CN108707960A - A kind of preparation method and applications of chlorine oxygen magnesium whisker - Google Patents
A kind of preparation method and applications of chlorine oxygen magnesium whisker Download PDFInfo
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- CN108707960A CN108707960A CN201810526251.1A CN201810526251A CN108707960A CN 108707960 A CN108707960 A CN 108707960A CN 201810526251 A CN201810526251 A CN 201810526251A CN 108707960 A CN108707960 A CN 108707960A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention provides a kind of preparation method and applications of chlorine oxygen magnesium whisker, synthesizes chlorine oxygen magnesium whisker using brine-ammonia liquid phase method, includes the following steps：1) the magnesium chloride supersaturated solution for configuring 2.5-4mol/L, pours into reactor, then reactor is positioned in 25-35 DEG C of water bath with thermostatic control, stirs fully dissolving, obtains magnesium chloride solution；2) ammonium hydroxide is added drop-wise in the magnesium chloride solution in step 1), is stirred to react, obtain saturation mother liquor；3) the saturation mother liquor aging crystallization in step 2) is nucleated；4) it waits in step 3) after aging crystallization nucleation, washing drying obtains chlorine oxygen magnesium whisker.Chlorine oxygen magnesium whisker is applied to and is prepared in chlorine oxygen magnesium whisker/epoxy resin composite material.The thermal stability that the present invention prepares composite material is strong, and compressive strength is up to 120MPa, and thermal stability is improved with the increase of chlorine oxygen magnesium Whisker Content.And the raw material of the present invention is easy to get, preparation process is simple, and can large-scale production use.
Description
Technical field
The invention belongs to field of composite material preparation, and in particular to be a kind of preparation method of chlorine oxygen magnesium whisker and its answer
With chlorine oxygen magnesium whisker/epoxy resin composite material and preparation method thereof.
Background technology
With the development of the social economy, the increase of material wealth, population and building are more and more intensive, increase fire hair
Raw frequency.There are several serious fire incidents every year in China：Such as Tianjin Rui Hai companies fire explosion in 2015；
Dalian " 5.21 " fire incident in 2016, these fire incidents have direct or indirect relationship with the construction material used.For
Fire hazard in building, it was recognized that having to look for that inflammable or combustible is made to become difficult to light or be detached from burning things which may cause a fire disaster
The substance of energy self-extinguish.
Epoxy resin is a kind of very important high molecular material, is widely used in coating, adhesive, electronic apparatus material
Material, engineering plastics and the various aspects such as composite material and civil material.But its limit oxygen index is very low, only
19.8%, therefore it belongs to combustible material.Inflammable material is easy to cause fire, causes various losses so that epoxy resin exists
It is very restricted when use, therefore how research improves the thermal stability of epoxy resin and be very important.
How a direction that the thermal stability of epoxy resin be its research and development is improved.Not with electric and electronic industry
Disconnected development, the application field of composite material are gradually widened, the development active demand environment-friendly materials of the mankind so that improve epoxy resin
Thermal stability have very important status.Inorganic combustion inhibitor has the advantages that more than organic fire-retardant, for example synthesizes work
Skill is simple, thermal stability is high, flue gas toxity is small and at low cost etc., meets the requirement now to fire retardant low toxicity, few cigarette.
And magnesium oxychloride product is non-ignitable fire proofing material.Chlorine oxygen magnesium whisker can be used as fire retardant for construction material and product
In, improve its flame retardant property.Chlorine oxygen magnesium whisker (5Mg (OH)2·MgCl2·8H2O) it is a kind of novel flame-retardant, reinforcing fiber material
Material as having been achieved with certain scientific achievement in applying filler to plastics, paper stock, adhesive, but is used as hindering
It is also seldom come the heat-staple report for improving epoxy resin to fire agent.Chlorine oxygen magnesium whisker has due in its structure containing 8 crystallizations water
There is flame retardant property, but it is applied in epoxy resin to the conclusion not yet that whether meets the requirements.In addition for chlorine oxygen magnesium whisker
Although preparation had many research, there is no a best experimental program is determined, so brilliant for chlorine oxygen magnesium
Preparing for palpus still also has certain research space.
Therefore, for the problem of epoxy resin thermostabilization difference, using the fire protecting performance of chlorine oxygen magnesium, chlorine oxygen magnesium is prepared in research
Whisker/epoxy resin composite material is to be of great significance with the thermal stability for improving epoxy resin.
Invention content
Purpose of the present invention is to overcome above-mentioned the problems of the prior art defect, and a kind of preparation of the chlorine oxygen magnesium whisker proposed
Method and its application, chlorine oxygen magnesium whisker/epoxy resin composite material and preparation method thereof.The present invention prepare chlorine oxygen magnesium whisker/
Epoxy resin composite material is to improve the thermal stability of epoxy resin.Meanwhile the technical solution is also the application of chlorine oxygen magnesium whisker
Provide reference value and practical significance.And the advantages of technical scheme of the present invention is that raw material is easy to get, is simple for process, and can advise
Mould produces and uses.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of preparation method of chlorine oxygen magnesium whisker, the preparation method synthesize chlorine oxygen magnesium whisker using brine-ammonia liquid phase method,
The preparation method includes the following steps：
1) the magnesium chloride supersaturated solution for configuring 2.5-4mol/L, pours into reactor, reactor is then positioned over 25-
In 35 DEG C of water bath with thermostatic control, stirring fully dissolves, obtains magnesium chloride solution；
2) ammonium hydroxide is added drop-wise in the magnesium chloride solution in step 1), is stirred to react, obtain saturation mother liquor；
3) the saturation mother liquor aging crystallization in step 2) is nucleated；
4) wait for that in step 3) after aging crystallization nucleation, washing is dry, obtains chlorine oxygen magnesium whisker.
Preparation method as described above, it is preferable that in the step 1), the magnesium chloride supersaturation for configuring 3-3.5mol/L is molten
Liquid pours into reactor；Preferably, reactor is positioned in 30 DEG C of water bath with thermostatic control, is stirred, fully dissolved, obtain magnesium chloride
Solution.
Preparation method as described above, it is preferable that in the step 2), ammonia concn 26-30%；More preferably, ammonium hydroxide
A concentration of 28%.
Preparation method as described above, it is preferable that in the step 2), ammonium hydroxide is dripped with the speed of 10ml/min~20ml/min
It is added in the magnesium chloride solution of steady temperature.
Preparation method as described above, it is preferable that in the step 2), the molar ratio of magnesium chloride and ammonium hydroxide is respectively 3: 5-6:
1。
Preparation method as described above, it is preferable that in the step 2), the magnesium chloride solution that ammonium hydroxide is added drop-wise in step 1)
In, it is stirred to react 1-2h；More preferably, it is stirred to react 1.5h.
Preparation method as described above, it is preferable that in the step 3), by saturation mother liquor aging crystallization nucleation, specific steps
Refer to：It is saturated mother liquor aging crystallization at 50-60 DEG C, digestion time 55-65h.
Preparation method as described above, it is preferable that saturation mother liquor aging crystallization at 55 DEG C, digestion time 60h.
Preparation method as described above, it is preferable that in the step 4), wait in step 3) after aging crystallization nucleation, first
It is washed with distilled water, filters, then washed with absolute ethyl alcohol, the product after washing is put into 45-55 DEG C of drying in air dry oven
8-12h obtains chlorine oxygen magnesium whisker；Preferably, the product after washing is put into 50 DEG C of drying 10h in air dry oven.
A kind of application for the chlorine oxygen magnesium whisker that any one as above is prepared, chlorine oxygen magnesium whisker is applied to and prepares chlorine oxygen magnesium crystalline substance
In palpus/epoxy resin composite material, i.e., chlorine oxygen magnesium whisker is compound with epoxy resin and then prepares chlorine oxygen magnesium whisker/epoxy resin
Composite material improves the stability and anti-flammability of epoxide resin material.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect：
The thermal stability that the present invention prepares chlorine oxygen magnesium whisker/epoxy resin composite material is strong, and the compression of composite material
Intensity is up to 120MPa, and thermal stability is improved with the increase of chlorine oxygen magnesium Whisker Content.And technical scheme of the present invention
Advantage be raw material be easy to get, preparation process it is simple, and can large-scale production use.It has a extensive future.
Description of the drawings
The XRD spectrum of difference chlorine oxygen magnesium whisker when density of magnesium chloride is 3mol/L in Fig. 1 specific embodiment of the invention 1-4.
The XRD diagram of difference chlorine oxygen magnesium whisker when density of magnesium chloride is 3.5mol/L in Fig. 2 specific embodiment of the invention 5-7
Spectrum.
The XRD spectrum for the chlorine oxygen magnesium whisker that in Fig. 3 comparative examples 1 of the present invention prepared by micro emulsion method.
The scanning electron microscopic picture of different chlorine oxygen magnesium whiskers in Fig. 4 specific embodiment of the invention 1-7；
Density of magnesium chloride 3mol/L：(a) magnesium chloride and ammonium hydroxide molar ratio 3: 5；(b) magnesium chloride and ammonium hydroxide molar ratio 4: 1；
(c) magnesium chloride and ammonium hydroxide molar ratio 5: 1；(d) magnesium chloride and ammonium hydroxide molar ratio 6: 1；
Density of magnesium chloride 3.5mol/L：(e) magnesium chloride and ammonium hydroxide molar ratio 4: 1；(f) magnesium chloride and ammonium hydroxide molar ratio 5: 1；
(g) magnesium chloride and ammonium hydroxide molar ratio 6: 1.
The pressure resistance of chlorine oxygen magnesium whisker/epoxy resin composite material in Fig. 5 specific embodiment of the invention 8-13 and comparative example 2
Degree test tendency chart.
The TG curves of Fig. 6 specific embodiment of the invention chlorine oxygen magnesium whisker/epoxy resin composite material.
The DSC curve of Fig. 7 specific embodiment of the invention chlorine oxygen magnesium whisker/epoxy resin composite material.
The scanning electron microscope (SEM) photograph of Fig. 8 specific embodiment of the invention chlorine oxygen magnesium whisker/epoxy resin composite material plane of disruption；Chlorine oxygen
Magnesium whisker incorporation：(a) 0%；(b) 5%；(c) 10%；(d) 20%；(e) unmodified 5%.
The XRD spectrum of Fig. 9 specific embodiment of the invention chlorine oxygen magnesium whisker/epoxy resin composite material plane of disruption.Chlorine oxygen
Magnesium Whisker Content：(a) 0%；(b) 5%；(c) 10%；(d) 20%.
Figure 10 specific embodiment of the invention chlorine oxygen magnesium whisker, epoxy resin and composite material (chlorine oxygen magnesium Whisker Content 10%)
Infared spectrum；(a) chlorine oxygen magnesium whisker；(b) epoxy resin；(c) composite material.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
The every other embodiment that logical technical staff is obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention can be combined with each other.
Specific embodiments of the present invention provide a kind of preparation method and applications of chlorine oxygen magnesium whisker, and chlorine oxygen magnesium whisker/
Epoxy resin composite material and preparation method thereof.Technical scheme of the present invention is mainly using magnesium chloride, ammonium hydroxide as raw material, using halogen
Water-ammonia method prepares chlorine oxygen magnesium whisker, is modified to whisker surface using Silane coupling agent KH550, by modified whisker
It uniformly mixes, causes, chlorine oxygen magnesium whisker/epoxy resin composite material is prepared in polymerization with epoxy resin adhesive liquid.Pass through infrared light
The microcosmic knot of spectrum (IR), scanning electron microscope (SEM), X-ray diffractometer (XRD) characterization chlorine oxygen magnesium whisker/epoxy resin composite material
Structure and form, universal testing machine test its mechanical property, and heat analysis characterizes its thermal stability.The result shows that：Chlorine oxygen magnesium whisker/ring
The compressive strength maximum of epoxy resin composite material reaches 120MPa, and thermal stability is improved with the increase of chlorine oxygen magnesium Whisker Content.
Chlorine oxygen magnesium whisker is synthesized using liquid phase method in specific embodiments of the present invention, in order to obtain best chlorine oxygen magnesium whisker
(phase 5) has formulated two kinds of I methods (brine-ammonia process), II methods (micro emulsion method) experimental programs.Chlorine oxygen magnesium whisker is prepared with brine-ammonia process
Experimentation in, have the concentration of magnesium chloride solution, the addition of ammonium hydroxide, feed time and anti-to the principal element that nucleation influences
Temperature is answered, wherein the addition of the mainly density of magnesium chloride and ammonium hydroxide that are affected.
A kind of preparation method of chlorine oxygen magnesium whisker provided by the invention, this method are prepared using method I (brine-ammonia process),
The preparation method includes the following steps：
1) configure 2.5-4mol/L (such as 2.6mol/L, 2.7mol/L, 2.8mol/L, 2.9mol/L, 3.0mol/L,
3.1mol/L、3.2mol/L、3.3mol/L、3.4mol/L、3.5mol/L、3.6mol/L、3.7mol/L、3.8mol/L、
3.9mol/L, 3.95mol/L) magnesium chloride supersaturated solution, pour into reactor, reactor be then positioned over 25-35 DEG C
(such as 26 DEG C, 26.5 DEG C, 27 DEG C, 27.5 DEG C, 28 DEG C, 28.5 DEG C, 29 DEG C, 29.5 DEG C, 30 DEG C, 30.5 DEG C, 31 DEG C, 31.5 DEG C,
32 DEG C, 32.5 DEG C, 33 DEG C, 33.5 DEG C, 34 DEG C, 34.5 DEG C) water bath with thermostatic control in, stirring, fully dissolve, obtain magnesium chloride solution；
2) ammonium hydroxide is added drop-wise in the magnesium chloride solution in step 1), is stirred to react, obtain saturation mother liquor；
3) the saturation mother liquor aging crystallization in step 2) is nucleated；
4) wait for that in step 3) after aging crystallization nucleation, washing is dry, obtains chlorine oxygen magnesium whisker.
Further preferably, in step 1), configuration 3-3.5mol/L (such as 3.1mol/L, 3.15mol/L, 3.2mol/L,
3.25mol/L, 3.3mol/L, 3.35mol/L, 3.4mol/L, 3.45mol/L) magnesium chloride supersaturated solution, pour into reactor
In, then reactor is positioned in 30 DEG C of water bath with thermostatic control, is stirred, fully dissolved, obtain magnesium chloride solution.
Further preferably, in step 2), ammonia concn be 26-30% (such as 26.5%, 27%, 27.5%, 28%,
28.5%, 29%, 29.5%, 29.8%).More preferably, ammonia concn 28%.
In step 2), ammonium hydroxide with 10ml/min~20ml/min (such as 11ml/min, 12ml/min, 13ml/min,
14ml/min, 15ml/min, 16ml/min, 17ml/min, 18ml/min, 19ml/min) speed be added drop-wise to steady temperature
In magnesium chloride solution.
In step 2), the molar ratio of magnesium chloride and ammonium hydroxide be respectively 3: 5-6: 1 (such as 4: 5,1: 1,1.5: 1,2: 1,2.5:
1、3∶1、3.5∶1、4∶1、4.5∶1、5∶1、5.5∶1、6∶1)。
Preferably, ammonium hydroxide is added drop-wise in the magnesium chloride solution in step 1), be stirred to react 1-2h (such as 1.1h, 1.2h,
1.3h,1.4h,1.5h,1.6h,1.7h,1.8h,1.9h).More preferably, it is stirred to react 1.5h.
Further preferably, in step 3), by saturation mother liquor aging crystallization nucleation, specific steps refer to：Mother liquor is saturated in 50-
60 DEG C (such as 51 DEG C, 51.5 DEG C, 52 DEG C, 52.5 DEG C, 53 DEG C, 53.5 DEG C, 54 DEG C, 54.5 DEG C, 55 DEG C, 55.5 DEG C, 56 DEG C,
56.5 DEG C, 57 DEG C, 57.5 DEG C, 58 DEG C, 58.5 DEG C, 59 DEG C, 59.5 DEG C) under aging crystallization, digestion time be 55-65h (such as
55.5h,56h,56.5h,57h,57.5h,58h,58.5h,59h,59.5h,60h,61.5h,62h,63h,64h).Preferably,
It is saturated mother liquor aging crystallization at 55 DEG C, digestion time 60h.
Further preferably, it in step 4), after waiting for that aging crystallization is nucleated in step 3), is first washed with distilled water, filters,
Washed again with absolute ethyl alcohol, by the product after washing be put into air dry oven 45-55 DEG C (such as 46 DEG C, 47 DEG C, 48 DEG C, 49
DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C, 54.5 DEG C) drying 8-12h (such as 8.5h, 9h, 9.5h, 10h, 10.5h, 11h,
11.5h, 12h), obtain chlorine oxygen magnesium whisker.Preferably, the product after washing is put into 50 DEG C of drying 10h in air dry oven.
It is chlorine oxygen magnesium whisker is compound with epoxy resin and then prepare the present invention also provides a kind of application of chlorine oxygen magnesium whisker
Chlorine oxygen magnesium whisker/epoxy resin composite material, the stability and anti-flammability of epoxide resin material are improved with this.
In addition, the present invention also provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material, the preparation method
Include the following steps：
1) modification of chlorine oxygen magnesium whisker
First water and absolute ethyl alcohol are put into reactor, the volume ratio of absolute ethyl alcohol and water be 8: 1-10: 1 (such as 8.2:
1,8.5:1,8.7:1,9:1,9.2:1,9.5:1,9.7:1,9.9:1,10:1)；Then modifying agent is added into reactor, stirs
Uniformly；Be added followed by chlorine oxygen magnesium whisker, and stir at normal temperatures 50-70min (such as 52min, 54min, 56min, 58min,
60min, 62min, 64min, 66min, 68min, 69min) after be warming up to 55-65 DEG C (such as 56 DEG C, 57 DEG C, 58 DEG C, 59 DEG C,
60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C, 64.5 DEG C) to remove ethyl alcohol, filtering, in 55-65 DEG C (such as 56 DEG C, 57 DEG C, 58 DEG C,
59 DEG C, 60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C, 64.5 DEG C) it is dry, obtain modified chlorine oxygen magnesium whisker；
2) preparation of chlorine oxygen magnesium whisker/epoxy resin composite material
Epoxy resin is put into reactor, and acetone is added into reactor and as solvent and stirs evenly；Then to
Modified chlorine oxygen magnesium whisker is added in reactor, it is dry after stirring evenly, to remove acetone；Curing agent is then added and stirs
It mixes uniformly, obtains mixture；
3) curing molding of chlorine oxygen magnesium whisker/epoxy resin composite material
In the mold that mixture in step 2) is poured into, it is put into vacuum drying chamber and vacuumizes to remove bubble, solidification；
It is demoulded after the completion of to be solidified, takes out sample, obtain chlorine oxygen magnesium whisker/epoxy resin composite material.
Further preferably, in step 1), the volume ratio of absolute ethyl alcohol and water is 9: 1.Modifying agent is silane coupling agent
(KH550).A concentration of 4-6% of silane coupling agent (such as 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%,
5.6%, 5.8%, 5.9%)；Preferably, silane coupling agent a concentration of 5%.
In step 1), chlorine oxygen magnesium whisker is added after being stirred evenly with glass bar, is risen after then stirring 60min under room temperature
Temperature, to remove ethyl alcohol, is finally filtered to 60 DEG C, is dried under the conditions of 60 DEG C with being put into after ethanol wash sample in vacuum drying chamber, is received
Collect modified chlorine oxygen magnesium whisker.
More preferably, step 1) is water and absolute ethyl alcohol with graduated cylinder measurement certain volume in beaker, it is desirable that anhydrous second
The volume ratio of alcohol and water is 9: 1,5% silane coupling agent (KH550) is then added into beaker, after being stirred evenly with glass bar
Chlorine oxygen magnesium whisker is added, 60 DEG C is then warming up under room temperature after stir about 60min to remove ethyl alcohol, finally filters, uses alcohol
It is put into after washing sample in vacuum drying chamber and is dried under the conditions of 60 DEG C, collect modified sample.
Further preferably, in step 2), the addition of modified chlorine oxygen magnesium whisker is the 5-25% of epoxy resin quality
(such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%,
21%, 22%, 23%, 24%).Preferably, the addition of chlorine oxygen magnesium whisker is the 8-15% of epoxy resin quality.Further preferably
Ground, the addition of chlorine oxygen magnesium whisker are the 10% of epoxy resin quality.
In step 2), it is added modified chlorine oxygen magnesium whisker into reactor, 1~1.5h of stirring (such as 1.1h, 1.15h,
1.2h, 1.25h, 1.3h, 1.35h, 1.4h, 1.45h) after be put into vacuum drying chamber 45-55 DEG C (such as 46 DEG C, 47 DEG C, 48
DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C, 54.5 DEG C) under the conditions of 1.5-2.5h (such as 1.6h, 1.7h, 1.8h,
1.9h, 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.45h), to remove acetone.Preferably, it is added into reactor modified
Chlorine oxygen magnesium whisker is put into vacuum drying chamber 2h under the conditions of 50 DEG C, to remove acetone after stirring 1.2h.
In step 2), the curing agent of addition is polyethylene polyamine.The addition of curing agent is the 10% of epoxy resin quality
~15% (such as 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%).
It is further preferred that in step 3), pours the mixture into the mold of 1cm × 1cm, be put into vacuum drying chamber and take out
Then vacuum is cured with removing bubble under the conditions of 60 DEG C.It is demoulded after the completion of to be solidified, takes out sample.
Embodiment 1
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are made using method I (brine-ammonia process)
Standby, which includes the following steps：
1) the magnesium chloride supersaturated solution for configuring 3mol/L, is poured into reactor (beaker of 150ml), then by reactor
It is positioned in 30 DEG C of water bath with thermostatic control, stirs, fully dissolve, obtain magnesium chloride solution；
2) a concentration of 28% ammonium hydroxide is added drop-wise to the magnesium chloride solution of steady temperature in step 1) with the speed of 15ml/min
In, it is stirred to react 1.5h, obtains saturation mother liquor；The molar ratio of magnesium chloride and ammonium hydroxide is 3: 5.
3) the saturation mother liquor aging crystallization in step 2) is nucleated, specific steps refer to：Saturation mother liquor is aged at 55 DEG C
Crystallization, digestion time 60h.
4) it after waiting for that aging crystallization is nucleated in step 3), is first washed with distilled water, filters, then washed with absolute ethyl alcohol,
Product after washing is put into 50 DEG C of drying 10h in air dry oven, obtains chlorine oxygen magnesium whisker.
Embodiment 2
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method I (brine-ammonia process)
The molar ratio of middle magnesium chloride and ammonium hydroxide is 4: 1.Other methods step is identical as in embodiment 1, and the present embodiment is no longer done herein
It repeats.
Embodiment 3
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method I (brine-ammonia process)
The molar ratio of middle magnesium chloride and ammonium hydroxide is 5: 1.Other methods step is identical as in embodiment 1, and the present embodiment is no longer done herein
It repeats.
Embodiment 4
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method I (brine-ammonia process)
The molar ratio of middle magnesium chloride and ammonium hydroxide is 6: 1.Other methods step is identical as in embodiment 1, and the present embodiment is no longer done herein
It repeats.
Embodiment 5
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method I (brine-ammonia process)
The magnesium chloride supersaturated solution of middle configuration 3.5mol/L.Other methods step is identical as in embodiment 2, and the present embodiment is herein not
It repeats again.
Embodiment 6
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method I (brine-ammonia process)
The magnesium chloride supersaturated solution of middle configuration 3.5mol/L.Other methods step is identical as in embodiment 3, and the present embodiment is herein not
It repeats again.
Embodiment 7
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method I (brine-ammonia process)
The magnesium chloride supersaturated solution of middle configuration 3.5mol/L.Other methods step is identical as in embodiment 4, and the present embodiment is herein not
It repeats again.
Comparative example 1
A kind of preparation method of chlorine oxygen magnesium whisker provided in this embodiment, this method are prepared using method II (micro emulsion method).
The preparation method includes the following steps：
1) CTAB (cetyl trimethylammonium bromide) for 1.1g is weighed in beaker, then adds 25mL successively into beaker
The magnesium chloride solution of a concentration of 3.5mol/L of hexamethylene and 0.5g of left and right, is finally constantly added dropwise 7mL into beaker while stirring
The n-butanol of left and right, until solution appearance becomes transparent, clarification；
2) 0.3g MgO are weighed to be slowly added into microemulsion, are stirred to react 4h, then use Ultrasound Instrument ultrasound half small
When, finally stood 12h；
3) liquid after standing is transferred in centrifuge tube, 5min is centrifuged with the centrifugal speed of 4500r/min, is then removed
Centrifugate collects white depositions；
4) sediment after washing centrifugation with absolute ethyl alcohol, is put into low temperature drying 10h in drying box and obtains chlorine oxygen magnesium whisker
Sample.
Embodiment 8
The present embodiment provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material, which includes
Following steps：
1) modification of chlorine oxygen magnesium whisker
The water of certain volume is measured with graduated cylinder and absolute ethyl alcohol is put into reactor (beaker), the volume of absolute ethyl alcohol and water
Than being 9: 1；Then a concentration of 5% modifying agent silane coupling agent (KH550) is added into reactor, after being stirred evenly with glass bar
Chlorine oxygen magnesium whisker is added, 60 DEG C is warming up to remove ethyl alcohol after 60min is then stirred under room temperature, finally filters, washed with alcohol
It washs to be put into vacuum drying chamber after sample and be dried under the conditions of 60 DEG C, collect modified chlorine oxygen magnesium whisker.
2) preparation of chlorine oxygen magnesium whisker/epoxy resin composite material
Epoxy resin is put into reactor, and acetone is added into reactor and as solvent and stirs evenly；Then to
Modified chlorine oxygen magnesium whisker is added in reactor, after stirring 1.2h, 2h under the conditions of 50 DEG C is put into vacuum drying chamber after stirring,
To remove acetone；Curing agent polyethylene polyamine is then added and stirs evenly, obtains mixture.Modified chlorine oxygen magnesium whisker adds
Enter 0% that amount is epoxy resin quality.The addition of curing agent is the 12% of epoxy resin quality.
3) curing molding of chlorine oxygen magnesium whisker/epoxy resin composite material
Mixture in step 2) is poured into the mold of 1cm × 1cm, is put into vacuum drying chamber and vacuumizes to remove degassing
Bubble, is then cured under the conditions of 60 DEG C；It is demoulded after the completion of to be solidified, takes out sample, obtain chlorine oxygen magnesium whisker/asphalt mixtures modified by epoxy resin
Resin composite material.
Embodiment 9
It is modified in the preparation the present embodiment provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material
Chlorine oxygen magnesium whisker addition be epoxy resin quality 5%.Other methods step is identical as in embodiment 9, this implementation
Example no longer repeats herein.
Embodiment 10
It is modified in the preparation the present embodiment provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material
Chlorine oxygen magnesium whisker addition be epoxy resin quality 10%.Other methods step is identical as in embodiment 9, this implementation
Example no longer repeats herein.
Embodiment 11
It is modified in the preparation the present embodiment provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material
Chlorine oxygen magnesium whisker addition be epoxy resin quality 15%.Other methods step is identical as in embodiment 9, this implementation
Example no longer repeats herein.
Embodiment 12
It is modified in the preparation the present embodiment provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material
Chlorine oxygen magnesium whisker addition be epoxy resin quality 20%.Other methods step is identical as in embodiment 9, this implementation
Example no longer repeats herein.
Embodiment 13
It is modified in the preparation the present embodiment provides a kind of preparation method of chlorine oxygen magnesium whisker/epoxy resin composite material
Chlorine oxygen magnesium whisker addition be epoxy resin quality 25%.Other methods step is identical as in embodiment 9, this implementation
Example no longer repeats herein.
Comparative example 2
The present embodiment provides a kind of preparation methods of chlorine oxygen magnesium whisker/epoxy resin composite material, are added in the preparation
It is unmodified chlorine oxygen magnesium whisker, the addition of unmodified chlorine oxygen magnesium whisker is the 5% of epoxy resin quality.Other methods walk
Suddenly identical as in embodiment 9, the present embodiment no longer repeats herein.
Above-described embodiment 1-13 respectively mutually analyzes sample topography with object with SEM with XRD with comparative example 1-2.
IR analyses and the test of strength character are also carried out simultaneously.To the chlorine oxygen magnesium whisker/epoxy resin composite wood prepared in embodiment
Material carries out heat analysis.
When carrying out XRD analysis, the chlorine oxygen magnesium whisker sample of preparation is pressed onto on the glass plate of sample preparation, it is desirable that surface is flat
It is whole, for non-breakable chlorine oxygen magnesium/epoxy resin composite material bulk sample, it is firmly sticked to sample using plasticine
On frame, it is desirable that then sample surfaces and sample holder flush are analyzed.Using German Bruker X-ray diffractometers.
The pipe pressure and tube current of ray tube are respectively 40kV and 35mA, and sweep speed is 10 °/min, and minimum step is 0.0001 °, scanning
Ranging from 5 °~80 °.
When carrying out sem analysis, using JSM-6390LV type scanning electron microscope, sample is non-conductive sample, institute
To be handled sample before scanning.It needs that first sample is sticked on copper specimen holder with conducting resinl, then vacuum metallizing postposition
In scanning electron microscope example room.It is that the charge accumulated generated in the case where electron beam irradiates is avoided to influence in the gold-plated purpose of material surface
To image quality, sample can also be protected from thermal damage.Sample is observed with reference to GB/16594-1996, SY/T 5162-1997
Cross-section morphology.Analyze the situations such as each microscopic appearance feature for forming phase, crystal shape, each object interphase slip, microcrack.
When carrying out IR analyses, using Fourier infrared spectrum analyzer, using KBr method of tableting, concrete operations are to take less
Grind into powder in the agate mortar after amount powder sample is mixed with the KBr of about 100~200 times of weight, it is desirable that sample powder
Grind very uniform with potassium bromide, otherwise the uneven diffraction that will produce of particle be easy to cause baseline injustice.In addition KBr should be infrared
Ability tabletting after fully being dried under lamp, this is because potassium bromide is easy the moisture absorption, it otherwise can be in about 1640cm-1And 3300cm-1Occur
The absorption of water and influence experimental result.
When carrying out strength character test analysis, machine and fixture pair are tested using RG3010 type microcomputer controlled electronics are omnipotent
Sample carries out intensity test, it is desirable that two bottom surface of sample polishes flat, and the non-perpendicularity of sample bottom surface and center line is less than
The nonparallelism of 0.2mm/cm, upper bottom surface and bottom surface is less than 0.10mm/cm, and there is no obviously scarce side and crackles.
When chlorine oxygen magnesium whisker/epoxy resin composite material carries out heat analysis, show that difference is swept using thermogravimetric analyzer and DSCQ100
Calorimeter is retouched, using nitrogen as protective gas, TG-DSC analyses, by the way of constant heatingrate, speed are carried out to the sample of synthesis
For 20 DEG C/min, ranging from 0~800 DEG C of experimental temperature, the amount of sample is generally 5~10mg.
The chemical structure of general formula of chlorine oxygen magnesium is Mgx(OH)yClz·mH2O (2x-y-z=0,0≤m≤6).It is primarily present
Mutually have 3 kinds, they are Mg respectively2(OH)3Cl·4H2O (phase 3), Mg3(OH)5Cl·4H2O (phase 5) and Mg10(OH)18Cl2·
5H2O (phase 9).
Be density of magnesium chloride as shown in Figure 1 it is 3mol/L, the molar ratio of magnesium chloride and ammonium hydroxide is respectively 4: 1,5: 1,6: 1 Hes
The XRD spectrum of chlorine oxygen magnesium whisker sample obtained under the conditions of 3: 5.As shown in Figure 1, when the molar ratio of magnesium chloride and ammonium hydroxide is 4: 1
When, the material phase analysis result of sample is Mg3(OH)5Cl·4H2O (i.e. 5Mg (OH)2·MgCl2·8H2O, pure phase 5, spreads out with powder
It is completely corresponding to penetrate card PDF#07-0420), occur without others crystalline phase, effect is preferable；When mole of magnesium chloride and ammonium hydroxide
When than being 5: 1, the main object of sample is mutually Mg3(OH)5Cl·4H2O, in addition there are a small amount of Mg3(OH)5Cl·3H2O is (unstable
Determine phase) occur；When the molar ratio of magnesium chloride and ammonium hydroxide is 6: 1, the main object of sample is mutually Mg3(OH)5Cl·4H2O, in addition
Also there is a small amount of unstable phase Mg3(OH)5Cl·3H2O occurs；And when the molar ratio of magnesium chloride and ammonium hydroxide is 3: 5, sample
Main object be mutually Mg (OH)2, only a small amount of 5Mg (OH)2·MgCl2·8H2O is generated, this may be the concentration mistake because of alkali
Greatly, Mg (OH) has been directly generated2, it is unfavorable for the generation of chlorine oxygen magnesium whisker.
Be density of magnesium chloride as shown in Figure 2 it is 3.5mol/L, the molar ratio of magnesium chloride and ammonium hydroxide is respectively 4: 1,5: 1 and 6:
The XRD spectrum of chlorine oxygen magnesium whisker sample obtained under the conditions of 1.As shown in Figure 2, when the molar ratio of magnesium chloride and ammonium hydroxide is 4: 1,
There are three types of the structure phases of sample, they are Mg respectively3(OH)5Cl·3H2O (unstable phase) and Mg3(OH)5Cl·4H2O (phase 5)
And a small amount of Mg (OH)2；When the molar ratio of magnesium chloride and ammonium hydroxide is 5: 1, there are two types of sample structure phases, they are Mg3
(OH)5Cl·4H2O (phase 5) and unstable phase Mg2(OH)3Cl·3H2O；When the molar ratio of magnesium chloride and ammonium hydroxide is 6: 1, sample
Structure mutually in total there are four types of, they are Mg respectively3(OH)5Cl·4H2O (phase 5) and unstable phase Mg2(OH)3Cl·3H2O with
And a small amount of Mg10(OH)18Cl2·5H2O (phase 9) and Mg2(OH)3Cl·4H2O (phase 3).Comparison diagram 1 is it can be found that increase chlorination
The concentration of magnesium solution can cause sample multiple phases occur, be unfavorable for generating purer 5Mg (OH)2·MgCl2·8H2O.And
Under same concentrations, increase the molar ratio of magnesium chloride and ammonium hydroxide, the generation for chlorine oxygen magnesium whisker pure phase 5 is also unfavorable.
It is to use method II, the i.e. XRD spectrum of sample made from microemulsion method as shown in Figure 3.As can be seen from Figure 3 institute
The structure for obtaining sample is mainly mutually MgO, and there is no the objects of chlorine oxygen magnesium whisker sample mutually to occur, and illustrating reaction system, there is no occur
Chemical reaction.This is because caused by MgO is not the reasons such as nanoscale or experiment for improper.
Show 5Mg (OH) by the studies above2·MgCl2·8H2The quantity of O (phase 5) is more, and crystallization is better, and intensity is just
It is higher.It will be noted from fig. 1 that when molar ratio is 4: 1, the peak shape of sample is sharp and narrow, illustrates that the sample crystallization of synthesis is preferable,
Occur without others dephasign, the purity of crystalline phase is high.In production, it is intended to 5Mg (OH) more as possible2·MgCl2·8H2O
(phase 5) generates.Therefore, by above-mentioned analysis, the chlorine oxygen magnesium whisker for using brine-ammonia process to prepare in of the invention is best.
The SEM pictures of different samples as shown in Figure 4, wherein a, b, c, d be respectively density of magnesium chloride be 3mol/L when, chlorine
The molar ratio of change magnesium and ammonium hydroxide is respectively the scanning electron microscopic picture of sample obtained under the conditions of 3: 5,4: 1,5: 1 and 6: 1.From picture
In a it can be seen that when molar ratio is 3: 5, obtained Sample crystals pattern is in bulk, only minimal amount of spicule.b,c,d
Crystal whisker-shaped is presented, comparison finds that the sample in b figures generates complete and smooth, good dispersion, uniform diameter and thinner whisker,
The average-size of whisker is 19.6um × 484.2nm, and average aspect ratio is about 40, and effect is preferable；C pattern product whisker growths compared with
To be complete, but whisker morphology is short and thick, and the average-size of whisker is 6.5um × 278.7nm, and average aspect ratio is about 20；d
Pattern product whisker surface is not smooth enough, and thickness is uneven.E, f, g be respectively density of magnesium chloride be 3.5mol/L when, magnesium chloride with
The molar ratio of ammonium hydroxide is respectively the scanning electron microscopic picture of sample obtained under the conditions of 4: 1,5: 1 and 6: 1.E pattern product whisker growths
Completely, pattern is preferable, and the average-size of whisker is 18.3um × 575.6nm, and draw ratio is more than 30；F pattern product whiskers are in fiber
Netted, pattern is sufficiently complete；And g pattern product are in netted non-whisker object, only a small amount of crystal whisker-shaped exists.It can be with from picture
Find out, with the increase of the molar ratio of magnesium chloride and ammonium hydroxide, whisker morphology increasingly unobvious.This is because density of magnesium chloride becomes
Height, the degree of supersaturation of solution cross ambassador's system and are in extremely unstable state, cause crystal to be nucleated rapidly, influence crystal along single
Direction is grown, to cannot get the preferable whisker of pattern.
It can be obtained by above-mentioned XRD and sem analysis, using brine-ammonia process, control a concentration of 3mol/L of magnesium chloride solution, chlorination
When the molar ratio of magnesium and ammonium hydroxide is 4: 1, it is mutually 5Mg (OH) that can prepare intact whisker morphology, draw ratio 40, object2·
MgCl2·8H2The chlorine oxygen magnesium whisker of O.
Compressive strength such as 1 institute of table of chlorine oxygen magnesium whisker/epoxy resin composite material in above-described embodiment 8-13 and comparative example 2
Show：
The compressive strength of 1 composite material of table/(MPa)
It is the compression strength of chlorine oxygen magnesium whisker/epoxy resin composite material as shown in table 1 and Fig. 5.As can be seen from Figure 5
When chlorine oxygen magnesium whisker is unmodified, the 5% of epoxy resin quality is added, the compressive strength of epoxy resin just declines about 50%.
This illustrates that no chlorine oxygen magnesium whisker modified cannot be added directly into epoxy resin.This is because chlorine oxygen magnesium whisker is nothing
Machine object, is combined with ionic bond, and epoxy resin is organic high molecular compound, is connected with each other by covalent bond and Van der Waals key
, the intermiscibility of the two is bad.So dispersion performance is bad in the epoxy for chlorine oxygen magnesium whisker, to compromise epoxy resin
Mechanical property.For the chlorine oxygen magnesium whisker after modification, with the increase of chlorine oxygen magnesium Whisker Content, compression strength appearance first increases
The changing rule reduced after big.Illustrate after being surface-treated to chlorine oxygen magnesium whisker using Silane coupling agent KH550, epoxy resin
A strong covalent bond is formed between chlorine oxygen magnesium whisker, substantially improves chlorine oxygen magnesium whisker in epoxy resin-base
Dispersibility, so the compression strength of composite material is improved.When the incorporation of chlorine oxygen magnesium whisker is epoxy resin quality
When 10%, the compressive strength of composite material is maximum, about 120MPa, and the compression strength than pure epoxy resin improves 20% left side
It is right.When the content of chlorine oxygen magnesium whisker is the 15% of epoxy resin quality, the compression strength of composite material is declined, but still and
The compression strength of pure epoxy resin is suitable.So in the case where not influencing the preceding topic of epoxy resin compression strength, chlorine oxygen magnesium whisker is most
Large dosage can be 15%.When the content of chlorine oxygen magnesium whisker is more than 15%, the compression strength of epoxy resin can be caused significantly
Decline.
It is the chlorine of epoxy resin, chlorine oxygen magnesium whisker/epoxy resin composite material of 5% content, 10% content as shown in Figure 6
The TG curves of oxygen magnesium whisker/epoxy resin composite material sample.From fig. 6 it can be seen that the TG curve weightlessness portion of epoxy resin
Point slope have apparent difference, illustrate that its pyrolysis is completed by two processes, the first stage about from 280 DEG C to
437 DEG C, weight-loss ratio 60%, second stage is then from 437 DEG C to 800 DEG C or so, weight-loss ratio about 34%.At 800 DEG C, ring
The residue of oxygen resin remains little, and illustrates that it is soon all decomposed.The chlorine oxygen magnesium metal whisker composite of 5% content is 297
DEG C start to decompose, quality decline slow after 400 DEG C, and 17% or so is had dropped from 400-800 DEG C of quality, residual to 800 DEG C
Excess is 17.7%.The chlorine oxygen magnesium metal whisker composite of 10% content starts to decompose at 304 DEG C, and quality declines after 378 DEG C
Slowly, 15% or so is had dropped from 378-800 DEG C of quality, is 24.2% to 800 DEG C of residues.Epoxy resin is at 280 DEG C
Start to decompose, and the heat decomposition temperature of chlorine oxygen magnesium whisker/epoxy resin composite material is higher than pure epoxy resin.Illustrate chlorine oxygen magnesium
The addition of whisker improves the thermal stability of epoxy resin.Residue quality is carried with the increase of chlorine oxygen magnesium Whisker Content
Height illustrates that the chlorine oxygen magnesium whisker being added is more, and the thermal stability of composite material is better.But the degradation temperature range of composite material with
It the increase of chlorine oxygen magnesium Whisker Content and narrows.
It is that (chlorine oxygen magnesium Whisker Content is for pure epoxy resin and chlorine oxygen magnesium whisker/epoxy resin composite material as shown in Figure 7
10%) DSC curve.It is as shown in table 2 that the starting exothermic peak and skeleton of epoxy resin and composite material crack highest exothermic peak：
The starting of 2 sample of table/termination decomposition caused heat release peak temperature
It can be seen that compared with pure epoxy resin, the initial decomposition temperature of epoxy resin can be made after addition chlorine oxygen magnesium whisker
2 DEG C or so are improved, shows that chlorine oxygen magnesium whisker can improve the thermal stability of epoxy resin at low temperature；The skeleton of epoxy resin is set to split
Solving temperature reduces by 69 DEG C, shows that chlorine oxygen magnesium whisker can improve the thermal stability of epoxy resin at high temperature.It is multiple from 726-800 DEG C
The exotherm rate of condensation material is significantly less than the exotherm rate of pure epoxy resin, shows that chlorine oxygen magnesium whisker was thermally decomposed in epoxy resin
Cheng Zhongneng forms stable compound.Curve can also be seen that addition of the thermal discharge with chlorine oxygen magnesium whisker in decline from Fig. 7
Trend illustrates that the heat released when the addition of chlorine oxygen magnesium whisker makes sample decompose is reduced.This is because chlorine oxygen magnesium whisker crystalline phase
In contain 8 crystallizations water, water slow release when being heated in crystalline phase is vapor, and the vapor of generation can reduce sample temperature
Degree, while vapor evaporation can also take away a part of heat, to inhibit transmission of the heat from heat source to sample, make releasing
Heat decline.
Influence of the chlorine oxygen magnesium whisker to epoxy resin mechanical property and thermal stability discussed above.The result shows that epoxy
The thermal stability of resin is improved with the increase of chlorine oxygen magnesium Whisker Content, and compression strength is with the increasing of chlorine oxygen magnesium Whisker Content
There is the phenomenon that first increases and then decreases greatly, when chlorine oxygen magnesium Whisker Content is less than 10%, the compression strength of epoxy resin increases；When
When the content of chlorine oxygen magnesium whisker is more than 10%, the compression strength of epoxy resin reduces.And when unmodified chlorine oxygen magnesium whisker is added,
The compression strength of epoxy resin drastically declines.In order to further appreciate that influence of the chlorine oxygen magnesium whisker to epoxy resin mechanical property,
The present invention is investigated its deployment conditions in the epoxy.It is that part chlorine oxygen magnesium whisker/epoxy resin is compound as shown in Figure 8
The scanning electron microscopic picture of the material sample plane of disruption.Wherein a is the SEM figures of the pure epoxy resin plane of disruption, and b, c, d are respectively chlorine oxygen magnesium
The SEM figures of the plane of disruption for the composite material that Whisker Content is 5%, 10% and 20%, e is contained without modified chlorine oxygen magnesium whisker
Amount is schemed for the SEM in 5% fracture of composite materials face.A can be seen that the plane of disruption of epoxy resin is more smooth, closeer from figure
Real, without gap, this, which is also epoxy resin itself, has the reason of excellent mechanical property.B does not see chlorine oxygen magnesium from figure
Whisker, this may be that the amount that is added due to chlorine oxygen magnesium whisker is very little or be not uniformly dispersed, no gap but section remains unchanged,
So its mechanical property is not much different with pure epoxy resin.E in comparison diagram, also without seeing chlorine oxygen magnesium whisker, but it is disconnected
Occur many apertures on face, whisker is pulled out the aperture left when that may be fracture, this is to cause epoxy resin pressure resistance
The reason of degree declines.Illustrate bad without the chlorine oxygen magnesium whisker of modification and the compatibility of epoxy resin.In fact, without
Chlorine oxygen magnesium whisker and the polarity spectrum on epoxy resin-base surface for crossing modification are very big, become stress raiser, are to cause
The reason of its intensity declines.C, d can be seen that whisker is evenly dispersed in resin in figure, and gap is few, be formed with epoxy resin
Faying face is preferable.Therefore through the processed chlorine oxygen magnesium whisker of silane coupling agent, the mechanical property of epoxy resin makes moderate progress for addition.
This is because when the faying face that chlorine oxygen magnesium whisker and epoxy resin-base are formed is preferable, under external force, they hold jointly
Carry on a shoulder pole load.And chlorine oxygen magnesium whisker can also absorb energy, can inhibit the extension of crackle and the diffusion of acceleration energy, so compound
The compression strength of material can increase.But with the increase of chlorine oxygen magnesium Whisker Content, the effect of epoxy molecule interchain
Power can decline, so chlorine oxygen magnesium whisker addition can excessively cause intensity to decline.
It is the XRD spectrum of part chlorine oxygen magnesium whisker/epoxy resin composite material sample as shown in Figure 9.Wherein a, b, c, d points
Chlorine oxygen magnesium Whisker Content is not represented as the XRD spectrum of 0%, 5%, 10% and 20% sample of epoxy resin quality.A in Fig. 9
It is the XRD spectrum of pure epoxy resin, as can be seen from Figure 9 occurs without other peaks, only there are one big bulge, illustrate epoxy
Resin is amorphous substance.B, c, d have peak appearance in Fig. 9, and the peak of b is miscellaneous peak in Fig. 9 by analysis, does not occur chlorine oxygen
The peak of magnesium whisker.This is because chlorine oxygen magnesium whisker volume is very little, peak value may be covered by the peak of certain impurity.C, d have in Fig. 9
The peak of chlorine oxygen magnesium whisker occurs, and with the increase of chlorine oxygen magnesium Whisker Content, the quantity that peak occurs is more, and the intensity at peak is also got over
It is high.
It is that (chlorine oxygen magnesium Whisker Content is asphalt mixtures modified by epoxy resin lipid for chlorine oxygen magnesium whisker, epoxy resin and composite material as shown in Figure 10
Amount 10%) infrared spectrogram, wherein a is the infrared spectrogram of chlorine oxygen magnesium whisker, and b is the infrared spectrogram of epoxy resin, c
It is the infrared spectrogram of chlorine oxygen magnesium whisker/epoxy resin composite material.The modified chlorine oxygen magnesium whiskers of a, 2960cm in Figure 10-1、
2925cm-1、2855cm-1Occur, compared with weak absorbing peak, representing modified group-CH2C-H stretching vibrations, 1563cm-1For N-H
Characteristic absorption peak, 1465cm-1、1391cm-1And 1080cm-1For Si-O-CH2CH3The characteristic peak of group, modified chlorine oxygen magnesium
There is the characteristic peak of Silane coupling agent KH550 in whisker sample, this illustrates that the modified chlorine oxygen magnesium whisker surface in surface is successfully grafted
KH550.B in figure, 2966cm-1For the asymmetric stretching vibration peak of C-H in methyl in epoxy resin, 1608cm-1And 1511cm-1For phenyl ring skeletal vibration peak, 1181cm-1And 1038cm-1For the skeletal vibration peak of C-O, 831cm-1For C (CH3)2Vibration peak.
C in figure, 3680cm-1And 3647cm-1For OH in chlorine oxygen magnesium whisker structure water-1Stretching vibration peak, 1645cm-1And 1617cm-1
For OH in chlorine oxygen magnesium whisker structure water-1Flexural vibrations peak, 3421cm-1For OH in the chlorine oxygen magnesium whisker crystallization water-1Stretching vibration
Peak, 2959cm-1For the asymmetric stretching vibration peak of C-H in methyl in epoxy resin, 1512cm-1For phenyl ring skeletal vibration peak,
1179cm-1And 1034cm-1For the skeletal vibration peak of C-O, 831cm-1For C (CH3)2Vibration peak.It, can be with reference to a and b in figure
Find out both occurred the characteristic peak of epoxy resin in composite material, also there is the characteristic peak of chlorine oxygen magnesium whisker, chlorine oxygen magnesium whisker and ring
The absorption vibration peak of the group of oxygen resin does not have significant change, illustrates chlorine oxygen magnesium whisker with there is no change between epoxy resin
Learn reaction.
By the above XRD and infrared analysis, chlorine oxygen magnesium whisker is added in epoxy resin, not with epoxy resin
Reaction is learned, therefore chlorine oxygen magnesium whisker is added in epoxy resin in the form of filler
To sum up, the present invention is directed to the problem of Thermal Stability of Epoxy Resin difference, the fire protecting performance and crystalline substance of chlorine oxygen magnesium are utilized
Palpus toughening principle, prepares chlorine oxygen magnesium/epoxy resin composite material.And its object phase and microstructure and partial properties are carried out
Characterization, analyzes the addition of chlorine oxygen magnesium whisker to the thermostabilization of epoxy resin and the influence of mechanical property.Main Conclusions is such as
Under：
(1) it can prepare that pattern is preferable using brine-ammonia process, object compares pure chlorine oxygen magnesium whisker.Its optimum synthesis condition
It is：The molar ratio of a concentration of 3mol/L of magnesium chloride, magnesium chloride and ammonium hydroxide is 4: 1, and reaction temperature is 30 DEG C, and digestion time is
60h。
(2) surface modification is carried out to chlorine oxygen magnesium whisker with Silane coupling agent KH550, the optimum amount of silane coupling agent is chlorine
5% or so of oxygen magnesium whisker quality does not change mutually with the microscopic appearance of modified chlorine oxygen magnesium whisker and object before modified.
(3) unmodified chlorine oxygen magnesium whisker is very poor with the compatibility of epoxy resin.Modified chlorine oxygen magnesium whisker can improve
The mechanical property of epoxy resin, when 10% whisker is added, compression strength can improve 20% or so, not influence epoxy resin
Mechanical property under conditions of, the maximum adding quantity of chlorine oxygen magnesium whisker is 15%.
(4) addition of chlorine oxygen magnesium whisker, can improve the thermal stability of epoxy resin, and addition is more, and thermal stability is better.
(5) there is no chemical reactions to occur between chlorine oxygen magnesium whisker and epoxy resin.
In conclusion the present invention also has following advantageous effects：
The thermal stability that the present invention prepares chlorine oxygen magnesium whisker/epoxy resin composite material is strong, and the compression of composite material
Intensity is up to 120MPa, and thermal stability is improved with the increase of chlorine oxygen magnesium Whisker Content.And technical scheme of the present invention
Advantage be raw material be easy to get, preparation process it is simple, and can large-scale production use.It has a extensive future.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and principle within, any modification, equivalent replacement, improvement and so on, accompanying claims protection domain of the present invention it
It is interior.
Claims (10)
1. a kind of preparation method of chlorine oxygen magnesium whisker, which is characterized in that the preparation method synthesizes chlorine using brine-ammonia liquid phase method
Oxygen magnesium whisker, the preparation method include the following steps：
1) the magnesium chloride supersaturated solution for configuring 2.5-4mol/L, pours into reactor, reactor is then positioned over 25-35 DEG C
Water bath with thermostatic control in, stirring, fully dissolve, obtain magnesium chloride solution；
2) ammonium hydroxide is added drop-wise in the magnesium chloride solution in step 1), is stirred to react, obtain saturation mother liquor；
3) the saturation mother liquor aging crystallization in step 2) is nucleated；
4) wait for that in step 3) after aging crystallization nucleation, washing is dry, obtains chlorine oxygen magnesium whisker.
2. preparation method as described in claim 1, which is characterized in that in the step 1), configure the chlorination of 3-3.5mol/L
Magnesium supersaturated solution, is poured into reactor；
Preferably, reactor is positioned in 30 DEG C of water bath with thermostatic control, is stirred, fully dissolved, obtain magnesium chloride solution.
3. preparation method as described in claim 1, which is characterized in that in the step 2), ammonia concn 26-30%；
More preferably, ammonia concn 28%.
4. preparation method as described in claim 1, which is characterized in that in the step 2), ammonium hydroxide is with 10ml/min~20ml/
The speed of min is added drop-wise in the magnesium chloride solution of steady temperature.
5. preparation method as described in claim 1, which is characterized in that in the step 2), the molar ratio of magnesium chloride and ammonium hydroxide
Respectively 3: 5-6: 1.
6. preparation method as described in claim 1, which is characterized in that in the step 2), ammonium hydroxide is added drop-wise in step 1)
Magnesium chloride solution in, be stirred to react 1-2h；
More preferably, it is stirred to react 1.5h.
7. preparation method as described in claim 1, which is characterized in that in the step 3), will saturation mother liquor aging crystallization at
Core, specific steps refer to：It is saturated mother liquor aging crystallization at 50-60 DEG C, digestion time 55-65h.
8. preparation method as claimed in claim 7, which is characterized in that saturation mother liquor aging crystallization at 55 DEG C, ageing
Time is 60h.
9. preparation method as described in claim 1, which is characterized in that in the step 4), wait in step 3) aging crystallization at
It after core, is first washed with distilled water, filters, then washed with absolute ethyl alcohol, the product after washing is put into air dry oven
45-55 DEG C of drying 8-12h, obtains chlorine oxygen magnesium whisker；
Preferably, the product after washing is put into 50 DEG C of drying 10h in air dry oven.
10. a kind of application for the chlorine oxygen magnesium whisker prepared such as any one of claim 1-9, preparation is applied to by chlorine oxygen magnesium whisker
In chlorine oxygen magnesium whisker/epoxy resin composite material, i.e., chlorine oxygen magnesium whisker and epoxy resin it is compound so that prepare chlorine oxygen magnesium whisker/
Epoxy resin composite material improves the stability and anti-flammability of epoxide resin material.
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| CN110590320A (en) * | 2019-10-21 | 2019-12-20 | 湖北九之日建筑装饰工程有限公司 | Preparation method of light high-strength waterproof electromagnetic radiation-resistant building material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110590320A (en) * | 2019-10-21 | 2019-12-20 | 湖北九之日建筑装饰工程有限公司 | Preparation method of light high-strength waterproof electromagnetic radiation-resistant building material |
| CN110590320B (en) * | 2019-10-21 | 2022-01-25 | 湖北九之日建筑装饰工程有限公司 | Preparation method of light high-strength waterproof electromagnetic radiation-resistant building material |
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Application publication date: 20181026 |