CN107057091B - A kind of nylon-polymethyl methacrylate alloy microballoon and its preparation method and application - Google Patents
A kind of nylon-polymethyl methacrylate alloy microballoon and its preparation method and application Download PDFInfo
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- CN107057091B CN107057091B CN201710110323.XA CN201710110323A CN107057091B CN 107057091 B CN107057091 B CN 107057091B CN 201710110323 A CN201710110323 A CN 201710110323A CN 107057091 B CN107057091 B CN 107057091B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
Abstract
The invention discloses a kind of nylon-polymethyl methacrylate alloy microballoons, and the alloy microballoon includes nylon micro-sphere and polymethyl methacrylate；The content of nylon micro-sphere is 30~90wt% in the alloy microballoon, and the content of polymethyl methacrylate is 10~70wt%；The alloy microballoon is wherein through-hole structure inside nylon micro-sphere using nylon micro-sphere as skeleton, and the polymethyl methacrylate is dispersed in the hole of apertures nylon micro-sphere, surface or both has；The alloy microballoon is spherical or subsphaeroidal particle, and partial size is 1~100 μm.In alloy microballoon proposed by the present invention, the ester group in apertures nylon micro-sphere in a large amount of amido bond and carboxyl and amino and polymethyl methacrylate easily forms hydrogen bond, and two kinds of components are cross-linked with each other in inierpeneirating network structure, is not necessarily to compatilizer, has good compatibility.
Description
Technical field
The present invention relates to technical field of polymer materials.It is closed more particularly, to a kind of nylon-polymethyl methacrylate
Gold microsphere and its preparation method and application.
Background technique
Polyamide (PA), is commonly called as nylon, is one of five large-engineering plastics, belong in engineering plastics yield is maximum, purposes most
Wide kind has mechanical strength high, and wear-resisting and self-lubrication is good, and impact flexibility is good, in automobile, machinery, electronics, building, army
The fields such as work, aerospace have a wide range of applications.As epoch progress needs, Rapid Manufacturing Technology gradually heaves in sight, has
Hope substitution conventional machining techniques, and 3D printing technique is called the third time industrial revolution as Rapid Manufacturing Technology of new generation
Mark.Nylon is used as 3D printing technique-selective laser sintering because of its excellent chemical stability and excellent mechanical performance
The essential high molecular consumptive material of technology (SLS).Currently, commercial nylon powder in the market mostly uses high temperature and high pressure method to be made, such as EOS
PA2200, PA3200GF of company, 3250MF, FS3400GF, PA3200 etc. of magnificent daybreak high-tech, these powder are burnt to laser
The drip molding performance of knot is really good, but still has some disadvantages: as understood because of the particle melted and not melting in sintering process
Edge effect caused by particle causes drip molding rough surface；In addition, polyamide powder can occur in laser fusing crystallisation by cooling
Certain shrinkage will affect the dimensional stability of product.
Polymethyl methacrylate (PMMA) is a kind of transparent polymer material, has excellent optical property and superficiality
Energy and good dimensional stability, good coloring can also create beautiful appearance, and product glossiness is good, and feel is thin
It is greasy；However PMMA surface hardness is small, the disadvantages of wearing no resistance, limits it and is more widely applied.Therefore the prior art takes long benefit
It is short, PMMA is combined to the blend prepared and have the two advantage performance with the advantage of nylon, mainly using physical blending
Dry PA powder is mixed with PMMA material in high speed machine kneading machine, obtains PMMA/PA12 composite powder by mode,
The mechanograph that composite powder is sintered has better smooth surface and better dimensional stability compared to pure powder, still
The composite powder two-phase associativity that this mode obtains is bad, and dispersion is uneven, and mechanical property is lower.
The invention proposes a kind of nylon-polymethyl methacrylate alloy microballoons, by the way of in-situ polymerization, utilize
Intermolecular hydrogen bonding effect between ester group in polyamide in a large amount of amido bond and PMMA, selects acrylic monomer MMA
It is better to obtain dimensional stability, surface flatness and mechanical property inside apertures nylon micro-sphere and in situ Polymerization for property
PA/PMMA alloy powder.
Summary of the invention
It is an object of the present invention to provide a kind of nylon-polymethyl methacrylate alloy microballoons.The alloy microballoon
In, PMMA is dispersed in hole and/or the surface of apertures nylon micro-sphere, in PA a large amount of amido bond and carboxyl and amino with
Ester group in PMMA easily forms hydrogen bond, and two kinds of components are cross-linked with each other in inierpeneirating network structure, is not necessarily to compatilizer, has good phase
Capacitive.
It is another object of the present invention to provide a kind of nylon-polymethyl methacrylate alloy microballoon preparation sides
Method.The composite powder that the powder and physical blending mode that the alloy microballoon obtained by preparation method proposed by the present invention forms obtain
Have significantly different, have both the advantage of PA and PMMA, the PA and PMMA of opposite one-component, alloy microballoon have better mechanical property
Can, certain translucidus, water absorption rate is declined.
Third object of the present invention is to provide a kind of application of nylon-polymethyl methacrylate alloy microballoon.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of nylon-polymethyl methacrylate alloy microballoon, the alloy microballoon includes nylon micro-sphere and poly- methyl-prop
E pioic acid methyl ester；In the alloy microballoon, the content of nylon micro-sphere is 30~90wt%, and the content of polymethyl methacrylate is 10
~70wt%.
Preferably, the alloy microballoon is wherein through-hole structure inside nylon micro-sphere, is convenient for first using nylon micro-sphere as skeleton
Base methacrylate monomer is dispersed in polymethyl methacrylate inside apertures nylon micro-sphere and in situ Polymerization
In the hole of nylon micro-sphere, surface or both has.Nylon contains a large amount of amido bond, in carboxyl and amino, with PMMA
Ester group easily form hydrogen bond, two kinds of components are cross-linked with each other in inierpeneirating network structure, are not necessarily to compatilizer, have good compatibility.
Preferably, the alloy microballoon is spherical or subsphaeroidal particle, and partial size is 1~100 μm.Alloy microballoon is with nylon
Main body has higher force intensity and toughness, is filled with PMMA, while so that alloy is shown favorable comprehensive mechanical property
Have excellent dimensional stability and apparent property.
Preferably, the nylon micro-sphere is selected from 6 microballoon of nylon, nylon66 fiber microballoon, 12 microballoon of nylon, nylon 11 microballoon, Buddhist nun
One or more of imperial 1212 microballoons, nylon 612 microballoon, nylon 610 microballoon or nylon 1010 microballoon.
Preferably, 50~800m of the nylon micro-sphere specific surface area2/ g, porosity 5%~85%, aperture are 0.05~10
μm。
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of nylon-polymethyl methacrylate alloy microballoon, includes the following steps:
1) apertures nylon micro-sphere is added in a kind of solvent, and 1~2h is stirred at room temperature to be mixed to get uniform nylon micro-
Ball dispersion liquid；
2) catalyst is added into the nylon dispersion liquid in step 1), is passed through nitrogen discharge oxygen, is warming up to 30~50 DEG C
When, methyl methacrylate monomer is added, mixing is stirred at room temperature, then be warming up to 20~100 DEG C, through 6~48h of home position polymerization reaction
Stop reaction afterwards, obtain product and carry out decompression suction filtration, drying obtains nylon-polymethyl methacrylate alloy microballoon after washing.
Preferably, apertures nylon micro-sphere uses Chinese Patent Application No. to be molten in 201510765814.9 in step 1)
Solution-precipitation method are made, and are first formed nylon resin surely in 70 DEG C~90 DEG C dissolutions in good solvent in a manner of dissolution-precipitating
Determine clear solution, then the poor solvent containing dispersing agent PVP is added thereto, precipitate, post-processing obtains containing for favorable dispersibility
Hole nylon micro-sphere.Preferably, good solvent selection formic acid solvent used, nylon are with formic acid solvent mass ratio in dissolution-precipitation method
1:8~12；Poor solvent selects ethanol solution, and nylon and ethanol solution mass ratio are 1:10~15.
Preferably, solvent described in step 1) is selected from deionized water, methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol
It is one or more of.Keep nylon micro-sphere evenly dispersed and insoluble using the solvent in the present invention.
Preferably, solvent described in step 1) is ethyl alcohol and deionized water mixed solution, and the mass ratio of second alcohol and water is 1:
0.1~10；Further, the mass ratio of the second alcohol and water is 1:1~10,1:2~9,1:3~8,1:4~7,1:5~6 etc.；
It is highly preferred that the mass ratio of the second alcohol and water be 1:0.1~9,1:0.2~8,1:0.3~7,1:0.4~6,1:0.5~5,
1:0.6~4,1:0.7~3,1:0.8~2,1:0.9~1 etc..
Preferably, the additional amount of solvent described in step 1) is 1~100 times of apertures nylon micro-sphere quality；Further,
In certain specific embodiments of the invention, for example, the additional amount of the solvent is the 5~90 of apertures nylon micro-sphere quality
Again, 5~80 times, 5~70 times, 5~60 times, 5~50 times, 5~40 times, 5~30 times, 5~20 times, 10~20 times, 15~20 times
Deng；It is highly preferred that the additional amount of the solvent is 5~15 times, 8~15 times, 12~15 times etc. of apertures nylon micro-sphere quality；Into
One step, the additional amount of the solvent is 5~12 times of apertures nylon micro-sphere quality, 6~10 times, 7~10 times, 7~9 times, 8~
9 times etc..
Preferably, catalyst described in step 2) is water-soluble peroxide, convenient for catalysis reaction methyl-prop in aqueous solution
E pioic acid methyl ester monomer generates polymer, and catalyst is selected from one or more of hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate；It is excellent
Selection of land, catalyst described in step 2) are ammonium persulfate.
Preferably, catalyst charge described in step 2) is 0.1wt%~10wt% of methyl methacrylate monomer.
Preferably, the additional amount of methyl methacrylate monomer described in step 2) is the 0.1~5 of apertures nylon micro-sphere
Times.
Preferably, in step 2), heat reaction temperature be 50~100 DEG C, after heating the reaction time be 6~for 24 hours.
A kind of nylon-polymethyl methacrylate alloy powder material, the dusty material include nylon-polymethyl
Sour methyl esters alloy microballoon and antioxidant, the additional amount of the antioxidant are 0.05wt%~1wt% of alloy microballoon.
Preferably, the antioxidant is selected from antioxidant 2246, antioxidant 1010, irgasfos 168, antioxidant 1076, antioxygen
One or both of agent 1098；Preferably, the antioxidant is antioxidant 2246.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
A kind of application of nylon-polymethyl methacrylate alloy microballoon in chromatographic isolation, medicament slow release field.
A kind of nylon-polymethyl methacrylate alloy powder material is in functional paint, electrostatic spraying, 3D printing-selection
The application in the laser sintered field of property.
Preferably, when alloy microspherulite diameter is 20~90 μm in the alloy powder material, it is applied to 3D printing-selectivity
Laser sintering technology.
Preferably, when alloy microspherulite diameter is 50~80 μm in the alloy powder material, it is applied to electrostatic spraying.
Acrylic monomer MMA is utilized selectively inside apertures nylon micro-sphere and in situ Polymerization in the present invention
Intermolecular hydrogen bonding effect between ester group in polyamide in a large amount of amido bond and PMMA, so that two kinds of components are cross-linked with each other,
Collective effect, obtained nylon-polymethyl methacrylate alloy microballoon have both the advantage of PA and PMMA, and mechanical property is more preferable,
And there is certain translucidus, water absorption rate is declined.
In addition, unless otherwise specified, any range documented by the present invention includes any number between end value and end value
Any subrange that any number between value and end value or end value is constituted.
Beneficial effects of the present invention are as follows:
(1) in alloy microballoon proposed by the present invention, polymethyl methacrylate is dispersed in the hole of apertures nylon micro-sphere
Gap and/or surface, the ester group in PA in a large amount of amido bond and carboxyl and amino and PMMA easily form hydrogen bond, two kinds of group split-phases
Mutually crosslinking is in inierpeneirating network structure, is not necessarily to compatilizer, has good compatibility.
(2) had by the composite powder that the composite powder that alloy microballoon proposed by the present invention forms is obtained with physical blending mode
It is significantly different, the advantage of PA and PMMA are had both, the PA and PMMA of opposite one-component, alloy microballoon have better mechanical property
Can, certain translucidus, water absorption rate is declined.
(3) the alloy powder good flowing properties, can be in functional paint, chromatographic isolation, medicament slow release, selective laser sintering
Equal fields application；In application in electrostatic spraying, powdery paints coloring is good, it is magnificent can to create color, and have good
The spraying product of good wearability；When alloy powder is as consumptive material in 3D printing-Selective Laser Sintering, article surface
It is smooth that there is significant dimensional stability, especially suitable for mechanograph, the art work and personalized customization etc..
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Embodiment 1
The preparation of 6 microballoon of apertures nylon:
By 6 pellet of 40g nylon, 240ml formic acid, it is added in reaction kettle and is warming up to 80 DEG C, stirring 2h dissolves material sufficiently,
Then the ethanol solution that 400ml concentration is 10%g/ml polyvinylpyrrolidone (PVP-K30) is added, is stood after being vigorously stirred,
Powder is precipitated.It filters, ethanol washing, vacuum drying obtains 6 microballoon of apertures nylon；The average grain diameter of 6 microballoon of gained nylon is 60
μm, specific surface area 23m2/ g, porosity 77%, aperture are 0.1~2 μm, heap density 0.2g/mL.Its melting temperature, thermal decomposition temperature
The data such as degree, water imbibition, tensile strength are as shown in table 1.
Embodiment 2
The preparation of 12 microballoon of apertures nylon:
By 12 pellet of 40g nylon, 240ml acetic acid, it is added in reaction kettle and is warming up to 100 DEG C, stirring 2h keeps material sufficiently molten
Then solution is added the ethanol solution that 400ml concentration is 20%g/ml polyvinylpyrrolidone (PVP-K30), is vigorously stirred rear quiet
It sets, powder is precipitated.It filters, ethanol washing, vacuum drying obtains 12 microballoon of apertures nylon；12 microspherulite diameter of gained nylon is 60 μ
M, specific surface area 1.1m2/ g, porosity 62%, aperture are 0.1~4 μm, heap density 0.36g/mL.Its melting temperature, thermal decomposition
The data such as temperature, water imbibition, tensile strength are as shown in table 1.
Likewise, other apertures nylon 11 microballoons, nylon 1212 microballoon, nylon 612 microballoon, nylon in the embodiment of the present invention
610 microballoons or nylon 1010 microballoon are prepared using above-mentioned similar method.The partial size of gained apertures nylon micro-sphere,
The properties such as specific surface area, porosity aperture are different with preparation method and preparation condition and are varied.
Embodiment 3
The preparation of nylon 6/PMMA alloy microballoon, steps are as follows:
6 apertures microballoon of 5g nylon is taken to be added in the water and ethanol solution that 50g mass ratio is 1:1, in three mouthfuls of burnings of 150mL
Stirring 1h is mixed to get apertures nylon micro-sphere dispersion liquid in bottle；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, is warming up to
At 45 DEG C, methyl methacrylate monomer (MMA) 0.5g is added, then heats to 75 DEG C of reactions and stops reaction afterwards for 24 hours, produced
Object carries out decompression suction filtration, and drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.
Gained nylon 6/PMMA alloy microspherulite diameter is held essentially constant with former apertures nylon micro-sphere partial size, melting temperature
The data such as degree, thermal decomposition temperature, water imbibition, tensile strength are as shown in table 1.
Embodiment 4
The preparation of nylon 6/PMMA alloy microballoon
6 apertures microballoon of 5g nylon is taken to be added in the water and ethanol solution that 50g mass ratio is 1:1, in three mouthfuls of burnings of 150mL
It is stirred to obtain apertures nylon micro-sphere dispersion liquid in bottle；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, is warming up to 45
DEG C when, be added methyl methacrylate monomer (MMA) 1g, then heat to 75 DEG C reaction for 24 hours afterwards stop reaction, obtain product into
Row decompression filters, and drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.
Gained nylon 6/PMMA alloy microspherulite diameter is held essentially constant with former apertures nylon micro-sphere partial size, melting temperature
The data such as degree, thermal decomposition temperature, water imbibition, tensile strength are as shown in table 1.
Embodiment 5
The preparation of nylon 6/PMMA alloy microballoon
6 apertures microballoon of 5g nylon is taken to be added in the water and ethanol solution that 50g mass ratio is 1:1, in three mouthfuls of burnings of 150mL
It is stirred to obtain apertures nylon micro-sphere dispersion liquid in bottle；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, is warming up to 45
DEG C when, be added methyl methacrylate monomer (MMA) 5g, then heat to 75 DEG C reaction for 24 hours afterwards stop reaction, obtain product into
Row decompression filters, and drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.
Gained nylon 6/PMMA alloy microspherulite diameter is held essentially constant with former apertures nylon micro-sphere partial size, melting temperature
The data such as degree, thermal decomposition temperature, water imbibition, tensile strength are as shown in table 1.
Embodiment 6
The preparation of nylon 6/PMMA alloy microballoon
6 apertures microballoon of 5g nylon is taken to be added in the water and ethanol solution that 50g mass ratio is 1:1, in three mouthfuls of burnings of 150mL
It is stirred to obtain apertures nylon micro-sphere dispersion liquid in bottle；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, is warming up to 45
DEG C when, be added methyl methacrylate monomer (MMA) 10g, then heat to 75 DEG C reaction for 24 hours afterwards stop reaction, obtain product
Decompression suction filtration is carried out, drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.
Gained nylon 6/PMMA alloy microspherulite diameter is held essentially constant with former apertures nylon micro-sphere partial size, melting temperature
The data such as degree, thermal decomposition temperature, water imbibition, tensile strength are as shown in table 1.
Embodiment 7
The preparation of nylon 6/PMMA alloy microballoon
6 apertures microballoon of 5g nylon is taken to be added in the water and ethanol solution that 50g mass ratio is 1:1, in three mouthfuls of burnings of 150mL
It is stirred to obtain apertures nylon micro-sphere dispersion liquid in bottle；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, is warming up to 45
DEG C when, be added methyl methacrylate monomer (MMA) 25g, then heat to 75 DEG C reaction for 24 hours afterwards stop reaction, obtain product
Decompression suction filtration is carried out, drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.
Gained nylon 6/PMMA alloy microspherulite diameter is held essentially constant with former apertures nylon micro-sphere partial size, melting temperature
The data such as degree, thermal decomposition temperature, water imbibition, tensile strength are as shown in table 1.
Comparative example 1
6 apertures microballoon of 5g nylon is taken to be added in the water and ethanol solution that 50g mass ratio is 1:1, in three mouthfuls of burnings of 150mL
Stirring 1h is mixed to get apertures nylon micro-sphere dispersion liquid in bottle；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, is warming up to
At 45 DEG C, methyl methacrylate monomer (MMA) 50g is added, then heats to 75 DEG C of reactions and stops reaction afterwards for 24 hours, produced
Object carries out decompression suction filtration, and drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.
Gained nylon 6/PMMA alloy microspherulite diameter is held essentially constant with former apertures nylon micro-sphere partial size, melting temperature
The data such as degree, water imbibition, tensile strength are as shown in table 1.
The nylon 6/PMMA alloy microballoon properties of 1 difference PMMA content of table
As it can be seen from table 1 the heap density of alloy microballoon increases, and water absorption rate is declined slightly, power as PMMA content increases
It is little to learn performance change, and thermal stability decreases.But PMMA content crosses low-alloy and shows the performance of polyamide and reach
Has the effect of dimensional stability less than required alloy, PMMA is excessively high to be will lead to alloy mechanical property decline and influence actual use
Effect.And if obtaining alloy microballoon by the way of physical blending, PMMA and nylon micro-sphere associativity are bad, and injection molding batten is easy
Occur phenomenon of phase separation, have data find out the mode of physical blending be prepared nylon 6/PMMA alloy microballoon mechanical property compared with
Difference, it is difficult to reach performance requirement.
Comparative example 2
Nylon 6/PMMA alloy microballoon is prepared by the way of physical blending, wherein PMMA content 30wt%.Alloy
The properties index of microballoon is as shown in table 1.
Embodiment 8-13
Embodiment 3 is repeated, difference is only that, 6 microballoon of apertures nylon is changed to 12 microballoon of apertures nylon, apertures nylon respectively
11 microballoons, apertures nylon 1010 microballoon, apertures nylon66 fiber microballoon, apertures nylon 612 microballoon, apertures nylon 610 microballoon, remaining
Part is constant, and nylon/PMMA alloy microballoon is prepared.Its different nylon classification alloy microballoon properties indexes such as the following table 2 institute
Show.
Comparative example 3
Take the water and ethanol solution that 50g mass ratio is 1:1 in the three-necked flask of 150mL, stirring 1h is mixed to get dispersion
Liquid；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, when being warming up to 45 DEG C, is added methyl methacrylate monomer (MMA)
0.5g then heats to 75 DEG C of reactions and stops reaction afterwards for 24 hours, obtains product and carry out decompression suction filtration, dry and obtain after ethanol washing
PMMA resin.PMMA properties index is as shown in table 2 below.
The PA/PMMA alloy microballoon properties of the different nylon of table 2
It can be seen that compared with pure PMMA and pure nylon from the table, alloy is made in nylon addition PMMA in the present invention, can change
The water imbibition of kind polyamide, and will not influence its mechanical property
Embodiment 14-18
Embodiment 3 is repeated, difference is only that, reaction temperature is changed to 50 DEG C, 60 DEG C, 80 DEG C, 90 DEG C, 100 from 75 DEG C respectively
DEG C, remaining condition is constant, the nylon 6/PMMA alloy microballoon being prepared.Alloy microballoon properties and 3 phase of embodiment is made
Seemingly, illustrate in 50~100 DEG C of ranges of suitable reaction temperature, alloy microballoon performance change obtained is small.
Comparative example 4-5
Take respectively 6 apertures microballoon of 5g nylon be added to 50g mass ratio be 1:1 water and ethanol solution in, in 150mL A,
1h is stirred in B three-necked flask is mixed to get apertures nylon micro-sphere dispersion liquid；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen
Gas when being warming up to 45 DEG C, is added methyl methacrylate monomer (MMA) 0.5g, is then warming up to 20 DEG C respectively and reacts with 200 DEG C
Stop reaction afterwards for 24 hours, obtains product and carry out decompression suction filtration, drying obtains nylon 6/PMMA alloy microballoon after ethanol washing.It is made
Alloy is obtained through detection, reacts very slow under lower temperature, the PMMA content of synthesis is seldom, performance indicator and pure apertures nylon micro-sphere
It is similar；And alloy obtained under high temperature, apertures nylon micro-sphere are partly dissolved, the micro-sphere structure that cannot disperse and become blocky,
The micro-sphere structure product that cannot be needed；
It can be seen that from comparative example 4-5, reaction temperature is lower than 50 DEG C or is all unfavorable for the system of alloy microballoon higher than 100 DEG C
It is standby.
Embodiment 19-23
Embodiment 3 is repeated, difference is only that, catalyst 0.1g is changed to 1mg, 5mg, 10mg, 50mg, 0.5g respectively, remaining
Condition is constant, the nylon 6/PMMA alloy microballoon being prepared.It is similar to Example 3 that alloy microballoon properties are made, are urging
Agent additional amount is in the optimum range of 0.1wt%~10wt% of methyl methacrylate monomer, and the alloy being prepared is micro-
Ball performance change is small.
Comparative example 6-7
Embodiment 3 is repeated, difference is only that, catalyst 0.1g is changed to 0g, 0.1mg respectively, remaining condition is constant, is prepared into
The nylon 6/PMMA alloy microballoon arrived.It is similar to pure nylon micro-sphere that product property is made, illustrates not having to catalyst or catalyst mistake
It will affect the generation of PMMA less.
Embodiment 24-25
Embodiment 3 is repeated, difference is only that, catalyst ammonium persulfate is changed to hydrogen peroxide, potassium peroxydisulfate respectively, remaining
Condition is constant, the nylon 6/PMMA alloy microballoon being prepared.It is similar to Example 3 that alloy microballoon properties are made, explanation
Two kinds of catalyst have preferable catalytic effect to the synthesis of PMMA.
Embodiment 26-30
Embodiment 3 is repeated, difference is only that, by the reaction time from being changed to 6h, 12h, 36h, 48h, 60h respectively for 24 hours, remaining
Condition is constant, the nylon 6/PMMA alloy microballoon being prepared.It is similar to Example 3 that alloy microballoon properties are made, reaction
It is little that time is at least the alloy microballoon performance change that 6h is prepared, but the reaction time too long will increase cost, therefore this
Invention selects for 6~reaction time for 24 hours.
Comparative example 8
Take 6 apertures microballoon of 5g nylon be added to 50g mass ratio be 1:1 water and ethanol solution in the three-necked flask of 150mL
In, stirring 1h is mixed to get dispersion liquid；0.1g ammonium persulfate is added, is passed through nitrogen discharge oxygen, when being warming up to 45 DEG C, first is added
Base methacrylate monomer (MMA) 0.5g stops reaction after then heating to 75 DEG C of reaction 5h, obtains product and carry out decompression pumping
It filters, drying obtains PA/PMMA alloy microballoon after ethanol washing.
PMMA content is less in alloy microballoon obtained by being detected, and it is required to illustrate that the reaction time is unfavorable for obtaining lower than 6h
Reaction product.
Embodiment 31-38
Repeat embodiment 3, difference is only that, by solvent quality 50g be changed to respectively 5g, 10g, 25g, 40g, 60g, 150g,
300g, 500g, remaining condition is constant, and nylon 6/PMMA alloy microballoon is prepared, and performance is as shown in table 3.
Alloy microballoon properties under 3 different solvents usage amount of table
In the range of solvent is using 1~100 times of amount that quality is nylon micro-sphere as can be seen from Table 3, alloy obtained is micro-
Ball properties are similar to Example 3, in the range of solvent is using 5~12 times of amounts that quality is nylon micro-sphere, conjunction obtained
Gold microsphere properties are optimal.And sediment is easily made to bond blocking, powder dispersibility if solvent for use less (comparative example 9)
Difference；Solvent uses more (comparative example 10) then and can make PMMA content in alloy lower and the PMMA generated in solution is easily adsorbed on
Microsphere surface causes PMMA to be unevenly distributed, and influences alloy microballoon performance.
Comparative example 9-10
Take 6 apertures microballoon of 5g nylon be added to 1g mass ratio be 1:1 water and ethanol solution in the three-necked flask A of 150mL
In, take 6 apertures microballoon of 5g nylon be added to 600g mass ratio be 1:1 water and ethanol solution in the three-necked flask B of 150mL；
Stirring 1h is mixed to get dispersion liquid, and 0.1g ammonium persulfate is added, and is passed through nitrogen discharge oxygen, when being warming up to 45 DEG C, methyl is added
Methacrylate monomer (MMA) 0.5g stops reaction after then heating to 75 DEG C of reaction 1h, obtains product and carry out decompression suction filtration,
Drying obtains PA/PMMA alloy microballoon after ethanol washing.
The alloy microballoon that cannot disperse through alloy obtained by detection A in blocky, illustrates that solvent is very few and is unfavorable for obtaining
Required reaction product.
Through detection B product in PMMA content is more in the solution and content is less in nylon micro-sphere, illustrate that solvent is excessive
It influences PMMA synthetic quantity in the alloy and influences alloy property.
Embodiment 39-43
Embodiment 3 is repeated, difference is only that, etoh solvent and deionized water quality ratio 1:1 are changed to 1:0.1,1 respectively:
0.5,1:2,1:5,1:10, remaining condition is constant, the nylon 6/PMMA alloy microballoon being prepared.Alloy microballoon items are made
Can have with 3 performance of embodiment and a little change, when the content of water in solvent is greater than ethyl alcohol, nylon micro-sphere is more easily broken, therefore solution
Middle aqueous solution is excessively unfavorable for obtaining alloy microballoon, and the more more pairing gold performances influences of ethanol content are smaller in solvent；But
When ethyl alcohol and water-soluble liquid proportional are more than 1:10 in solvent, it is unfavorable for catalyst in the solution miscible, and then pairing gold microsphere
Preparation has an impact.
Comparative example 11-12
It takes 6 apertures microballoon of 5g nylon to be added to 50g ethanol solution in the three-necked flask A of 150mL respectively, takes 5g nylon 6
Apertures microballoon is added to 50g aqueous solution in the three-necked flask B of 150mL, and stirring 1h is mixed to get dispersion liquid；0.1g over cure is added
Sour ammonium is passed through nitrogen discharge oxygen, when being warming up to 45 DEG C, methyl methacrylate monomer (MMA) 0.5g is added, then heats to
Stop reaction after 75 DEG C of reaction 1h, obtains product and carry out decompression suction filtration, drying obtains PA/PMMA alloy microballoon after ethanol washing.
Being detected obtained product A is nylon micro-sphere entirely, illustrates that PMMA cannot be synthesized when solvent is straight alcohol；And product B
Nylon micro-sphere is crushed substantially, and alloy illustrates to be unfavorable for obtaining required reaction product when solvent is aqueous solution in cotton-shaped.
Embodiment 44
By 3 gained nylon 6/PMMA alloy microballoon 50g of embodiment, antioxidant 2,2'- di-2-ethylhexylphosphine oxide-(4- methyl -6- is added
Tert-butyl phenol) (antioxidant 2246) 0.1g, the stirring and mixing 1h in vertical stirrer, 200 meshes excessively after material is mixed evenly,
It can be directly used for 3D printing-Selective Laser Sintering.
Embodiment 45
By 3 gained nylon 6/PMMA alloy microballoon 50g of embodiment, antioxidant 2,2'- di-2-ethylhexylphosphine oxide-(4- methyl -6- is added
Tert-butyl phenol) (antioxidant 2246) 0.1g, the stirring and mixing 1h in vertical stirrer, 200 meshes excessively after material is mixed evenly,
It can be directly used for electrostatic spraying.
Embodiment 46-49
Embodiment 40 is repeated, difference is only that, antioxidant 2246 is changed to antioxidant 1010, irgasfos 168, antioxygen respectively
Agent 1076, antioxidant 1098, alloy powder sieving obtained, can be directly used for electrostatic spraying or Selective Laser Sintering.
Embodiment 50
3 gained nylon 6/PMMA alloy microballoon 50g of embodiment is stirred continuously with the immersion of 90~95% ethyl alcohol except degassing
Column is filled after bubble, with the ethanol elution of 3-4 times of volume, be washed till eluent it is transparent and after being evaporated without residue.Again successively with 2-2.5 times
The elution of volume 5%NaOH aqueous solution is finally eluted to pH neutrality with distilled water, for stationary phase in column chromatography, protein isolate matter,
Flavone compound.
Embodiment 51
Nylon/acrylic resin alloy microballoon obtained by embodiment 1-43 can further pass through physically or chemically absorption carriage
Drug molecule is used as medicament slow release and studies.
Conclusion: apertures nylon micro-sphere and polymethyl methacrylate pass through hydrogen bond in the alloy microballoon that the present invention is prepared
It is cross-linked with each other, under the collective effect of the two, obtained nylon-polymethyl methacrylate alloy microballoon has both PA's and PMMA
Advantage, mechanical property is more preferable, and has certain translucidus, and water absorption rate is declined.Wherein PMMA content crosses low-alloy performance
Out the performance of polyamide and required alloy, which is not achieved, has the effect of dimensional stability, it is excessively high to will lead to alloy mechanical property decline
And influence practical effect.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (3)
1. a kind of nylon-polymethyl methacrylate alloy microballoon preparation method, which comprises the steps of:
1) apertures nylon micro-sphere is added in solvent, 1 ~ 2h is stirred at room temperature and is mixed to get uniform nylon micro-sphere dispersion liquid；Institute
The additional amount for stating solvent is 1 ~ 100 times of apertures nylon micro-sphere quality, and the solvent is ethyl alcohol and deionized water mixed solution, second
The mass ratio of alcohol and water is 1:0.1~10；
2) catalyst is added in the nylon dispersion liquid into step 1), is passed through nitrogen discharge oxygen and adds when being warming up to 30 ~ 50 DEG C
Enter methyl methacrylate monomer, mixing is stirred at room temperature, then be warming up to 50 ~ 100 DEG C, through stopping after home position polymerization reaction 6 ~ for 24 hours
Reaction, obtains product and carries out decompression suction filtration, and drying obtains nylon-polymethyl methacrylate alloy microballoon, the first after washing
The additional amount of base methacrylate monomer is 0.1 ~ 5 times of apertures nylon micro-sphere；
The catalyst is selected from one or more of hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate.
2. a kind of nylon according to claim 1-polymethyl methacrylate alloy microballoon preparation method, feature exist
In catalyst charge described in step 2 is 0.1 ~ 10wt% of methyl methacrylate monomer.
3. a kind of nylon that preparation method as described in claim 1 is prepared-polymethyl methacrylate alloy microballoon system
The dusty material obtained, which is characterized in that the dusty material includes nylon-polymethyl methacrylate alloy microballoon and antioxygen
Agent, the additional amount of the antioxidant are 0.05wt% ~ 1wt% of alloy microballoon；The antioxidant is selected from antioxidant 2246, antioxidant
1010, one or both of irgasfos 168, antioxidant 1076, antioxidant 1098.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1534063A (en) * | 2003-03-15 | 2004-10-06 | 1 | Laser sintered powder, its preparation method and molded products obtained from it |
| CN101787138A (en) * | 2010-01-26 | 2010-07-28 | 广东冠昊生物科技股份有限公司 | Preparation method of micron-sized polymethylmethacrylate microsphere |
| CN104250437A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Modified nylon microsphere material and its application in 3D printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1534063A (en) * | 2003-03-15 | 2004-10-06 | 1 | Laser sintered powder, its preparation method and molded products obtained from it |
| CN101787138A (en) * | 2010-01-26 | 2010-07-28 | 广东冠昊生物科技股份有限公司 | Preparation method of micron-sized polymethylmethacrylate microsphere |
| CN104250437A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Modified nylon microsphere material and its application in 3D printing |
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| "无皂乳液聚合制备SiO2/PMMA纳米复合胶体微球";陈金庆等;《塑料工业》;20111031;第39卷(第10期);第31页1.2实验过程部分 * |
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