CN109694478A - A kind of ultrabranching polyamide and its preparation method and application - Google Patents
A kind of ultrabranching polyamide and its preparation method and application Download PDFInfo
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- CN109694478A CN109694478A CN201811622362.9A CN201811622362A CN109694478A CN 109694478 A CN109694478 A CN 109694478A CN 201811622362 A CN201811622362 A CN 201811622362A CN 109694478 A CN109694478 A CN 109694478A
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
Abstract
The present invention relates to a kind of ultrabranching polyamides and its preparation method and application, the present invention passes through esterification, with 4,4'- diaminodiphenylsulfone and Trimesic acid or mesitylene formyl chloride are primary raw material, synthesize the Hyperbranched polyphenylene sulfone amine of different molecular weight, the novel dissaving polymer rich in sulfuryl and phenyl ring of the present invention, has property resistant to high temperature, is having certain application prospect as epoxy resin high temperature resistant curing agent direction.Compared with prior art, the present invention can obtain epoxy resin cured product resistant to high temperature as epoxy curing agent, and carry out certain modification.Invention synthesis is simple, structure is special, has a good application prospect.
Description
Technical field
The present invention relates to a kind of ultrabranching polyamide, present invention relates particularly to the preparation method of this ultrabranching polyamide and
Purposes.
Background technique
Epoxy resin has good mechanical property, processing performance, electrical insulating property, chemical stability and reaction mechanism clear
The advantages that clear, at low cost, is widely used in the fields such as electronics, chemical industry, automobile, aerospace.In recent years, epoxy resin-matrix is compound
Material deepens continuously in the application of aerospace field, due to use condition harshness, proposes stringenter want to its performance
It asks: meeting outside basic mechanical property requirements, also there is good high temperature resistance.
The universal degree of functionality with higher of dissaving polymer, unimolecule effective functionality, which can be, reaches linear molecule
Several times even ten several times, and there is the high structural advantage of functional group's activity.It, can be great using dissaving structure as curing agent
The degree of functionality for improving curing agent, to improve the high temperature resistance of epoxide resin material.In addition, dissaving polymer also have it is molten
The characteristic that solution degree is high, viscosity is low, it is not only preferable with epoxy resin compatibility, the flowing of epoxy matrix can be significantly reduced after blending
Property, improve its processability.
For this purpose, the present invention comes into being.
Summary of the invention
Diamino diphenyl sulfone has the characteristics that resistant to high temperature as the solidfied material that epoxy curing agent obtains.As
After monomer obtains dissaving structure, the degree of functionality of curing agent is increased, can be further improved the high temperature resistance of epoxy resin,
Improve mechanical property and mobility.Diamino-diphenyl ether has structure similar with diamino diphenyl sulfone, and has more
High reactivity.Obtained dissaving polymer can also obtain the property of similar Hyperbranched polyphenylene sulfone amine.In view of upper, in order to
Epoxy resin is further improved in heat-resisting quantity, mechanical property and mobility etc., the present invention provides a kind of hyperbranched polyamides
Amine, which is characterized in that shown in monomer general structure such as formula (1):
Particularly, first generation dissaving polymer therein, shown in monomer general structure such as formula (2):
Wherein, intramolecular group R1Selected from-SO2Sulfuryl ,-O- ehter bond；End group (including R2、R3、R4) include but unlimited
In :-H hydrogen ,-OH hydroxyl etc..
Polyamide in the technical program has the beneficial effect that
The present invention utilizes functional group and dissaving structure in above-mentioned polymer, improves the heat resistance and mechanics of epoxy resin
Performance.
Preferably, this amide is by the monomer containing trifunctional, phenyl ring and contains two functional groups, phenyl ring, sulfuryl or ehter bond
Monomer be prepared.
Preferably, the monomer containing trifunctional and phenyl ring is 1,3,5- benzenetricarboxylic acids or 1,3,5- benzene, three formyl
Chlorine.
Preferably, the monomer containing two functional groups, phenyl ring, sulfuryl can be diamino diphenyl sulfone；Containing two functions
Group, phenyl ring, ehter bond monomer be diamino-diphenyl ether.
Preferably, above-mentioned ultrabranching polyamide, has the feature that
Matter average molecular weight is 750-30000g/mol, weight average molecular weight 750-90000g/mol；
Molecular weight distributing index is 1-4；
The degree of branching is 0.1-1；
Glass transition temperature is 200 to 300 DEG C.
Purposes the present invention also provides above-mentioned ultrabranching polyamide as curing agent.Functional group in above-mentioned polymer
And dissaving structure is used as epoxy curing agent, can improve epoxy resin so that polymer has biggish degree of functionality
Heat resistance and mechanical property.
Raw material is the synthesis process of branched monomer using 1,3,5- benzenetricarboxylic acids in the present invention, comprising the following steps:
(1) by 1,3,5- benzenetricarboxylic acid, pyridine, diamino diphenyl sulfone or diamino-diphenyl ether N- crassitude
Ketone dissolution, heating；
(2) triphenyl phosphite is slowly added into；
(3) temperature, reaction are kept.
Preferably, reaction temperature is 110~150 DEG C in step (1), (2) and (3)；In step (3) reaction time be 3~
24h。
Raw material is the synthesis process of branched monomer using 1,3,5- benzene, three formyl chloride in the present invention, comprising the following steps:
(1) under anhydrous condition, by diamino diphenyl sulfone or diamino-diphenyl ether and triethylamine N- crassitude
Ketone or n,N-Dimethylformamide dissolution, it is cooling；
(2) three formyl chloride of 1,3,5- benzene is slowly added into using N-Methyl pyrrolidone or N,N-dimethylformamide；
(3) it heats, reaction.
Preferably, cooling temperature is 0 DEG C~room temperature in step (1), (2), the reaction temperature in step (3) refers to 60~
110℃；Reaction time in step (3) refers to 3~for 24 hours.
Detailed description of the invention
Fig. 1 is the schematic diagram for the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes.
Fig. 2 is the schematic diagram of the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes block.
Fig. 3 is the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes1HNMR spectrogram.
Fig. 4 is the GPC spectrogram for the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes.
Fig. 5 is the DSC spectrogram for the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes.
Fig. 6 is the schematic diagram for the Hyperbranched polyphenylene sulfone amine that embodiment 3 synthesizes.
Fig. 7 is the GPC spectrogram for the Hyperbranched polyphenylene sulfone amine that embodiment 3 synthesizes.
Fig. 8 is the schematic diagram for the generation Hyperbranched polyphenylene sulfone amine that embodiment 4 synthesizes.
Fig. 9 is the generation Hyperbranched polyphenylene sulfone amine that embodiment 4 synthesizes1HNMR spectrogram.
Figure 10 is the schematic diagram for the generation Hyperbranched polyphenylene sulfone amine that embodiment 5 synthesizes.
Figure 11 is the schematic diagram for the generation Hyperbranched polyphenylene ether amines that embodiment 6 synthesizes.
Figure 12 is the generation Hyperbranched polyphenylene ether amines that embodiment 6 synthesizes1HNMR spectrogram.
Figure 13 is the schematic diagram for the Hyperbranched polyphenylene ether amines that embodiment 7 synthesizes.
Figure 14 is the Hyperbranched polyphenylene ether amines that embodiment 7 synthesizes1HNMR spectrogram.
Figure 15 is the DSC spectrogram of the solidfied material obtained after being used as curing agent and AFG-90 to solidify simultaneously DDS and TMA.
Figure 16 is the DSC spectrogram of the solidfied material obtained after solidifying the product of example 1 as curing agent and AFG-90.
Figure 17 is the DSC spectrogram of the solidfied material obtained after solidifying DDS as curing agent and AFG-90.
Figure 18 is the solidfied material obtained after dendritic Boltorn H20 solidifies as curing agent and AFG-90
DSC spectrogram.
Figure 19 be HPSA, DMTDA, THPA respectively with the thermogravimetric analysis (TGA) of the obtained solidfied material of epoxy resin AFG-90
Figure.
Specific embodiment
The present invention provides a kind of ultrabranching polyamide and its preparation method and purposes.
Compared with prior art, the present invention utilizes diaminodiphenylsulfone or diamino-diphenyl ether and 1,3,5- benzene three for the first time
Formic acid obtains dissaving polymer as epoxy curing agent as polymerized monomer.Contain a large amount of phenyl ring and sulfone in polymer
Base, the heat resistance for enabling to the product after solidifying to have, and hyperbranched structure is for mechanical property and mobility
Due to certain improvement.Each attached drawing is explained as follows:
Fig. 1 is the schematic diagram for the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes；Fig. 2 is the Hyperbranched polyphenylene that embodiment 1 synthesizes
The schematic diagram of sulfone amine block；Fig. 3 is the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes1HNMR spectrogram；Fig. 4 is to implement
The GPC spectrogram for the Hyperbranched polyphenylene sulfone amine that example 1 synthesizes；Fig. 5 is the DSC spectrogram for the Hyperbranched polyphenylene sulfone amine that embodiment 1 synthesizes；Figure
The schematic diagram of the 6 Hyperbranched polyphenylene sulfone amine synthesized for embodiment 3；Fig. 7 is the GPC for the Hyperbranched polyphenylene sulfone amine that embodiment 3 synthesizes
Spectrogram；Fig. 8 is the schematic diagram for the generation Hyperbranched polyphenylene sulfone amine that embodiment 4 synthesizes；Fig. 9 is the generation over-expense that embodiment 4 synthesizes
Change polyphenylsulfone amine1HNMR spectrogram；Figure 10 is the schematic diagram for the generation Hyperbranched polyphenylene sulfone amine that embodiment 5 synthesizes；Figure 11 is real
Apply the schematic diagram of the generation Hyperbranched polyphenylene ether amines of the synthesis of example 6；Figure 12 is the generation Hyperbranched polyphenylene ether amines that embodiment 6 synthesizes
's1HNMR spectrogram；Figure 13 is the schematic diagram for the Hyperbranched polyphenylene ether amines that embodiment 7 synthesizes；Figure 14 is the over-expense that embodiment 7 synthesizes
Change polyphenyl ether amines1HNMR spectrogram；Figure 15 is the solidification obtained after being used as curing agent and AFG-90 to solidify simultaneously DDS and TMA
The DSC spectrogram of object；Figure 16 is the DSC spectrogram of the solidfied material obtained after solidifying the product of example 1 as curing agent and AFG-90；
Figure 17 is the DSC spectrogram of the solidfied material obtained after solidifying DDS as curing agent and AFG-90；Figure 18 is dendritic
The DSC spectrogram for the solidfied material that Boltorn H20 is obtained after solidifying as curing agent and AFG-90；Figure 19 be HPSA, DMTDA,
THPA respectively with thermogravimetric analysis (TGA) figure of the obtained solidfied material of epoxy resin AFG-90.
It elaborates below in conjunction with attached drawing to the embodiment of the present invention.Specific embodiment is with technical solution of the present invention
Premised on implemented, including detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
State embodiment.
Embodiment 1
The Hyperbranched polyphenylene sulfone amine preparation method of the present embodiment includes the following steps:
As shown in Figure 1, by monomer diaminodiphenylsulfone (3.75mmol), branched monomer 1,3,5- benzenetricarboxylic acid
(2.5mmol), pyridine (3.75ml) and 20ml N-Methyl pyrrolidone are added in reactor.150 DEG C are heated to, so that single
Body is completely dissolved.Triphenyl phosphite (1.95ml) is slowly dropped into.It keeps hot thermotonus 24 hours, obtains polymerizate
HPSA。
As shown in Fig. 2, being blocked for test GPC to product amino that may be present and carboxyl.First to being likely to occur
Amino blocked.It reacts and 1,3,5- benzenetricarboxylic acids (1.25mmol) is added in obtained mixed solution, pyridine (1.27ml),
It is reacted at 100 DEG C for 24 hours, methanol extraction is added, filtered, vacuum drying.
Then product carboxyl that may be present is blocked.Product obtained in the previous step, paraphenetidine
(3.75mmol), pyridine (2ml), triphenyl phosphite (1ml) are added in reactor, are dissolved with N-Methyl pyrrolidone, 120
It is reacted 24 hours at DEG C.
200ml methanol extraction is added, centrifugation obtains faint yellow solid, is dried in vacuo, obtains black liquor, then by black
Liquid precipitates in 100ml methanol, obtains faint yellow solid, is centrifuged, and vacuum drying obtains the inclined black solid of brown, at 200 DEG C
Lower vacuum drying, obtains black solid.
As shown in figure 3, the nuclear-magnetism structure confirmation data of the polymer is as follows:1HNMR(DMSO-d6, ppm):
10.99,10.93,8.69,8.03,8.29-7.75,7.73,7.67,7.53,7.51,6.94,6.92,6.61,
6.58,3.73。
According to the ratio of hydrogen atom on amide group in nuclear magnetic data and branched monomer phenyl ring, estimate the degree of branching on 20% left side
It is right.
As shown in figure 4, GPC measure product matter average molecular weight be 6203g/mol, weight average molecular weight 21946g/mol,
Molecular weight distribution index is 3.538.
Embodiment 2
The Hyperbranched polyphenylene sulfone amine preparation method of the present embodiment includes the following steps:
As shown in Figure 1, by monomer diaminodiphenylsulfone (18.75mmol), branched monomer 1,3,5- benzenetricarboxylic acid
(12.5mmol) and pyridine (17.5ml) are added in reactor, are dissolved using N-Methyl pyrrolidone.110 DEG C are heated to, is made
Monomer is obtained to be completely dissolved.Triphenyl phosphite (9ml) is slowly dropped into.It is heated to 150 DEG C to react 24 hours, obtains polymerizate
HPSA。
Product is concentrated.Methanol extraction is added, vacuum drying is repeated twice.
Embodiment 3
The Hyperbranched polyphenylene sulfone amine preparation method of the present embodiment includes the following steps:
As shown in fig. 6, in anhydrous conditions, by monomer diaminodiphenylsulfone (7mmol), n,N-Dimethylformamide
(7.5ml), triethylamine (1ml) are added in reactor.It is cooled to 0 DEG C.Trimesoyl chloride (5mmol) is used into N, N- dimethyl methyl
It is added dropwise after amide (7.5ml) dissolution.Reaction is heated to 90 DEG C of reactions after 18 hours.Product precipitates in ice ether, filters, and does
It is dry, obtain HPSA.
As shown in Fig. 2, being blocked for test GPC to product carboxyl that may be present.By HPSA (1.95g), diamino
Diphenyl sulphone (DPS) (4mmol), pyridine (1.14ml), N-Methyl pyrrolidone (16ml), triphenyl phosphite (1.24ml) are added to instead
It answers in device, is reacted 3 hours at 100 DEG C.Product precipitates in methyl alcohol, filters, dry.
As shown in fig. 7, GPC measure product matter average molecular weight be 7172g/mol, weight average molecular weight 26403g/mol,
Molecular weight distribution index is 3.681.
Embodiment 4
The amide amine preparation method of the present embodiment includes the following steps:
As shown in figure 8, in anhydrous conditions, by monomer diaminodiphenylsulfone (0.33mmol), n,N-Dimethylformamide
(4ml), triethylamine (0.5ml) are added in reactor.It is cooled to 0 DEG C.Trimesoyl chloride (0.1mmol) is used into N, N- dimethyl
It is added dropwise after formamide (7.5ml) dissolution.When reacting 6.Product precipitates in ice ether, filters, dry, obtains HPSA.
Embodiment 5
The amide preparation method of the present embodiment includes the following steps:
As shown in Figure 10, by monomer diaminodiphenylsulfone (9.9mmol), 1,3,5- benzenetricarboxylic acids (3mmol) and pyridine
(1.1ml) is added in reactor, is dissolved using N-Methyl pyrrolidone.Triphenyl phosphite (1.75ml) is slowly dropped into.
It is heated to 90 DEG C to react 30 hours, obtains product liquid.
Product is concentrated.Methanol extraction, vacuum drying is added.
Embodiment 6
The amide preparation method of the present embodiment includes the following steps:
As shown in figure 11, by monomer diaminodiphenyl ether (9.9mmol), 1,3,5- benzenetricarboxylic acids (3mmol) and pyridine
(1.4ml) is added in reactor, is dissolved using N-Methyl pyrrolidone.Triphenyl phosphite (1.75ml) is slowly dropped into.
It is heated to 90 DEG C to react 12 hours, obtains product liquid.
Product is concentrated.Methanol extraction, vacuum drying is added.
Embodiment 7
The amide preparation method of the present embodiment includes the following steps:
As shown in figure 13, by monomer diaminodiphenyl ether (1.875mmol), 1,3,5- benzenetricarboxylic acids (1.25mmol) and pyrrole
Pyridine (1.4ml) is added in reactor, uses N, N-dimethylformamide dissolution.Triphenyl phosphite (1.47ml) is slowly dripped
Enter.It is heated to 80 DEG C to react 7.5 hours, obtains product.
Product is concentrated.Methanol extraction is added, vacuum drying is repeated twice.
By the Hyperbranched polyphenylene sulfone amine (HPSA) that example 1 obtains and the generation Hyperbranched polyphenylene sulfone amine (HPSA that example 4 obtains
(small molecule)), and high temperature resistant curing agent 4 as a comparison, 4'- diphenyl sulphone (DPS) diamines (DDS), dimethythiotoluene diamine
(DMTDA), cis- 1,2,3,6- tetrabydrophthalic anhydride (THPA), commercially available hyperbranched curing agent Bo ltorn
H20 and epoxy resin AFG-90 solidifies.Condition of cure are as follows: 100 DEG C are reacted 1 hour, and 120 DEG C are reacted 1 hour, and 150 DEG C of reactions 1 are small
When, 180 DEG C are reacted 2 hours, and 200 DEG C are reacted 1 hour.Dissolubility after mixing at 100 DEG C is with as shown below.
DSC (shown in Figure 16, Figure 17) is carried out to finally obtained cured product, solidfied material Thermal Decomposition Data such as Figure 19 institute
Show.
Mechanical property comparison is as follows:
The present invention innovatively provides a kind of novel ultrabranching polyamide, passes through amide by diaminodiphenylsulfone and phenyl ring
Key connection composition, and provide preparation method.The present invention utilizes functional group and dissaving structure in above-mentioned polymer, as
Epoxy curing agent improves the heat resistance and mechanical property of epoxy resin.
Under the teaching of the present invention and the above embodiments, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
The above disclosure is just a few specific examples of the present application, however, this application is not limited to this, any this field
Technical staff can think variation, should all fall in the protection domain of the application.
Claims (10)
1. a kind of ultrabranching polyamide, which is characterized in that shown in monomer general structure such as formula (1):
Particularly, first generation dissaving polymer therein, shown in monomer general structure such as formula (2):
Wherein, intramolecular group R1Selected from-SO2Sulfuryl ,-O- ehter bond；End group (including R2、R3、R4) include but is not limited to :-
H hydrogen ,-OH hydroxyl etc..
2. ultrabranching polyamide as described in claim 1, it is characterised in that: by the monomer containing trifunctional, phenyl ring and contain
There is the monomer of two functional groups, phenyl ring, sulfuryl or ehter bond to be prepared.
3. ultrabranching polyamide as claimed in claim 2, it is characterised in that: the monomer containing trifunctional and phenyl ring is
Three formyl chloride of 1,3,5- benzenetricarboxylic acid or 1,3,5- benzene.
4. ultrabranching polyamide as claimed in claim 3, it is characterised in that: it is described containing two functional groups, phenyl ring, sulfuryl list
Body can be diamino diphenyl sulfone；Monomer containing two functional groups, phenyl ring, ehter bond is diamino-diphenyl ether.
5. the ultrabranching polyamide as described in Claims 1 to 4, it is characterised in that:
Matter average molecular weight is 750-30000g/mol, weight average molecular weight 750-90000g/mol；
Molecular weight distributing index is 1-4；
The degree of branching is 0.1-1；
Glass transition temperature is 200 to 300 DEG C.
6. a kind of purposes of ultrabranching polyamide as described in Claims 1 to 5 as curing agent.
7. the preparation method of ultrabranching polyamide as claimed in claim 4, which is characterized in that raw material uses 1,3,5- benzene front threes
Acid is the synthesis process of branched monomer, comprising the following steps:
(1) 1,3,5- benzenetricarboxylic acid, pyridine, diamino diphenyl sulfone or diamino-diphenyl ether N-Methyl pyrrolidone is molten
Solution, heating；
(2) triphenyl phosphite is slowly added into；
(3) temperature, reaction are kept.
8. the preparation method of ultrabranching polyamide as claimed in claim 7, which is characterized in that anti-in step (1), (2) and (3)
Answering temperature is 110~150 DEG C；In step (3) reaction time be 3~for 24 hours.
9. the preparation method of ultrabranching polyamide as claimed in claim 4, which is characterized in that raw material uses 1,3,5- benzene front threes
Acyl chlorides is the synthesis process of branched monomer, comprising the following steps:
(1) under anhydrous condition, by diamino diphenyl sulfone or diamino-diphenyl ether and triethylamine N-Methyl pyrrolidone or
N,N-Dimethylformamide dissolution, it is cooling；
(2) three formyl chloride of 1,3,5- benzene is slowly added into using N-Methyl pyrrolidone or N,N-dimethylformamide；
(3) it heats, reaction.
10. the preparation method of ultrabranching polyamide as claimed in claim 9, which is characterized in that cooling temperature in step (1), (2)
Degree is 0 DEG C~room temperature, and the reaction temperature in step (3) refers to 60~110 DEG C；Reaction time in step (3) refers to 3~for 24 hours.
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| CN113024833A (en) * | 2021-03-16 | 2021-06-25 | 西北工业大学 | Epoxy end group fluorine-containing hyperbranched structure interface compatilizer and preparation method thereof, and wave-transparent composite material and preparation method thereof |
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| CN110343242A (en) * | 2019-07-04 | 2019-10-18 | 岭南师范学院 | Photochromic hyperbranched azopolyamide of one kind and preparation method thereof |
| CN113024833A (en) * | 2021-03-16 | 2021-06-25 | 西北工业大学 | Epoxy end group fluorine-containing hyperbranched structure interface compatilizer and preparation method thereof, and wave-transparent composite material and preparation method thereof |
| CN113024833B (en) * | 2021-03-16 | 2022-02-15 | 西北工业大学 | Epoxy end group fluorine-containing hyperbranched structure interface compatilizer and preparation method thereof, and wave-transparent composite material and preparation method thereof |
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