CN110483716A - A kind of original position self-reinforcing polyimides composite material and preparation method - Google Patents
A kind of original position self-reinforcing polyimides composite material and preparation method Download PDFInfo
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- CN110483716A CN110483716A CN201910766501.3A CN201910766501A CN110483716A CN 110483716 A CN110483716 A CN 110483716A CN 201910766501 A CN201910766501 A CN 201910766501A CN 110483716 A CN110483716 A CN 110483716A
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A kind of self-reinforcing polyimides composite material and preparation method in situ being covalently attached by imine linkage, belongs to technical field of composite materials.The present invention is stirred evenly after amino silane, dialdehyde, diamines are dissolved in isopropanol or alcohol solvent, is then heated 72~120 hours at 55~65 DEG C, is obtained polyimides；It is crushed into powder last 80~120 mesh of mistake, then 55~110min of hot pressing is formed at 80~95kPa, 60~70 DEG C, obtains self-reinforcing polyimides composite material in situ.The present invention is adjusted using the raw material of different proportion and then synthesizes polyimides material, it is covalent by the imines metathesis reaction formation imine linkage of dynamic covalent chemical in polyimides material, the amino silane of addition can be used as crosslinking agent and form silica inorganic reinforced phase, the mechanical performance of material is further improved, to obtain the polyimides composite material of the self-reinforcing in situ with certain mechanical performance.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of self-reinforcing in situ being covalently attached by imine linkage
Polyimides composite material and preparation method.
Background technique
Current widely applied plastics are broadly divided into two class of thermosetting plastics and thermoplastic, and wherein thermosetting plastics has
There are good mechanical strength and physicochemical property, but can not reuse.Thermoplastic can repeat processing and use, but
It is that there are huge defects in mechanical properties.Then, it repeats processing and utilization and the material with certain mechanical performance has
Broad application prospect.
Chinese patent CN 104788911A is prepared for high thermal conductivity, low viscosity by dispersing inorganic filler in the epoxy
Epoxy resin composite material, but it is during the preparation process, and curing agent need to be added, and preparation process is more complex, and temperature is higher and consumes
When it is longer.Chinese patent CN 104130509A discloses that a kind of viscosity is high, density is low, intensity is big, low-heat-generation and has receipts
The preparation method of the strong sticky cross-linking body material of contracting rebound memory toughness, but it needs special addition crosslinking agent during the preparation process.
Chinese patent CN 104356505A discloses that a kind of Industrial Solid Waste loading is big, density is low, mechanical property is good, shock resistance
The method of strong lightweight general-purpose plastics composite material, however its preparation process needs high temperature, coupling agent and various added materials simultaneously
It cannot mix in any proportion, adjustability is low.
It follows that although the preparation method of composite material is more at present, there are some problems in synthetic method, if any
A little preparation process need to add crosslinking agent, catalyst, the adjustability of most of composite materials different composition ratio during the preparation process
It is low, it is overall even if being that usually there is still a need for coupling agents etc. by chemistry key connection, but between each phase between some nanocomposite constituents
For preparation process is complicated, temperature is excessively high, takes a long time.
Summary of the invention
Present invention aims at developing, a kind of " one kettle way " is prepared by being covalently keyed, mixed proportion is adjustable, nothing
Need added binding agents, can green processing molding and in-situ preparation inorganic reinforcement phase self-reinforcing polyimides composite material in situ
And preparation method thereof.
The present invention is different from polyamide, polyimides and polyurethane using polyimides material prepared by dialdehyde and diamines,
Amido (or imido grpup) is connected by carbon nitrogen singly-bound with acyl group in polyamide, polyimides and polyurethane, is had very high
Metathesis exchange reaction can not occur for chemical stability.And the macromolecular chain of polyimides composite material prepared by the present invention is logical
Carbon-to-nitrogen double bon connection is crossed, the imines metathesis reaction of dynamic covalent chemical can occur at 60~70 DEG C, there is cold plasticity.This hair
The polyimides material that the bright raw material using different proportion is adjusted and then synthesized, passes through the imines metathesis reaction of dynamic covalent chemical
It forms imine linkage to be covalently attached, and the amino silane added can be used as crosslinking agent, wherein inorganic reinforcement phase is formed, it can be in low temperature
The polyimides composite material with certain mechanical performance is obtained under hot pressing condition.
A kind of preparation side of self-reinforcing polyimides composite material in situ being covalently attached by imine linkage of the present invention
Method is with amino silane instead of traditional crosslinking agent, and its step are as follows:
(1) by amino silane (for the silane compound with primary amine group, including but not limited to 3- aminopropyl trimethoxy
Silane, 3- aminopropyl triethoxysilane, 3- aminopropyl dimethoxy methyl-monosilane, 3- aminopropyl diethoxymethylsilane,
3- (2- aminoethyl methyl) dimethylamine oxygroup methyl-monosilane, 3- (2- aminoethyl methyl) propyl trimethoxy silicane, 3- (2- ammonia
Ethyl-methyl) propyl-triethoxysilicane, [3- (6- ammonia hexyl methyl) propyl) trimethoxy silane etc.), dialdehyde (including but not
It is limited to the aliphatic dialdehydes such as glutaraldehyde, hexandial, dialdehyde in heptan and its two aldehyde derivatives with side chain, such as terephthalaldehyde, neck
The aromatic dialdehydes such as phthalaldehyde, m-terephthal aldehyde), diamines (including but not limited to diethylenetriamine, N, bis- (the 2- amino second of N-
Base) -1,3- propane diamine etc.) be dissolved in isopropanol or alcohol solvent after stir evenly, then at 55~65 DEG C heat treatment 72~
120 hours, obtain polyimides；Wherein, the mole dosage ratio of dialdehyde, amino silane and diamines be 2.000:(1.000~
1.750): (1.500~1.125)；
(2) polyimides that step (1) obtains are ground into powder, cross 80~120 meshes；
(3) the polyimides powder for obtaining step (2) 55~110min of hot pressing at 80~95kPa, 60~70 DEG C is formed,
Obtain self-reinforcing polyimides composite material in situ.
Detailed description of the invention
Fig. 1: self-reinforcing polyimides composite material in situ (product corresponding to 1 the third line data of table) prepared by embodiment 1 is no
The infared spectrum of same processing mode (hot pressing and non-hot pressing) and raw material；Uncured represents non-hot-pressing processing sample, and Cured is represented
Hot-pressing processing sample, APTMS, GA, DETA respectively represent 3- aminopropyl trimethoxysilane, glutaraldehyde, diethylenetriamine.
Fig. 2: the X of self-reinforcing polyimides composite material in situ (product corresponding to 1 the third line data of table) prepared by embodiment 1
X ray diffraction map；
Fig. 3: self-reinforcing polyimides composite material in situ (product corresponding to 1 the third line data of table) prepared by embodiment 1
Optical photograph, right side sample are the sample for not carrying out repeating to crush hot pressing processing preparation, and left side sample is by repeating to crush heat
The sample of pressure processing preparation.
Fig. 4: the stress strain curve of 8 kinds of self-reinforcing polyimides composite materials in situ prepared by embodiment 1；
Fig. 5: the stretch modulus scatter plot of 8 kinds of self-reinforcing polyimides composite materials in situ prepared by embodiment 1；
Fig. 6: the tensile toughness scatter plot of 8 kinds of self-reinforcing polyimides composite materials in situ prepared by embodiment 1；
Fig. 7: the elongation at break scatter plot of 8 kinds of self-reinforcing polyimides composite materials in situ prepared by embodiment 1；
Fig. 8: the tensile strength scatter plot of 8 kinds of self-reinforcing polyimides composite materials in situ prepared by embodiment 1；
Fig. 9: the stress strain curve of 4 kinds of hot repressing original position self-reinforcing polyimides composite materials prepared by embodiment 2；
Figure 10: the stretching of 4 kinds of hot repressings 1,3,5,7 time self-reinforcing polyimides composite material in situ prepared by embodiment 2
Modulus scatter plot；
Figure 11: the stretching of 4 kinds of hot repressings 1,3,5,7 time self-reinforcing polyimides composite material in situ prepared by embodiment 2
Toughness scatter plot；
Figure 12: the fracture of 4 kinds of hot repressings 1,3,5,7 time self-reinforcing polyimides composite material in situ prepared by embodiment 2
Elongation scatter plot；
Figure 13: the stretching of 4 kinds of hot repressings 1,3,5,7 time self-reinforcing polyimides composite material in situ prepared by embodiment 2
Intensity scatter plot.
Specific embodiment
Embodiment 1
(1) a series of material is obtained
Original polyimides material: it is solution A in the isopropanol of 100mL that the glutaraldehyde of 75.6mL (0.4mmol), which is dissolved in,
Diethylenetriamine and 3- aminopropyl trimethoxysilane (crosslinking agent) are dissolved in the isopropyl of 100mL according to the usage ratio of table 1
It is second liquid in alcohol；Liquid A and liquid B is distinguished magnetic agitation to be uniformly mixed, then second liquid is instilled in solution A dropwise, is stirred simultaneously,
It is moved containers into 60 DEG C of baking ovens after 5min and carries out heat treatment 96 hours, obtain the polyimides material of solid (except the first row
Outside ratio)；
Table 1: the polyimides prepolymer experimental data of different monomers ratio
(2) the original polyimides material solid for obtaining step (1) is ground into powder, crosses 80 meshes；
(3) above-mentioned sample (product of material rate shown in the second row to the 9th row in table 1) 0.8g, In is weighed respectively
9MPa, the self-reinforcing polyimides composite material in situ of 8 kinds of different material ratios, gained composite wood is made in hot pressing 60min at 60 DEG C
Material is 40mm × 10mm × 1mm thin slice.
(4) powder for the composition of the same race that the powder of the composite material obtained to step (3) and non-hot-pressing processing obtain carries out
Infrared detection comparison.
As shown in fig. 1, with carrying out hot-pressing processing to polyimides composite material preparation process, in infrared figure
1637cm-1The absorption peak at place acutely enhances, and in the polyimides material of preparation, the functional group containing partial monosomy, and
And 1033cm is also had more-1The imine linkage at place.Meanwhile from figure 2 it may also be seen that containing in the polyimides powder being prepared
Unformed silica.Further, from figure 3, it can be seen that in molding range, sample reheating after repeating to process
Treated that composite sheet darkens for pressure, and becomes the bad polyimides sample of translucency from the good sample of transparency
Product, being further continued for processing will cause internal inhomogeneities.In conclusion illustrating in polyimides material through imines metathesis reaction
Covalent linkage is formd, and forms silica reinforced phase, further improves the mechanical performance of material, to be had
There is the polyimides composite material of the self-reinforcing in situ of certain mechanical performance.
Embodiment 2
8 kinds of self-reinforcing polyimides composite materials (the 2nd row~the 9th row product in table 1) in situ that embodiment 1 is obtained are again
It is respectively crushed into powder, crosses 80 meshes；It weighs polyimides material powder 0.80g respectively to be put into mold, smooth powder surface；So
Hot pressing 60min is formed under the conditions of 90kPa, 60 DEG C afterwards, can obtain self-reinforcing polyimides composite material in situ again, gained is multiple
Condensation material is 40mm × 10mm × 1mm thin slice.It is repeatedly crushed according to this, hot press operation, by a series of prepared poly- Asias
Amine composite material carries out measuring mechanical property, and test result is as shown in table 2.The result shows that the product of any material rate preparation is all
It can form, be able to maintain good hardness and tensile strength, tensile modulus of elasticity becomes larger as the additive amount of crosslinking agent increases,
And strain-stress relation follows certain rule.
The complete test data of the ABSE-Pi mechanical performance of table 2:ABSE-Pi and reprocessing
The above, best specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
Any to be familiar with those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all
It is covered by the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of original position self-reinforcing polyimides composite material, its step are as follows:
(1) it stirs evenly after amino silane, dialdehyde, diamines being dissolved in isopropanol or alcohol solvent, then adds at 55~65 DEG C
Heat treatment 72~120 hours, obtains polyimides；Wherein, the mole dosage ratio of dialdehyde, amino silane and diamines is 2.000:
(1.000~1.750): (1.500~1.125)；
(2) polyimides that step (1) obtains are ground into powder, cross 80~120 meshes；
(3) the polyimides powder for obtaining step (2) 55~110min of hot pressing at 80~95kPa, 60~70 DEG C is formed, and is obtained
Self-reinforcing polyimides composite material in situ.
2. a kind of preparation method of self-reinforcing polyimides composite material in situ as described in claim 1, it is characterised in that: amino
Silane is 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, 3- aminopropyl dimethoxy methyl-monosilane, 3- ammonia
Propyl diethoxymethylsilane, 3- (2- aminoethyl methyl) dimethylamine oxygroup methyl-monosilane, 3- (2- aminoethyl methyl) third
Base trimethoxy silane, 3- (2- aminoethyl methyl) propyl-triethoxysilicane or [3- (6- ammonia hexyl methyl) propyl) trimethoxy
Base silane.
3. a kind of preparation method of self-reinforcing polyimides composite material in situ as described in claim 1, it is characterised in that: dialdehyde
For glutaraldehyde, hexandial, dialdehyde in heptan, terephthalaldehyde, neck phthalaldehyde or m-terephthal aldehyde.
4. a kind of preparation method of self-reinforcing polyimides composite material in situ as described in claim 1, it is characterised in that: diamines
For diethylenetriamine or N, bis- (2- the amino-ethyl) -1,3- propane diamine of N-.
5. a kind of original position self-reinforcing polyimides composite material, it is characterised in that: be as described in Claims 1 to 4 any one
Method is prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912802A (en) * | 2021-10-21 | 2022-01-11 | 四川大学 | Ionic type polyimine network material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070066765A1 (en) * | 2005-09-16 | 2007-03-22 | General Electric Company | Polyarlyl ether ketone polymer blends |
| US20070112120A1 (en) * | 2000-07-31 | 2007-05-17 | Didier Vasseur | Tread for a tire |
| CN101883824A (en) * | 2007-10-01 | 2010-11-10 | 圣戈班磨料公司 | The liquid resin composition that is used for abrasive article |
| JP2011256394A (en) * | 2011-08-09 | 2011-12-22 | Asahi Kasei E-Materials Corp | Photosensitive heat-resistant resin precursor composition |
| WO2012166832A2 (en) * | 2011-06-02 | 2012-12-06 | Milliken & Company | Porous, low density nanoclay composite |
| CN105647111A (en) * | 2016-04-12 | 2016-06-08 | 吉林大学 | Polyimide composite material connected by imide bond covalence and preparation method thereof |
-
2019
- 2019-08-20 CN CN201910766501.3A patent/CN110483716B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070112120A1 (en) * | 2000-07-31 | 2007-05-17 | Didier Vasseur | Tread for a tire |
| US20070066765A1 (en) * | 2005-09-16 | 2007-03-22 | General Electric Company | Polyarlyl ether ketone polymer blends |
| CN101883824A (en) * | 2007-10-01 | 2010-11-10 | 圣戈班磨料公司 | The liquid resin composition that is used for abrasive article |
| WO2012166832A2 (en) * | 2011-06-02 | 2012-12-06 | Milliken & Company | Porous, low density nanoclay composite |
| JP2011256394A (en) * | 2011-08-09 | 2011-12-22 | Asahi Kasei E-Materials Corp | Photosensitive heat-resistant resin precursor composition |
| CN105647111A (en) * | 2016-04-12 | 2016-06-08 | 吉林大学 | Polyimide composite material connected by imide bond covalence and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MASAKO MIKI ET AL: "Structure–property relationships of hyperbranched polyimide–silica hybrid membranes with different degrees of modification", 《APPLIED POLYMER》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912802A (en) * | 2021-10-21 | 2022-01-11 | 四川大学 | Ionic type polyimine network material and preparation method thereof |
| CN113912802B (en) * | 2021-10-21 | 2022-08-12 | 四川大学 | Ionic polyimine network material and preparation method thereof |
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