CN107099116A - The preparation method of polyamide polyamines intercalation phyllosilicate composite - Google Patents
The preparation method of polyamide polyamines intercalation phyllosilicate composite Download PDFInfo
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- CN107099116A CN107099116A CN201710350367.XA CN201710350367A CN107099116A CN 107099116 A CN107099116 A CN 107099116A CN 201710350367 A CN201710350367 A CN 201710350367A CN 107099116 A CN107099116 A CN 107099116A
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- polyamide polyamines
- intercalation
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- polyamide
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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
- C08K3/346—Clay
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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
- C08G59/50—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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The application provides a kind of preparation method of polyamide polyamines intercalation phyllosilicate composite, comprises the following steps：By polyamide polyamines, deionized water, coupling agent, defoamer and laminar silicate compounds are well mixed, 110 DEG C ~ 150 DEG C are warming up in nitrogen atmosphere, maintain pressure 0.2MPa ~ 0.6MPa, stirring 1 ~ 3 hour, flowed back 1 ~ 4 hour after slow pressure release to normal pressure, dehydration, 160 DEG C ~ 200 DEG C are warming up to again, stirring 2 ~ 6 hours, it is cooled to again more than the fusing point of polyamide polyamines and carries out peeling off restructuring intercalation, obtain polyamide polyamines intercalation phyllosilicate composite, the polyamide intercalation phyllosilicate composite is used for the solidification of epoxy resin, solidfied material heat distortion temperature improves more than 30 DEG C, toughness, caking property, wearability, intensity etc. has obtained further raising.
Description
Technical field
The present invention relates to modified polyamide polyamines, more particularly to a kind of polyamide polyamines intercalation phyllosilicate composite wood
Material.
Background technology
Polyamide polyamines are widely used in ring because of the toughness that its caking property having had the advantages that, cured product have had
The solidification of oxygen tree fat, but the heat resistance of its solidfied material is low（80 DEG C of heat distortion temperature ＜）, the shortcomings of rigidity is low, wearability is poor
It is restricted its application.
The method of traditional solution polyamide polyamines shortcoming is to be formulated by adjusting, such as add some specific epoxy trees
Fat or the curing agent for adding some properties, to improve its performance.But be difficult to there is formula to keep its good bonding
Property, toughness while, moreover it is possible to improve its heat resistance, rigidity, wearability etc., have in addition can also increase toxicity.
The content of the invention
Based on this, it is necessary to multiple there is provided a kind of polyamide polyamines intercalation phyllosilicate the problem of in background technology
The preparation method of condensation material, the polyamide polyamines intercalation phyllosilicate composite that the preparation method is prepared, is not only solved
Polyamide polyamines heat resistance is low, rigidity is low, the shortcomings of wear no resistance, the advantages of also enhancing its good caking property and toughness.
A kind of preparation method of polyamide polyamines intercalation phyllosilicate composite, comprises the following steps：
Obtain polyamide polyamines；
The polyamide polyamines, deionized water, coupling agent, defoamer and laminar silicate compounds are well mixed, in nitrogen
110 DEG C ~ 150 DEG C are warming up in atmosphere, pressure 0.2MPa ~ 0.6MPa is maintained, stirred 1 ~ 3 hour, is returned after slow pressure release to normal pressure
Stream 1 ~ 4 hour, dehydration, then it is warming up to 160 DEG C ~ 200 DEG C, stir 2 ~ 6 hours, obtain polyamide polyamines intercalation phyllosilicate and answer
Compound；
The polyamide polyamines intercalation layered silicate composite is carried out to peel off restructuring intercalation, polyamide polyamines intercalation layer is obtained
Shape silicate composite material.
In one of the embodiments, the polyamide polyamines intercalation layered silicate composite peel off recombinating and inserted
Layer, the step of obtaining polyamide polyamines intercalation phyllosilicate composite is specially：
By the polyamide polyamines intercalation layered silicate composite, it is more than the fusing point for being cooled to the polyamide polyamines, stirring 1
~ 5 hours, obtain polyamide polyamines intercalation phyllosilicate composite.
In one of the embodiments, the mass ratio relation between each raw material is as follows：
50.5 ~ 96.8 parts of polyamide polyamines；
1 ~ 10 part of deionized water；
0.1 ~ 3.5 part of coupling agent；
0.1 ~ 1.0 part of defoamer；
2 ~ 35 parts of laminar silicate compounds.
In one of the embodiments, the mass ratio relation between each raw material is as follows：
73.7 ~ 94.4 parts of polyamide polyamines；
2 ~ 8 parts of deionized water；
0.3 ~ 2.5 part of coupling agent；
0.3 ~ 0.8 part of defoamer；
3 ~ 15 parts of laminar silicate compounds.
In one of the embodiments, layered silicate compound is the inorganic laminated silicate based on clay
Or the organic modified sheet silicate based on clay.
In one of the embodiments, the mesh of the fineness of layered silicate compound >=300.
In one of the embodiments, the defoamer in tributyl phosphate, methyl-silicone oil and octanol at least one
Kind.
In one of the embodiments, the coupling agent is amino silicane coupling agent, and the amino silicane coupling agent is selected from
Aminopropylsiloxane, phenylaminomethyl siloxanes and γ-（Ethylenediamine base）At least one in hydroxypropyl methyl dimethoxysilane
Kind.
The preparation method of above-mentioned polyamide polyamines intercalation phyllosilicate composite, is first prepared using polyamide polyamines
Polyamide polyamines intercalation layered silicate composite, then the polyamide polyamines intercalation layered silicate composite is subjected to stripping weight
Group intercalation, the polyamide intercalation phyllosilicate composite prepared is used for the solidification of epoxy resin, solidfied material thermal deformation temperature
Degree improves more than 30 DEG C, and toughness, caking property, wearability, intensity etc. have obtained further raising.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, specific reality below to the present invention
The mode of applying is described in detail.Many details are elaborated in the following description to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
A kind of preparation method of polyamide polyamines intercalation phyllosilicate composite, comprises the following steps：
S110, acquisition polyamide polyamines.
It should be noted that the polyamide polyamines fusing point can both be synthesized within 100 DEG C by existing method,
Can be commercially available.
S120, above-mentioned polyamide polyamines, deionized water, coupling agent, defoamer and laminar silicate compounds are mixed equal
It is even, 110 DEG C ~ 150 DEG C are warming up in nitrogen atmosphere, pressure 0.2MPa ~ 0.6MPa is maintained, stirred 1 ~ 3 hour, slow pressure release is extremely
Flowed back 1 ~ 4 hour after normal pressure, dehydration, then it is warming up to 160 DEG C ~ 200 DEG C, stir 2 ~ 6 hours, obtain polyamide polyamines intercalation stratiform
Silicate composite.
Wherein, the mass ratio relation between each raw material is as follows：
50.5 ~ 96.8 parts of polyamide polyamines；
1 ~ 10 part of deionized water；
0.1 ~ 3.5 part of coupling agent；
0.1 ~ 1.0 part of defoamer；
2 ~ 35 parts of laminar silicate compounds.
It is preferred that, the mass ratio relation between above-mentioned each raw material is as follows：
73.7 ~ 94.4 parts of polyamide polyamines；
2 ~ 8 parts of deionized water；
0.3 ~ 2.5 part of coupling agent；
0.3 ~ 0.8 part of defoamer；
3 ~ 15 parts of laminar silicate compounds.
Wherein, laminar silicate compounds are the inorganic laminated silicate based on clay（As montmorillonite, rectorite,
Sepiolite, bentonite, kaolin etc.）Or the organic modified sheet silicate based on clay（Such as organobentonite, You Jimeng
De- soil etc.）.
It is preferred that, the mesh of the fineness of above-mentioned laminar silicate compounds >=300.
Wherein, defoamer is selected from least one of tributyl phosphate, methyl-silicone oil and octanol.
Coupling agent is amino silicane coupling agent.
It is preferred that, above-mentioned amino silicane coupling agent be selected from aminopropylsiloxane, phenylaminomethyl siloxanes and γ-（Second
Two amidos）Hydroxypropyl methyl dimethoxysilane.
S130, by above-mentioned polyamide polyamines intercalation layered silicate composite carry out peel off restructuring intercalation, obtain polyamide
Polyamines intercalation phyllosilicate composite.
Specifically, by above-mentioned polyamide polyamines intercalation layered silicate composite, being cooled to the molten of the polyamide polyamines
More than point, stir 1 ~ 5 hour, obtain polyamide polyamines intercalation phyllosilicate composite.
The preparation method of above-mentioned polyamide polyamines intercalation phyllosilicate composite, is first prepared using polyamide polyamines
Polyamide polyamines intercalation layered silicate composite, then the polyamide polyamines intercalation layered silicate composite is subjected to stripping weight
Group intercalation, the polyamide intercalation phyllosilicate composite prepared is used for the solidification of epoxy resin, solidfied material thermal deformation temperature
Degree improves more than 30 DEG C, and toughness, caking property, wearability, intensity etc. have obtained further raising.
It is specific embodiment below.
Embodiment 1
By 1000g polyamide polyamines（The fusing point of the polyamide polyamines is 40 DEG C）, 50g deionized waters, 8g aminopropyl-triethoxies
The sodium-based montmorillonite of silane, 6g tributyl phosphates and the mesh of 60g 500 is well mixed, and 110 DEG C, pressure are warming up in nitrogen atmosphere
Control is stirred 2.5 hours in 0.25MPa, is flowed back 2 hours after slow pressure release to normal pressure, dehydration, is warming up to 170 DEG C of stirrings 3 small
When, it is cooled to≤60 DEG C and stirs 3 hours, that is, obtains polyamide polyamines intercalation phyllosilicate composite.
For epoxy resin cure：Sampling and bisphenol A type epoxy resin（E-51）Mix and solidify, measure heat distortion temperature
114℃。
Embodiment 2
By 1000g polyamide polyamines（The fusing point of the polyamide polyamines is 40 DEG C）, 70g deionized waters, 15g aminopropyl-triethoxies
Silane, 6g tributyl phosphates and the mesh sodium-based montmorillonites of 100g 500 are well mixed, and 120 DEG C, pressure are warming up in nitrogen atmosphere
Control is stirred 2.5 hours in 0.3MPa, slowly lets out to normal pressure backflow 2 hours, and dehydration is warming up to 170 DEG C and stirred 3 hours, drop
Extremely≤60 DEG C of temperature is stirred 3 hours, that is, obtains polyamide polyamines intercalation phyllosilicate composite.
For epoxy resin cure：Sampling and bisphenol A type epoxy resin（E-51）Mix and solidify, measure heat distortion temperature
119℃。
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (8)
1. a kind of preparation method of polyamide polyamines intercalation phyllosilicate composite, it is characterised in that comprise the following steps：
Obtain polyamide polyamines；
The polyamide polyamines, deionized water, coupling agent, defoamer and laminar silicate compounds are well mixed, in nitrogen
110 DEG C ~ 150 DEG C are warming up in atmosphere, pressure 0.2MPa ~ 0.6MPa is maintained, stirred 1 ~ 3 hour, is returned after slow pressure release to normal pressure
Stream 1 ~ 4 hour, dehydration, then it is warming up to 160 DEG C ~ 200 DEG C, stir 2 ~ 6 hours, obtain polyamide polyamines intercalation phyllosilicate and answer
Compound；
The polyamide polyamines intercalation layered silicate composite is carried out to peel off restructuring intercalation, polyamide polyamines intercalation layer is obtained
Shape silicate composite material.
2. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In the polyamide polyamines intercalation layered silicate composite is carried out to peel off restructuring intercalation, polyamide polyamines intercalations layer is obtained
The step of shape silicate composite material is specially：
By the polyamide polyamines intercalation layered silicate composite, it is more than the fusing point for being cooled to the polyamide polyamines, stirring 1
~ 5 hours, obtain polyamide polyamines intercalation phyllosilicate composite.
3. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In the mass ratio relation between each raw material is as follows：
50.5 ~ 96.8 parts of polyamide polyamines；
1 ~ 10 part of deionized water；
0.1 ~ 3.5 part of coupling agent；
0.1 ~ 1.0 part of defoamer；
2 ~ 35 parts of laminar silicate compounds.
4. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In the mass ratio relation between each raw material is as follows：
73.7 ~ 94.4 parts of polyamide polyamines；
2 ~ 8 parts of deionized water；
0.3 ~ 2.5 part of coupling agent；
0.3 ~ 0.8 part of defoamer；
3 ~ 15 parts of laminar silicate compounds.
5. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In layered silicate compound is the inorganic laminated silicate or organically-modified based on clay based on clay
Phyllosilicate.
6. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In the mesh of fineness >=300 of, layered silicate compound.
7. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In the defoamer is selected from least one of tributyl phosphate, methyl-silicone oil and octanol.
8. the preparation method of polyamide polyamines intercalation phyllosilicate composite according to claim 1, its feature exists
In the coupling agent is amino silicane coupling agent, and the amino silicane coupling agent is selected from aminopropylsiloxane, phenylaminomethyl
Siloxanes and γ-（Ethylenediamine base）At least one of hydroxypropyl methyl dimethoxysilane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108611919A (en) * | 2018-03-29 | 2018-10-02 | 句容市茂源织造厂 | A kind of fluting medium reinforcing agent and preparation method thereof |
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