranched poly of diamines with good thermal and mechanical property
Benzoxazine.The object of the invention is also to provide the preparation methods of a kind of-three phenolic Hyperbranched polyphenylene of diamines and oxazines.
- three phenolic Hyperbranched polyphenylene of diamines and oxazines of the invention has the following structure formula:
- three phenolic Hyperbranched polyphenylene of diamines of the invention and oxazines the preparation method comprises the following steps:
Diamine compound, three phenolic compounds, paraformaldehyde and organic solvent are added into container, wherein diamine compound,
The mass ratio of the material of three phenolic compounds and paraformaldehyde is 3:2:12, 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-three phenolic hyperbranched poly of diamines
Benzoxazine, the weight average molecular weight of product are 6000~55000, and molecular weight distributing index (PDI) is 1.7~3.5.
The preparation method of-three phenolic Hyperbranched polyphenylene of diamines of the invention and oxazines can also include:
1, three phenolic compounds are one of triphenol methylmethane or 1,1,1- tri- (4- hydroxy phenyl) ethane.
2, the diamine compound is polyetheramine D-230, polyetheramine D-400, aliphatic diamine (H2N-(CH2)n-NH2, n
=2~8), bis- (3- the aminopropyl) -1,1,3,3- tetramethyl disiloxanes of 1,3- or aminopropyl block dimethyl silicone polymer
One of (molecular weight: 1070).
3, the organic solvent is one of benzene, toluene, chloroform or dioxane.
The present invention passes through control using commercialized three phenolic compound and diamine compounds as raw material by MOLECULE DESIGN
Reaction time processed, monomer concentration and two kinds of monomers the conditions such as ratio synthesized a series of-three phenolic Hyperbranched polyphenylenes of diamines
And oxazines and preparation method thereof.There is many on the market can be directly used for A2+B3The monomer of polymerization reaction, not only reduces
Between monomer synthesis step, improve production efficiency, and can reduce production cost, it is super to realize quick and cheap preparation
Branched polymer.
The structural characterization of-three phenolic Hyperbranched polyphenylene of diamines and oxazines of the invention utilizes infrared spectroscopy (Spotlight
100, PE company, the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker), examination of infrared spectrum is using potassium bromide pressure
Piece method, Sample Scan 4 times, resolution ratio 4cm-1, scanning range to 4000~500cm-1；Nuclear magnetic resonance spectroscopy is with tetramethylsilane
Alkane (TMS) makees internal standard, deuterated dimethyl sulfoxide (DMSO-d6) make solvent；Polymer performance test using thermogravimetric analyzer (TGA,
TA company, the U.S.) and dynamic thermomechanical analysis apparatus (DMA, TA company, the U.S.).Wherein TGA uses nitrogen atmosphere, and heating rate is
20℃/min；DMA uses air atmosphere, single-cantilever mode, and heating rate is 3 DEG C/min.
The present invention is by MOLECULE DESIGN, using three phenolic compounds and diamine compounds as Material synthesis diamines-triphenol
Type hyperbranched poly benzo oxazines.Multiple oxazines rings make that its cured product crosslink density is high, molecular weight is big, with excellent hot
Energy and mechanical property, can be used for manufacturing high performance structures material, electronic package material etc., can be widely used in electronics, aviation and machine
The fields such as tool manufacture.
Detailed description of the invention
The nuclear magnetic resonance spectroscopy 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.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein to be, the embodiment of the present invention is only
It is used to further illustrate the present invention, but should not be understood as limiting the scope of the invention, the technology in the field is ripe
Practice personnel and some nonessential modifications and adaptations are made according to the content of aforementioned present invention.
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-Nitrae-dioxane are molten
Agent, is warming up to 100 DEG C, after isothermal reaction 72h, NaOH solution alkali cleaning, washing, rotary evaporation by reaction solution through 0.2mol/L,
Vacuum drying, obtains polyetheramine D-230- triphenol methylmethane base hyperbranched poly benzo oxazines powder, yield 83%, the weight of polymer
Average molecular weight is 36000, PDI 3.2.
Nuclear magnetic resonance spectroscopy test result (500M, DMSO-d6, ppm): 6.65~7.28ppm is proton hydrogen on phenyl ring
Chemical shift；It is respectively O-CH on oxazines ring at 5.34ppm and 4.88ppm2- N and Ar-CH2The characteristic peak of-N；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 absorption peak at place belongs to
The O-H stretching vibration in phenolic hydroxyl group, 2976cm-1And 2868cm-1The absorption peak at place belongs to the stretching vibration of saturation c h bond,
1665cm-1And 1613cm-1The absorption peak at place belongs to phenyl ring skeleton stretching vibration, 1512cm-1And 823cm-1Place is on phenyl ring 1,
2,4- tri- replace absorption peak, 1256cm-1The absorption peak at place is the asymmetric stretching vibration of C-O-C, 1101cm-1The absorption peak at place
Belong to the asymmetric stretching vibration of C-N-C, 746cm-1And 702cm-1Place is the out-of-plane bending vibration of c h bond, 921cm-1Place
Absorption peak is the characteristic absorption peak that oxazines ring is had on phenyl ring (see Fig. 2).Institute is confirmed in conjunction with nuclear magnetic resonance spectroscopy and infrared spectroscopy
Obtaining product is target 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, specific curing cycle are as follows: 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h, utilizes
DMA and TGA tests final solidfied material.Finally obtained ether amines D-230- triphenol methylmethane base hyperbranched poly benzo oxazines
The glass transition temperature of resin (is abbreviated as Tg) be 193 DEG C, weightlessness 5% and 10% corresponding to thermal decomposition temperature (be abbreviated as T5
And T10) it is respectively 358 and 383 DEG C, the carbon yield at 800 DEG C (is abbreviated as Yc) it is 46.5%.
Embodiment 2
Except polyetheramine D-230 is replaced with ethylenediamine (0.18g, 3mmol) outside, other conditions are finally obtained with embodiment 1
Ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazines, yield 87%, the weight average molecular weight of polymer are that 24500, PDI is
2.7。
Nuclear magnetic resonance spectroscopy test result (500M, DMSO-d6, ppm): 6.64~7.27,5.32,4.77,3.83,
2.76,0.98~1.03；Examination of infrared spectrum result (KBr, cm-1): 3433,2944,2852,1671,1613,1496,820,
1330,1231,1118,921,872,748,701.Confirm products therefrom for target production in conjunction with nuclear magnetic resonance spectroscopy and infrared spectroscopy
Object.
Solidification and test condition finally obtain ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazines tree with embodiment 1
The T of rougeg、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 obtain ethylenediamine-triphenol methylmethane with embodiment 2
Base hyperbranched poly benzo oxazines, yield 85%, the weight average molecular weight of polymer are 19700, PDI 2.3.
Solidification and test condition finally obtain ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazines tree with embodiment 1
The T of rougeg、T5、T10And YcValue is respectively 227 DEG C, 367 DEG C, 382 DEG C and 39.8%.
Embodiment 4
In addition to changing temperature outside 70 DEG C, other conditions finally obtain 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 obtain ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazines tree with embodiment 1
The T of rougeg、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 to chloroform, other conditions finally obtain ethylenediamine-triphenol methylmethane base with embodiment 4
Hyperbranched poly benzo oxazines, yield 82%, the weight average molecular weight of polymer are 16800, PDI 1.8.
Solidification and test condition finally obtain ethylenediamine-triphenol methylmethane base hyperbranched poly benzo oxazines tree with embodiment 1
The T of rougeg、T5、T10And YcValue is respectively 225 DEG C, 368 DEG C, 384 DEG C and 40.1%.
Embodiment 6
Except triphenol methylmethane is changed to 1,1,1- tri- (4- hydroxy phenyl) ethane (0.52g, 2mmol) outside, other conditions are same
Embodiment 1 finally obtains polyetheramine D-230-1,1,1- tri- (4- hydroxy phenyl) ethyl group hyperbranched poly benzo oxazines, yield
84%, the weight average molecular weight of polymer is 20800, PDI 2.1.
Nuclear magnetic resonance spectroscopy test result (500M, DMSO-d6, ppm): 6.67~7.32,5.41,4.83,3.82,
2.70,0.98~1.03；Examination of infrared spectrum result (KBr, cm-1): 3434,2947,2854,1669,1613,1495,820,
1330,1232,1116,921,870,751,701.Confirm products therefrom for target production in conjunction with nuclear magnetic resonance spectroscopy and infrared spectroscopy
Object.
Solidification and test condition finally obtain polyetheramine D-230-1,1,1- tri- (4- hydroxy phenyl) ethane with embodiment 1
The T of base hyperbranched poly benzo oxazines 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 to 70 DEG C, solvent is changed to outside chloroform, and other conditions finally obtain polyetheramine D- with embodiment 6
230-1,1,1- tri- (4- hydroxy phenyl) ethyl group hyperbranched poly benzo oxazines, the weight average molecular weight of yield 82%, polymer are
21900, PDI 2.2.
Solidification and test condition finally obtain polyetheramine D-230-1,1,1- tri- (4- hydroxy phenyl) ethane with embodiment 1
The T of base hyperbranched poly benzo oxazines resing、T5、T10And YcValue is respectively 201 DEG C, 355 DEG C, 379 DEG C and 42.8%.
Simultaneously oxazines resin shows excellent heat resistance to prepared-three phenolic Hyperbranched polyphenylene of diamines in the present invention,
It can be used for manufacturing high performance structures material, electronic package material, high-temperature Resistance Adhesives, ablation resistant material, resistant material etc.,
The fields such as electronics, aerospace, machine-building are with a wide range of applications.
Claims (6)
1. a kind of-three phenolic Hyperbranched polyphenylene of diamines and oxazines, it is characterized in that: by the formula that has the following structure being prepared
Compound:
The preparation specifically includes: diamine compound, three phenolic compounds, paraformaldehyde and organic solvent are added into container,
Wherein, the mass ratio of the material of diamine compound, three phenolic compounds and paraformaldehyde is 3:2:12, is warming up to 60~110 DEG C, constant temperature
After reacting 10~75h, NaOH solution alkali cleaning, washing, rotary evaporation, vacuum drying by reaction solution through 0.2mol/L obtain two
- three phenolic Hyperbranched polyphenylene of amine and oxazines, the weight average molecular weight of product are 6000~55000, molecular weight distributing index is 1.7~
3.5。
2. the preparation method of a kind of-three phenolic Hyperbranched polyphenylene of diamines described in claim 1 and oxazines, 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 mass ratio of the material of paraformaldehyde is 3:2:12, is warming up to 60~110 DEG C, and after 10~75h of isothermal reaction, reaction solution is passed through
NaOH solution alkali cleaning, washing, rotary evaporation, the vacuum drying of 0.2mol/L obtains-three phenolic Hyperbranched polyphenylene of diamines and dislikes
Piperazine, the weight average molecular weight of product are 6000~55000, and molecular weight distributing index is 1.7~3.5.
3. the preparation method of-three phenolic Hyperbranched polyphenylene of diamines according to claim 2 and oxazines, it is characterized in that: described
Three phenolic compounds be one of triphenol methylmethane or 1,1,1- tri- (4- hydroxy phenyl) ethane.
4. the preparation method of-three phenolic Hyperbranched polyphenylene of diamines according to claim 2 or 3 and oxazines, it is characterized in that: institute
The diamine compound stated is polyetheramine D-230, polyetheramine D-400, aliphatic diamine, bis- (3- the aminopropyl) -1,1,3,3- of 1,3-
One of tetramethyl disiloxane or aminopropyl sealing end dimethyl silicone polymer.
5. the preparation method of-three phenolic Hyperbranched polyphenylene of diamines according to claim 2 or 3 and oxazines, it is characterized in that: institute
The organic solvent stated is one of benzene, toluene, chloroform or dioxane.
6. the preparation method of-three phenolic Hyperbranched polyphenylene of diamines according to claim 4 and oxazines, it is characterized in that: described
Organic solvent be one of benzene, toluene, chloroform or dioxane.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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