CN104861146B - High performance magnetic Fe3O4/ polyurethane elastic composite preparation method - Google Patents
High performance magnetic Fe3O4/ polyurethane elastic composite preparation method Download PDFInfo
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- CN104861146B CN104861146B CN201510229904.6A CN201510229904A CN104861146B CN 104861146 B CN104861146 B CN 104861146B CN 201510229904 A CN201510229904 A CN 201510229904A CN 104861146 B CN104861146 B CN 104861146B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
The present invention relates to magnetic composite preparation method, specially high performance magnetic Fe3O4/ polyurethane elastic composite preparation method, the mechanical property and magnetic property for solving existing magnetic polyurethane elastic composite is difficult to raising simultaneously, magnetic particle loading is smaller, bad dispersibility the problem of, scheme is：1）、FeCl2·4H2O、FeCl3·6H2Fe is made with NaOH in O and surfactant3O4；Add the purification of organic solvent Magneto separate；Add the scattered obtained organic magnetic liquid of organic solvent supersonic；2）, addition tetrahydrofuran ether glycol, use anhydrous acid for adjusting pH；Addition toluene di-isocyanate(TDI) obtains base polyurethane prepolymer for use as；Chain extender, vacuumizing and defoaming and magnetic field heating vulcanization are added, Fe is made3O4/ polyurethane elastic composite.Its advantage is：1st, magnetic particle good dispersion, and cross-linked structure is formed with matrix in the elastomer；2nd, inorganic acid is added, the viscosity of polyurethane prepolymer objects system is reduced, it is ensured that magnetic particle high-concentration dopant；4th, the mechanics of magnetic polyurethane elastic composite, magnetic property are lifted simultaneously.
Description
Technical field
The present invention relates to magnetic composite preparation method, specially high performance magnetic Fe3O4The bluk recombination of/elastic polyurethane
Material preparation method.
Background technology
Fe3O4/ magnetic polyurethane elastic composite because with excellent properties, such as magnetism characteristic, lightweight, low magnetic loss,
Good stability, easy processing, thus can be widely applied to intelligent damping, electromagnetic shielding, light wide-band microwave absorbent, magnetic control sensing
The fields such as device, magnetic seal device.But, but there is a problem in the magnetic function composite, i.e., how to obtain mechanics all the time
The combination properties such as performance and magnetic property excellent composite.Mechanical property and having its source in that magnetic property can not optimize simultaneously
Fe3O4The preparation method of/magnetic polyurethane elastic composite.Fe made from conventional melt blending preparation method3O4/ poly- ammonia
Magnetic particle Fe in ester magnetic elastomeric composite material3O4Bad dispersibility in the elastomer, Fe3O4Magnetic particle is reunited existing
As more serious.Magnetic polyurethane elastic composite is prepared using situ aggregation method more than prior art, magnetic particle is in elasticity
Dispersiveness is increased in body, but the preparation method is by Fe3O4After magnetic particle is introduced, cause the viscous of polyurethane prepolymer
Degree is sharply increased, the polymerisation in scattered and later stage of the influence magnetic particle in base polyurethane prepolymer for use as, thus Fe3O4/ polyurethane
The doping of magnetic particle is typically small in magnetic elastomeric composite material（Less than 5.0wt%）, cause magnetic made from this method
The mechanics and magnetic property of elastic composite are relatively low, greatly limit the application of the magnetic functional material.Therefore, study
The excellent combination properties such as a kind of mechanical property and magnetic property, and doping is big in the elastomer, the magnetic of good dispersion for magnetic particle
Property polyurethane elastic composite preparation method is extremely necessary.
The content of the invention
The mechanical property that the present invention solves existing magnetic polyurethane elastic composite is difficult to magnetic property while carrying
Height, magnetic particle loading is smaller when situ aggregation method prepares magnetic elastomeric composite material, bad dispersibility the problem of there is provided one
Plant high performance magnetic Fe3O4/ polyurethane elastic composite preparation method.
The present invention is achieved by the following technical solutions：High performance magnetic Fe3O4/ polyurethane elastic composite system
Preparation Method, comprises the following steps：
1）Prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H20.1 ~ 3.0wt% of O and molysite gross mass oleic acid or
The mixture of aqueous silane coupling agent or oleic acid and aqueous silane coupling agent arbitrary proportion is dissolved in 90mL deionized waters, 50
DEG C and 600r/min mechanical agitations under be well mixed after, using 2 drops/sec be added dropwise 92.4mL concentration as 1.34mol/L NaOH
Continue to react after the aqueous solution, completion of dropping and stop after 90min, be cooled to room temperature, solution progress Magneto separate is obtained into black precipitate,
Supernatant liquor is removed, then with deionized water ultrasonic disperse, Magneto separate, until the pH of supernatant is in neutrality；Then Magneto separate is carried out
Water is removed, pure Fe is obtained3O4Black magnetic particle；
It is b, 80mL is volatile（Boiling point is less than 90 DEG C）, dissolved each other with water, PTMG, and with water, poly- tetrahydrochysene
Furans ether glycol（PTMG）The organic solvent not chemically reacted is added to above-mentioned 2.0g Fe3O4In magnetic particle, with 100r/
Min mechanical agitation, and ultrasonic disperse 30min simultaneously, subsequent Magneto separate remove upper liquid, then are divided with organic solvent ultrasound
Scattered, Magneto separate, obtains water-free Fe3O4Magnetic particle；
It is c, last, by water-free Fe3O4Magnetic particle ultrasonic disperse is formed in the organic solvent of certain volume
Concentration is the stable Fe of 0.01 ~ 0.08g/mL3O4Organic magnetic liquid.
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 40 ~ 60g,
With 400r/min speed stirring simultaneously while after 1.5 ~ 3h of ultrasonic disperse, 60 ~ 90 DEG C are warming up to, with 400r/min mechanical agitations
50min, stirring while add it is a certain amount of dissolved each other with PTMG and toluene di-isocyanate(TDI), and with poly- tetrahydrochysene
The anhydrous acid that furans ether glycol and toluene di-isocyanate(TDI) do not chemically react is so that the pH of reaction system is 5 ~ 6, Ran Housheng
Temperature vacuumizes 3 ~ 5h of holding to 100 ~ 120 DEG C under conditions of vacuum is 0.08kPa；
B, it is then cooled to 25 ~ 40 DEG C, 15 ~ 20g toluene di-isocyanate(TDI) is added in reaction system, in 400r/
Under the conditions of min mechanical agitation and 40 ~ 60 DEG C, after ultrasonic reaction 50min, system temperature is increased to 80 ~ 95 DEG C and continues to react
1.5 ~ 3h, obtains Fe3O4/ base polyurethane prepolymer for use as；
C, the chain extender methylene-bis-o-chloroaniline by 8 ~ 14g（MOCA）It is added to Fe3O4In/performed polymer, with 600r/min
Mechanical agitation 1min, 3 ~ 6min of vacuumizing and defoaming under conditions of room temperature and vacuum are 0.08kPa, pour into warmed-up 55 ~
In 65 DEG C of swage tool, vulcanize 10 ~ 15min under 55 ~ 65 DEG C of temperature, 10MPa pressure and additional 0 ~ 1.5T magnetic field conditions, then
100 ~ 120 DEG C are warming up to, continues to vulcanize 20 ~ 30min under 10MPa pressure and additional 0 ~ 1.5T magnetic field conditions, then be placed in 100 DEG C
After cure 24h in baking oven, obtains Fe3O4/ polyurethane elastic composite, the Fe3O4/ polyurethane elastic composite
Middle Fe3O4The doping of magnetic particle is more than 0 and less than or equal to 30wt%.
Prepare stable Fe3O4During organic magnetic liquid, FeCl is first used using this method2·4H2O、FeCl3·6H2O、
The NaOH aqueous solution reacts generation Fe in deionized water3O4Black magnetic particle.Oleic acid or aqueous silane coupling agent are in reactant
Play and the surface of magnetic particle is modified, be allowed to produce some functional groups and reacted with matrix, in magnetic particle and magnetic
Property particle, magnetic particle and matrix between form relatively stable cross-linked structure, improve the dispersiveness of magnetic particle in the base
And between matrix interface interaction power.Ultrasound, Magneto separate washing, neutrality is adjusted to by the pH value of product repeatedly.It is addition and water, poly-
Tetrahydrofuran ether glycol dissolves each other, and the organic solvent not chemically reacted with water, PTMG, repeatedly ultrasound point
Scattered, Magneto separate, to remove the moisture wherein remained, and prevents from reacting with the PTMG subsequently added.
Micro anhydrous acid is added in reaction system and carrys out adjustment and control system acidity, suppresses the life of the self-aggregate such as allophanate and biuret
Into the viscosity of reduction system, so as to increase Fe3O4The doping of magnetic particle.Heat up and vacuumize 3 ~ 5h of holding, with except
The moisture and organic solvent remained in dereaction system, it is anti-to prevent from occurring with the raw material toluene di-isocyanate(TDI) in next step
Should.Add toluene di-isocyanate(TDI), heating ultrasonic reaction generation base polyurethane prepolymer for use as.Addition chain extender, vacuumizing and defoaming, and outside
Plus vulcanization obtains Fe under the conditions of 0 ~ 1.5T of magnetic field3O4/ polyurethane elastic composite.Having, the mold pressing parameter without externally-applied magnetic field
It is lower that anisotropic magnetic composite and isotropism magnetic composite are made respectively.
The aqueous silane coupling agent is the mixture of KH550 or KH460 or KH550 and KH460 arbitrary proportions.Aqueous silicon
Alkane coupling agent is used for improving compatibility, dispersiveness and the interface interaction power between matrix of filler in the polymer.It is described organic
Solvent is tetrahydrofuran or absolute ethyl alcohol.The anhydrous acid is acyl chlorides or solid acetic acid.
The present invention has advantages below compared with prior art：1st, surfactant is with the addition of to carry out magnetic particle surface
Surface modification, is allowed to produce some functional groups and is reacted with matrix, in magnetic particle and magnetic particle, magnetic particle and matrix
Between form relatively stable cross-linked structure, improve magnetic particle dispersiveness in the base and the interface interaction between matrix
Power；2nd, micro anhydrous acid is added in reaction system and carrys out adjustment and control system acidity, suppresses the autohemagglutination such as allophanate and biuret
The generation of body, reduces the viscosity of system, so as to increase the doping of magnetic particle, and improves magnetic particle in composite preparation
The problem of easily reuniting in forming process；3rd, mechanical property and magnetic property are improved simultaneously, and performance is prepared compared with prior art
Material it is more excellent.
Brief description of the drawings
Fig. 1 is the Fe of stabilization in embodiment one and two3O4The optical photograph of-tetrahydrofuran magnetic liquid；
Fig. 2 is Fe in the present invention3O4The VSM curves of magnetic particle；
Fig. 3 is Fe in the present invention3O4The XRD of/polyurethane elastic composite；It can be seen that from XRD
30.5 °, 36.0 °, 54.0 ° and 63.0 ° are Fe3O4Characteristic peak, correspond respectively to cubic spinel structure Fe3O4's
(220), (311), (400), (511) and (440) crystal face, the broad peak occurred near 20 ° is polyurethane matrix peak；It can thus be appreciated that
Contain Fe in the material3O4Magnetic particle and polyurethane matrix；
The Fe that Fig. 4 is prepared for the present invention3O4The optical photograph that/polyurethane elastic composite thin slice is picked up by magnetite；
Fe is shown by figure3O4/ magnetic particle is scattered in polyurethane matrix well, and shows good magnetic property；
The Fe that Fig. 5 is prepared for the present invention3O4Stress-strain of/the polyurethane elastic composite under stretching condition is bent
Line；As can be seen from Figure, the material that prepared by the inventive method has good mechanical tensile strength and elasticity.
Embodiment
Embodiment one：
High performance magnetic Fe3O4/ polyurethane elastic composite preparation method, comprises the following steps：
1）, prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H2O and molysite gross mass 0.1wt% oleic acid are dissolved in
In 90mL deionized waters, under 50 DEG C and 600r/min of mechanical agitation, after being well mixed, with 2 drops/sec of dropwise addition 92.4mL
Concentration is the 1.34mol/L NaOH aqueous solution, continues after completion of dropping to react after 90min and stops, and is cooled to room temperature, solution is entered
Row Magneto separate obtains black precipitate, removes supernatant liquor, then with deionized water ultrasonic disperse, Magneto separate, until the pH of supernatant
In neutrality；Then carry out Magneto separate and remove water, obtain Fe3O4Black magnetic particle；
B, 80mL tetrahydrofurans are added to above-mentioned 2.0g Fe3O4In magnetic particle, in 100r/min mechanical agitation, and
Simultaneously after ultrasonic disperse 30min, Magneto separate removes upper liquid, then with the organic solvent ultrasonic disperse, Magneto separate, washes repeatedly
Wash, the Fe purified3O4Magnetic particle；
It is c, last, by the Fe of purification3O4Magnetic particle ultrasonic disperse is formed dense in the organic solvent of certain volume
Spend for Fe stable 0.025g/mL3O4- tetrahydrofuran magnetic liquid.
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 45g, with
After 400r/min mechanical agitation and simultaneously ultrasonic disperse 2.5h, 90 DEG C are warming up to, with 400r/min mechanical agitation 50min,
Simultaneously add a certain amount of acyl chlorides so that reaction system pH be 6, then heat to 110 DEG C, vacuum be 0.08kPa condition
Under vacuumize holding 3h；
B, it is then cooled to 35 DEG C, 16.78g toluene di-isocyanate(TDI) is added in reaction system, in 400r/min
Mechanical agitation and 45 DEG C under the conditions of, after ultrasonic reaction 50min, by system temperature be increased to 90 DEG C continue react 2h, obtain
Fe3O4/ base polyurethane prepolymer for use as；
C, 11.68g chain extender methylene-bis-o-chloroaniline is added to Fe3O4In/base polyurethane prepolymer for use as, with 600r/
Min mechanical agitation 1min, the vacuumizing and defoaming 5min under conditions of room temperature and vacuum are 0.08kPa, pours into warmed-up 65
DEG C swage tool in, vulcanize 15min under 65 DEG C of temperature, 10MPa pressure and additional 1T magnetic field conditions, then heat to 100 DEG C,
Continue to vulcanize 20min under 10MPa pressure and additional 1.5T magnetic field conditions, then be placed in after cure 24h in 100 DEG C of baking ovens, obtain
The doping of magnetic particle is 0.5wt% anisotropy Fe3O4/ polyurethane elastic composite.
Embodiment two：
High performance magnetic Fe3O4Poly-/urethane elastic composite preparation method, comprises the following steps：
1）, prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H2O and molysite gross mass 1wt% KH550 are dissolved in
In 90mL deionized waters, under 50 DEG C and 600r/min of mechanical agitation, after being well mixed, with 2 drops/sec of dropwise addition 92.4mL
Concentration is the 1.34mol/L NaOH aqueous solution, continues after completion of dropping to react after 90min and stops, and is cooled to room temperature, solution is entered
Row Magneto separate obtains black precipitate, removes supernatant liquor, then with deionized water ultrasonic disperse, Magneto separate, repeated washing, until upper
The pH of clear liquid is in neutrality；Then carry out Magneto separate and remove water, obtain Fe3O4Black magnetic particle；
B, 80mL absolute ethyl alcohols are added to above-mentioned 2.0g Fe3O4In magnetic particle, stirred with 100r/min speed, and
Ultrasonic disperse 30min, subsequent Magneto separate removing upper liquid, then with the organic solvent ultrasonic disperse, Magneto separate, wash repeatedly simultaneously
Wash, obtain purifying water-free Fe3O4Magnetic particle；
It is c, last, by the Fe of purification3O4Magnetic particle ultrasonic disperse is formed dense in the organic solvent of certain volume
Spend for Fe stable 0.01g/mL3O4- ethanol magnetic liquid.
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 40g, with
After 400r/min mechanical agitation and simultaneously ultrasonic disperse 1.5h, 60 DEG C are warming up to, with 400r/min mechanical agitation 50min,
A certain amount of solid acetic acid is added simultaneously so that the pH of reaction system is 5, then heat to 100 DEG C, in vacuum for 0.08kPa
Under the conditions of vacuumize holding 5h；
B, it is then cooled to 25 DEG C, 18g toluene di-isocyanate(TDI) is added in reaction system, with 400r/min machines
Tool stir and 50 DEG C under the conditions of, after ultrasonic reaction 50min, by system temperature be increased to 80 DEG C continue react 3h, obtain Fe3O4/ poly-
Urethane performed polymer；
C, 10g chain extender methylene-bis-o-chloroaniline is added to Fe3O4In/base polyurethane prepolymer for use as, with 600r/min's
Mechanical agitation 1min, the vacuumizing and defoaming 3min under conditions of room temperature and vacuum are 0.08kPa, pour into warmed-up 55 DEG C of iron
In mould, vulcanize 10min under the conditions of 60 DEG C of temperature, 10MPa pressure and without externally-applied magnetic field, then heat to 110 DEG C,
10MPa pressure and without continuing to vulcanize 30min under the conditions of externally-applied magnetic field, then is placed in after cure 24h in 100 DEG C of baking ovens, obtains magnetic
The doping of particle is 10wt% isotropism Fe3O4/ polyurethane elastic composite.
Embodiment three：
High performance magnetic Fe3O4/ polyurethane elastic composite preparation method, comprises the following steps：
1）, prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H2O and molysite gross mass 2wt% KH460 are dissolved in
In 90mL deionized waters, under 50 DEG C and 600r/min of mechanical condition, after being well mixed, with 2 drops/sec of dropwise addition 92.4mL concentration
Continue to react for the 1.34mol/L NaOH aqueous solution, after completion of dropping and stop after 90min, be cooled to room temperature, solution is subjected to magnetic
Isolated black precipitate, removes supernatant liquor, then with deionized water ultrasonic disperse, Magneto separate, repeated washing, until supernatant
PH in neutrality；Then carry out Magneto separate and remove water, obtain Fe3O4Black magnetic particle；
B, 80mL tetrahydrofurans are added to above-mentioned 2.0g Fe3O4In magnetic particle, stirred with 100r/min speed, and
Ultrasonic disperse 30min, subsequent Magneto separate removing upper liquid, then with the organic solvent ultrasonic disperse, Magneto separate, wash repeatedly simultaneously
Wash, obtain water-free Fe3O4Magnetic particle；
It is c, last, water-free Fe will be purified3O4Magnetic particle ultrasonic disperse in the organic solvent of certain volume,
It is the stable Fe of 0.05g/mL to form concentration3O4Organic magnetic liquid.
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 50g, with
After 400r/min mechanical agitation and simultaneously ultrasonic disperse 2h, 70 DEG C are warming up to, with 400r/min mechanical agitation 50min, together
When add a certain amount of acyl chlorides so that reaction system pH be 5.5, then heat to 120 DEG C, vacuum be 0.08kPa condition
Under vacuumize holding 4h；
B, it is then cooled to 40 DEG C, 15g toluene di-isocyanate(TDI) is added in reaction system, in 400r/min machines
Tool stir and 40 DEG C under the conditions of, after ultrasonic reaction 50min, by system temperature be increased to 95 DEG C continue react 1.5h, obtain Fe3O4/
Base polyurethane prepolymer for use as；
C, 8g chain extender methylene-bis-o-chloroaniline is added to Fe3O4In performed polymer, with 600r/min mechanical agitations
In 1min, the vacuumizing and defoaming 4min under conditions of room temperature and vacuum are 0.08kPa, the swage tool for pouring into warmed-up 55 DEG C,
Vulcanize 13min under 55 DEG C of temperature, 10MPa pressure and additional 0.5T magnetic field conditions, 105 DEG C are then heated to, in 10MPa pressure
Vulcanize 20min with continuation under additional 1T magnetic field conditions, then be placed in after cure 24h in 100 DEG C of baking ovens, obtain the doping of magnetic particle
Measure the anisotropy Fe for 20wt%3O4/ polyurethane elastic composite.
Example IV：
High performance magnetic Fe3O4/ polyurethane elastic composite preparation method, comprises the following steps：
1）, prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H2O and molysite gross mass 0.5wt% oleic acid and molysite
Gross mass 2.5wt% KH550 mixtures are dissolved in 90mL deionized waters, in 50 DEG C and 600r/min mechanical agitation
Under, after being well mixed, it is added dropwise using 2 drops/sec of 92.4mL after the NaOH aqueous solution of the concentration as 1.34mol/L, completion of dropping and continues anti-
Answer and stop after 90min, be cooled to room temperature, solution progress Magneto separate is obtained into black precipitate, supernatant liquor is removed, then use deionization
Water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant is in neutrality；Then carry out Magneto separate and remove water, obtain Fe3O4
Black magnetic particle；
B, 80mL absolute ethyl alcohols are added to above-mentioned 2.0g Fe3O4In magnetic particle, stirred with 100r/min speed, and
Ultrasonic disperse 30min, subsequent Magneto separate removing upper liquid, then with the organic solvent ultrasonic disperse, Magneto separate, wash repeatedly simultaneously
Wash, obtain purifying water-free Fe3O4Magnetic particle；
It is c, last, by the Fe of purification3O4Magnetic particle ultrasonic disperse is formed dense in the organic solvent of certain volume
Spend for Fe stable 0.08g/mL3O4Organic magnetic liquid.
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 60g, with
After 400r/min mechanical agitation and simultaneously ultrasonic disperse 3h, 80 DEG C are warming up to, with 400r/min mechanical agitation 50min,
A certain amount of solid acetic acid is added while stirring so that reaction system pH be 6, then heat to 105 DEG C, be in vacuum
Holding 3.5h is vacuumized under conditions of 0.08kPa；
B, it is then cooled to 30 DEG C, 20g toluene di-isocyanate(TDI) is added in reaction system, with 400r/min's
Mechanical agitation, is maintained at 55 DEG C, after ultrasonic reaction 50min, and system temperature is increased into 85 DEG C of reaction 2.5h, Fe is obtained3O4/
Base polyurethane prepolymer for use as；
C, 14g chain extender methylene-bis-o-chloroaniline is added to Fe3O4/ base polyurethane prepolymer for use as, with 600r/min machine
Tool stirs 1min, the vacuumizing and defoaming 6min under conditions of room temperature and vacuum are 0.08kPa, pours into warmed-up 60 DEG C of swage
In tool, vulcanize 11.5min under 60 DEG C of temperature, 10MPa pressure and additional 1.5T magnetic field conditions, then heat to 115 DEG C,
Continue to vulcanize 25min under 10MPa pressure and additional 0.5T magnetic field conditions, then be placed in after cure 24h in 100 DEG C of baking ovens, obtain magnetic
Property particle doping be 30wt% anisotropy Fe3O4/ polyurethane elastic composite.
Embodiment five：
High performance magnetic Fe3O4/ polyurethane elastic composite preparation method, comprises the following steps：
1）, prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H2O and molysite gross mass 1wt% oleic acid and molysite is total
Quality 0.5wt% KH550 and molysite gross mass 0.2wt% KH460 are dissolved in 90mL deionized waters, in 50 DEG C and 600r/
Under min mechanical agitation, after being well mixed, the NaOH aqueous solution of the concentration as 1.34mol/L is added dropwise using 2 drops/sec of 92.4mL,
Continue to react after completion of dropping and stop after 90min, be cooled to room temperature, solution progress Magneto separate is obtained in black precipitate, removing
Layer clear liquid, then with deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant is in neutrality；Then magnetic point is carried out
From water is removed, Fe is obtained3O4Black magnetic particle；
B, 80mL tetrahydrofurans are added to above-mentioned 2.0g Fe3O4In magnetic particle, with 100r/min mechanical agitation, and
Ultrasonic disperse 30min, subsequent Magneto separate removing upper liquid, then with the organic solvent ultrasonic disperse, Magneto separate, wash repeatedly simultaneously
Wash, the Fe purified3O4Magnetic particle；
It is c, last, by the Fe of purification3O4Magnetic particle ultrasonic disperse is formed dense in the organic solvent of certain volume
Spend for Fe stable 0.075g/mL3O4Organic magnetic liquid.
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 55g, with
After 400r/min mechanical agitation and simultaneously ultrasonic disperse 3h, 75 DEG C are warming up to, with 400r/min mechanical agitation 50min, together
When add a certain amount of acyl chlorides so that reaction system pH be 5, then heat to 115 DEG C, vacuum be 0.08kPa under conditions of
Vacuumize holding 4.5h；
B, it is then cooled to 32 DEG C, 19g toluene di-isocyanate(TDI) is added in reaction system, in 400r/min machines
Tool stir and 60 DEG C under the conditions of, after ultrasonic reaction 50min, by system temperature be increased to 88 DEG C continue react 2h, obtain Fe3O4/ poly-
Urethane performed polymer；
C, the chain extender methylene-bis-o-chloroaniline by 14g（MOCA）It is added to Fe3O4/ base polyurethane prepolymer for use as, with 600r/
Min mechanical agitation 1min, the vacuumizing and defoaming 6min under conditions of room temperature and vacuum are 0.08kPa, pour into warmed-up 60 DEG C
Swage tool in, vulcanize 15min under 65 DEG C of temperature, 10MPa pressure and additional 1T magnetic field conditions, then heat to 115 DEG C,
Continue to vulcanize 25min under 10MPa pressure and additional 0.5T magnetic field conditions, then be placed in after cure 24h in 100 DEG C of baking ovens, obtain magnetic
Property particle doping be 15wt% anisotropy Fe3O4/ polyurethane elastic composite.
Claims (4)
1. a kind of high performance magnetic Fe3O4/ polyurethane elastic composite preparation method, it is characterized in that：Comprise the following steps：
1）, prepare stable Fe3O4Organic magnetic liquid
A, by 3.58g FeCl2·4H2O、6.08g FeCl3·6H20.1 ~ 3.0wt% of O and molysite gross mass oleic acid or aqueous silicon
The mixture of alkane coupling agent or oleic acid and aqueous silane coupling agent arbitrary proportion is dissolved in 90mL deionized waters, at 50 DEG C and
Under 600r/min mechanical agitations, after being well mixed, 92.4mL concentration is added dropwise using 2 drops/sec water-soluble as 1.34mol/L NaOH
Continue to react after liquid, completion of dropping and stop after 90min, be cooled to room temperature, solution progress Magneto separate is obtained into black precipitate, removed
Supernatant liquor, then with deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant is in neutrality；Then magnetic is carried out
Water is separated off, Fe is obtained3O4Black magnetic particle；
B, 80mL is volatile, boiling point is less than 90 DEG C, is dissolved each other with water, PTMG, and with water, PTMG
The organic solvent that glycol does not chemically react is added to above-mentioned 2.0g Fe3O4In magnetic particle, stirred with 100r/min machinery
Mix, and ultrasonic disperse 30min simultaneously, subsequent Magneto separate removes upper liquid, then with the organic solvent ultrasonic disperse, Magneto separate,
Cyclic washing, obtains purifying water-free Fe3O4Magnetic particle；
It is c, last, by the Fe of purification3O4Magnetic particle ultrasonic disperse is in the organic solvent of certain volume, and forming concentration is
Fe stable 0.01 ~ 0.08g/mL3O4Organic magnetic liquid；
2）, magnetic control situ aggregation method prepare Fe3O4/ polyurethane elastic composite
A, the Fe by above-mentioned certain volume3O4Organic magnetic liquid is mixed with the liquid PTMGs of 40 ~ 60g, with
After 400r/min mechanical agitation and simultaneously 1.5 ~ 3h of ultrasonic disperse, 60 ~ 90 DEG C are warming up to, with 400r/min mechanical agitation
50min, stirring while add it is a certain amount of dissolved each other with PTMG and toluene di-isocyanate(TDI), and with poly- tetrahydrochysene
The anhydrous acid that furans ether glycol and toluene di-isocyanate(TDI) do not chemically react is so that the pH of reaction system is 5 ~ 6, Ran Housheng
Temperature vacuumizes 3 ~ 5h of holding to 100 ~ 120 DEG C under conditions of vacuum is 0.08kPa；
B, it is then cooled to 25 ~ 40 DEG C, 15 ~ 20g toluene di-isocyanate(TDI) is added in reaction system, in 400r/min
Under the conditions of mechanical agitation and 40 ~ 60 DEG C, after ultrasonic reaction 50min, by system temperature be increased to 80 ~ 95 DEG C continue to react 1.5 ~
3h, obtains Fe3O4/ base polyurethane prepolymer for use as；
C, 8 ~ 14g chain extender methylene-bis-o-chloroaniline is added to Fe3O4In/base polyurethane prepolymer for use as, with 600r/min machineries
1min is stirred, 3 ~ 6min of vacuumizing and defoaming under conditions of room temperature and vacuum are 0.08kPa pours into warmed-up 55 ~ 65 DEG C
In swage tool, vulcanize 10 ~ 15min under 55 ~ 65 DEG C of temperature, 10MPa pressure and additional 0 ~ 1.5T magnetic field conditions, then heat to
100 ~ 120 DEG C, continue to vulcanize 20 ~ 30min under 10MPa pressure and additional 0 ~ 1.5T magnetic field conditions, then be placed in 100 DEG C of baking ovens
After cure 24h, obtains Fe3O4/ polyurethane elastic composite, the Fe3O4Fe in/polyurethane elastic composite3O4
The doping of magnetic particle is more than 0 and less than or equal to 30wt%.
2. high performance magnetic Fe according to claim 13O4/ polyurethane elastic composite preparation method, its feature
For：The aqueous silane coupling agent is the mixture of KH550 or KH460 or KH550 and KH460 arbitrary proportions.
3. high performance magnetic Fe according to claim 1 or 23O4/ polyurethane elastic composite preparation method, it is special
Levy for：The organic solvent is tetrahydrofuran or absolute ethyl alcohol.
4. high performance magnetic Fe according to claim 33O4/ polyurethane elastic composite preparation method, its feature
For：The anhydrous acid is acyl chlorides or solid acetic acid.
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| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
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| Synthesis and investigation of thermal and mechanical properties of in situ prepared biocompatible Fe3O4/polyurethane elastomer nanocomposites;Abbas Mohammadi.Mehdi Barikani.Mohammad Barmar;<Polym. Bull.>;20141106;第72卷;第219-234页 * |
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