CN110054835A - A kind of preparation method of high magnification conductivity type polypropylene foaming beads - Google Patents
A kind of preparation method of high magnification conductivity type polypropylene foaming beads Download PDFInfo
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- CN110054835A CN110054835A CN201910238875.8A CN201910238875A CN110054835A CN 110054835 A CN110054835 A CN 110054835A CN 201910238875 A CN201910238875 A CN 201910238875A CN 110054835 A CN110054835 A CN 110054835A
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Abstract
The invention belongs to polypropylene foaming beads technical fields, more particularly to a kind of preparation method of high magnification conductivity type polypropylene foaming beads, the following steps are included: acrylic resin and conductive black are mixed in a certain ratio by A., process to obtain conducting masterbatch one by twin-screw extrusion；B. acrylic resin and conductive filler are mixed in a certain ratio, process to obtain conducting masterbatch two by twin-screw extrusion；C. acrylic resin, nucleating agent, conducting masterbatch one and two melt blending of conducting masterbatch are obtained into polypropylene microparticle；D. polypropylene microparticle made from step C is put into foamable reaction kettle together with decentralized medium and dispersing agent, be then passed through foaming agent to reaction kettle and heat pressurization, when reaching set temperature and pressure, pressure release obtains polypropylene foaming beads；E. conductivity type polypropylene foaming beads made from step D are subjected to air precompressed, make bead internal reservoir pressure-air, then carry out second time of foaming, obtains high magnification conductivity type polypropylene foaming beads.
Description
Technical field
The invention belongs to polypropylene foaming beads technical fields, and in particular to a kind of polypropylene expanded pearl of high magnification conductivity type
The preparation method of grain.
Background technique
With the continuous expansion of expanded polypropylene application field, market proposes functionalization expanded polypropylene increasingly harsh
It is required that.For example, electronic component causes to damage during packed and transported due to rubbing or hitting generation electrostatic in order to prevent,
Anti-static type expanded polypropylene comes into being.It on the one hand, can be with due to the excellent buffering of expanded polypropylene itself and energy absorption performance
The collision of effective protection product causes damage；On the other hand, Antistatic type expanded polypropylene product can effectively shift electronic component fortune
The electrostatic assembled during defeated due to frictional impact, to reach protecting effect.
But with the raising of market demands, packed and transported and high-end laboratory for some electronic components are equipped with
Or other special dimensions etc., Antistatic type expanded polypropylene have been far from satisfying demand.Therefore, semiconductive pickup is even conductive
Application of the type expanded polypropylene in these fields is constantly opened up.Currently, the production of conductivity type expanded polypropylene beads is wrapped substantially
Containing two ways.One is uniformly coating conduction by outer painting conductive auxiliary agent in expanded polypropylene article surface and being led to realize
Electricity Functional.This method is not only troublesome in poeration, high labor cost, but also conductive auxiliary agent is often coated and is difficult to uniformly, action time
Also shorter；The second is processing is blended by filling conductive filler in formula.Although this mode conductive effect duration
It is longer, but have the defects that be difficult to overcome.Because in order to reach the requirement of more highly conductive ability, it is necessary to toward resin matrix
The middle a large amount of conductive filler of filling, such as conductive black, electrically conductive graphite etc., and a large amount of fillings of conductive filler are to resin expanded
Performance brings adverse effect.So that abscess-size is uneven, electric conductivity is unstable, powerful expanded beads can not be especially produced
Grain.Higher filler is filled so that the expanded polypropylene beads abscess-size that this mode obtains is difficult to control, difficult forming, and
And product mechanical property cannot be guaranteed.Also, conductive filler itself is at high price, and high filler loading capacity undoubtedly make its application by
Greatly limitation.
Chinese patent literature CN107522942A discloses a kind of conducting polypropylene microcellular foam material and its production method,
It is filled out with the conduction of the first acrylic resin of 10-100 parts by weight, the second acrylic resin of 100 parts by weight, 5-15 parts by weight
Material and the dispersing agents of 0.1-1 parts by weight prepare conducting polypropylene microcellular foam material, wherein by carbon black or (and) metal powder
It mixes with carbon nanotube as conductive filler, to reduce the content of conductive filler, reduces cost, reduce and polypropylene is steeped
The damage of foam material property.But unmodified inorganic particle is directly added in organic resin by it, not by coupling agent modified
Conductive filler bad dispersibility, cannot not only obtain ideal conductive effect, also will affect polyacrylic foaming situation.It foamed
Cheng Zhong, polypropylene expanded expansion generate radial drawing effect, destroy the network structure for being filled in conductive filler therein.
European patent document EP3015497A1 discloses a kind of conducting polypropylene expanded bead preparation method.Its conduction is poly-
Propylene expanded bead includes the conductive black (being in terms of 100 by polypropylene weight part) of 11-25 parts by weight, prepares multiplying power at 25 times
The expanded polypropylene beads of left and right, product has more satisfied electric conductivity after molded molding.Chinese patent literature
CN104053713A discloses a kind of polypropylene-based resin expanded beads, preparation method and polypropylene-base expanded beads
Mechanograph, the additive amount of conductive carbon black is 6-14 part in every 100 parts by weight of base numerical value, but its after reexpansion prepared by
The sheet resistance of mechanograph (i.e. molded article) there was only 1.0 × 1015Ω, resistivity is excessive after second time of foaming, and electric conductivity is poor.
Summary of the invention
In order to obtain the polypropylene foaming beads with high foamability and high conduction performance simultaneously, the present invention is disclosed
A kind of preparation method of high magnification conductivity type polypropylene foaming beads, the polypropylene foaming beads can ensure high conductivity
High foamability is realized while energy.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of high magnification conductivity type polypropylene foaming beads, comprising the following steps:
A. it after being mixed in a certain ratio acrylic resin and conductive black uniformly, processes and is led by twin-screw extrusion
Goddess of lightning's material one；
B. it after being mixed in a certain ratio acrylic resin and conductive filler uniformly, processes and is led by twin-screw extrusion
Goddess of lightning's material two；
C. acrylic resin, stabilizer, nucleating agent, conducting masterbatch one and two melt blending of conducting masterbatch are obtained into polypropylene
Particle；
D., it is anti-that polypropylene microparticle made from step C is put into foaming together with decentralized medium, dispersing agent and surfactant
It answers in kettle, foaming agent is then continually fed into foamable reaction kettle and heats pressurization and is let out rapidly when reaching set temperature and pressure
Pressure, obtains conductivity type polypropylene foaming beads；
E. conductivity type polypropylene foaming beads made from step D are subjected to air precompressed, keep bead internal reservoir high pressure empty
Then gas carries out second time of foaming, obtain high magnification conductivity type polypropylene foaming beads；
In the step B conductive filler the preparation method comprises the following steps: by 55-95 parts of polyethylene powders, 10-40 parts of carbon nanotubes and
It is made after ultrasonic disperse, blending and stirring, being heated to reflux after 0.5-5 parts of ethyl alcohol mixing；
Acrylic resin in the step A-C is same acrylic resin, and acrylic resin is mole hundred
The polypropylene homopolymer and/or propylene of score >=50% and the copolymer of one or more comonomers.
Conductive black and conductive filler are mixed to prepare conducting masterbatch one and conducting masterbatch two with acrylic resin respectively, and
It is non-the two is disposably mixed into acrylic resin to prepare conducting masterbatch, it can be to avoid conductive black enters carbon nanotube and influences to lead
The formation of electric network is to influence electric conductivity.
Preferably, in above-mentioned steps A each component weight percent are as follows: acrylic resin 80-95%, conductive black 5-
20%；The weight percent of each component in the step B are as follows: acrylic resin 90-99%, conductive filler 1-10%.
Preferably, in above-mentioned steps C each component weight percent are as follows: acrylic resin 60-70%, stabilizer 0.5-
2%, two 10-20% of nucleating agent 0.1-3.0%, one 10-20% of conducting masterbatch and conducting masterbatch, the nucleating agent be calcium carbonate,
One or more of magnesium sulfate, talcum powder, aluminium hydroxide, silica, zinc borate.
Preferably, foaming agent in above-mentioned steps D be one of carbon dioxide, nitrogen, air, pentane and oxygen or
Several, decentralized medium is deionized water, dispersing agent be kaolin, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate,
One or more of silica and zinc borate, preferably kaolin；The weight of the decentralized medium dosage and polypropylene microparticle
Than for 1-3:1, the weight percent that dispersant dosage accounts for polypropylene microparticle is 0.02-2%, preferably 0.1-1%.
Preferably, surfactant is stearic acid, neopelex, glycine betaine and fat in above-mentioned steps D
One or more of acid glyceride, preferably neopelex；The dosage of surfactant accounts for polypropylene microparticle
Weight percent is 0.002-2%, preferably 0.1-0.3%.
Preferably, in above-mentioned steps D after rapid pressure release, by the polypropylene foaming beads of acquisition under the conditions of 70-80 DEG C
Keep the temperature 20-30min.When polypropylene foaming beads just come out from foamable reaction kettle, encounters cold air and be easy to shrink, in order to subtract
The contraction of few bead, keeps its original multiplying power, bead is recycled 20-30min in the pipeline of heating, keep its holding original
Bead state and multiplying power are more stable.
Preferably, above-mentioned conductive black partial size is 1-150nm, the carbon nanotube is single-walled carbon nanotube, adjacent benzene
Dibutyl carboxylic acid oil factor is 100-600ml/100g.Compared with multi-walled pipes, the distribution of single-walled pipe diameter is small, lacks
It falls into less, there is higher uniformity consistency, therefore it has more perfect electric conductivity.
Preferably, above-mentioned conductive black is silane coupler modified conductive black；The carbon nanotube is silane coupled
Agent modified carbon nano-tube.Conductive black and carbon nanotube are modified with silane coupling agent, is conducive to conductive black and carbon is received
Mitron is evenly dispersed in acrylic resin, avoids reuniting, to advantageously reduce the dosage of conductive black and carbon nanotube.
Preferably, above-mentioned silane coupling agent is Silane coupling agent KH550.Due to Silane coupling agent KH550 band polarized
Stronger amino, can not only make to combine between conductive black and carbon nanotube and acrylic resin even closer, also help
It is evenly dispersed in system in guidance conductive black and carbon nanotube, to form good conductive network；In addition, conductive charcoal
Black and carbon nanotube selects to be modified with KH550, the amino that denatured conductive carbon black and modified carbon nano tube pipe surface have it
Between react, be also beneficial to form continuous network between conductive black and carbon nanotube, enhance the electric conductivity of product.
Preferably, above-mentioned silane coupling agent are as follows:
(hereinafter referred to as: amino silicane coupling agent)
The amino silicane coupling agent the preparation method comprises the following steps: by molar ratio be 1:1 1- ethylene methacrylic amine and trimethoxy
Silane is added in reaction kettle, adds the Pt-PMVS catalyst of 20ppm, is heated to 85 DEG C, is stirred to react 8-10h, obtain amino
Silane coupling agent, reaction equation are as follows:
The carbon-chain structure of amino silicane coupling agent is similar to polypropylene carbon-chain structure, to conductive black and carbon nano-tube modification
Afterwards, be conducive to it is compatible between conductive black and carbon nanotube and acrylic resin, to be more conducive to the shape of conductive network
At, and help to reduce to polypropylene expanded influence.
The present invention have it is following the utility model has the advantages that
(1) conductive black and conductive filler are mixed to prepare conducting masterbatch one and conducting masterbatch with acrylic resin respectively
Two, rather than the two is disposably mixed into acrylic resin and prepares conducting masterbatch, carbon nanotube can be entered to avoid conductive black and
The formation of conductive network is influenced to influence electric conductivity；
(2) use of surfactant is conducive to polypropylene microparticle and disperses in a dispersion medium, to obtain better
Foaming effect；
(3) conductive black and carbon nanotube are modified with silane coupling agent, are conducive to conductive black and carbon nanotube
It is evenly dispersed in acrylic resin, it without using dispersing agent, avoids reuniting, to advantageously reduce conductive black and carbon is received
The dosage of mitron；
(4) the Silane coupling agent KH550 band stronger amino of polarized, select KH550 to conductive black and carbon nanotube into
Row is modified can not only to be made to combine between conductive black and carbon nanotube and acrylic resin even closer, additionally aid guidance
Conductive black and carbon nanotube are evenly dispersed in system, to form good conductive network；In addition, conductive black and carbon
Nanotube selects to be modified with KH550, reacts between the amino that denatured conductive carbon black and modified carbon nano tube pipe surface have,
It is also beneficial to form continuous network between conductive black and carbon nanotube, enhances the electric conductivity of product；
(5) carbon-chain structure of amino silicane coupling agent is similar to polypropylene carbon-chain structure, to conductive black and carbon nanotube
It is modified, be conducive to it is compatible between conductive black and carbon nanotube and acrylic resin, to be more conducive to conductive network
Formation, and help to reduce to polypropylene expanded influence, one step foaming multiplying power is 15 times or so, and second time of foaming multiplying power can be with
Reach 45 times or more, to obtain the smaller PP foam material of density.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the conductive network structural schematic diagram of conductivity type polypropylene foaming beads prepared by the present invention, wherein 1 is poly-
Propylene expanded bead；2 be carbon nanotube；3 be conductive black.
Fig. 2 is the SEM figure in the poly- third type expanded bead section of conductivity type prepared by the present invention.
Specific embodiment
Presently in connection with embodiment, the present invention is described in further detail.
The preparation method of high magnification conductivity type polypropylene foaming beads, comprising the following steps:
A. it after being mixed in a certain ratio acrylic resin and conductive black uniformly, processes and is led by twin-screw extrusion
Goddess of lightning's material one；
B. it after being mixed in a certain ratio acrylic resin and conductive filler uniformly, processes and is led by twin-screw extrusion
Goddess of lightning's material two；
C. acrylic resin, stabilizer, nucleating agent, conducting masterbatch one and two melt blending of conducting masterbatch are obtained into polypropylene
Particle；
D. polypropylene microparticle made from step C is put into foamable reaction kettle together with decentralized medium and dispersing agent, then
It is continually fed into foaming agent into foamable reaction kettle and heats pressurization, when reaching set temperature and pressure, rapid pressure release obtains conduction
Type polypropylene foaming beads；
E. conductivity type polypropylene foaming beads made from step D are subjected to air precompressed, keep bead internal reservoir high pressure empty
Then gas carries out second time of foaming, obtain high magnification conductivity type polypropylene foaming beads；
Wherein, in step B conductive filler the preparation method comprises the following steps: by 55-95 parts of polyethylene powders, 1-40 parts of carbon nanotubes and
It is made after ultrasonic disperse, blending and stirring, being heated to reflux after 0.5-5 parts of ethyl alcohol mixing.It is specific the preparation method comprises the following steps: (a) according to
Ratio weighs above-mentioned polyethylene, carbon nanotube；(b) it is connected with above in the three-necked flask of reflux condensing tube and ethyl alcohol is added, stir
It mixes down and is slowly added to polyethylene powder and carbon nanotube；(c) ultrasonic water bath is heated to 60 DEG C, ultrasonic 2800W, after being condensed back 4h,
Make the ethyl alcohol in mixture volatilize in ventilating kitchen to finish, remaining black solid powder is conductive filler.
Polypropylene microparticle is specific the preparation method comprises the following steps: by acrylic resin, stabilizer, nucleating agent, conducting masterbatch in step C
One, conducting masterbatch is second-class mixes in proportion, and by extruder mixing, extrusion, wire drawing, pelletizing and drying, adjusts extruder
The identical polypropylene microparticle of grain size specification is prepared, is packaged spare；Each area's temperature of extruder is controlled substantially at 180-250 DEG C, micro-
Grain length is in 1.0-3.0mm, weight 0.5-2.0mg.
The set temperature being previously mentioned in step D is 135-160 DEG C, pressure 0.5-4.5MPa.
Rapid pressure releasing method is previously mentioned in step D is: opening dispensing valve when temperature and pressure reaches setting value, starts
Foaming, the pressure during this in foamable reaction kettle remain unchanged, and release material constantly out of kettle.
The pressure of air precompressed is 0.3-0.8MPa in step E, and the time is in 9-48h.
Silane coupler modified conductive black the preparation method comprises the following steps: 720g ethyl alcohol and 80g water is taken to be made into alcohol solution, will
200g silane coupling agent is added thereto, and is thoroughly mixed uniformly, is obtained silane coupling agent hydrolyzate, conductive black is dispersed
In hydrolyzate, stirring or ultrasonic vibration 30-60min are filtered, dry.
The method of silane coupler modified carbon nanotube is consistent with the method for silane coupler modified conductive black.
Wherein, one step foaming multiplying power is 15 times or so, and second time of foaming multiplying power can achieve 45 times or more.
See Table 1 for details for embodiment 1-11 each component and its weight percent.
Table 1
Embodiment 12 is substantially the same manner as Example 10, the difference is that, in step D after rapid pressure release, by the poly- of acquisition
Propylene expanded bead keeps the temperature 30min under the conditions of 70 DEG C；
Embodiment 13 is substantially the same manner as Example 10, the difference is that, in step D after rapid pressure release, by the poly- of acquisition
Propylene expanded bead keeps the temperature 20min under the conditions of 80 DEG C；
In embodiment 12 and 13 in step D after rapid pressure release, by the polypropylene foaming beads of acquisition in 70-80 DEG C of condition
Lower heat preservation 20-30min.Concrete operation method are as follows: the expanded bead just come out from foamable reaction kettle is put into a helical form
Utilidor in, temperature is maintained at 70-80 DEG C, and the length of helical form insulating tube is in 30-50m, bead circle transmission wherein
In the process, after pipeline remains that steady temperature, bead recycle 20-30min in the duct, into savings bag.
Comparative example 1 is substantially the same manner as Example 10, the difference is that, comparative example 1 replaces embodiment 10 with conductive black
Single-walled carbon nanotube in step B；
Comparative example 2, it is substantially the same manner as Example 10, the difference is that, comparative example 2 replaces implementing with single-walled carbon nanotube
Conductive black in 10 step A of example.
Comparative example 3, it is essentially identical with comparative example 1, the difference is that, comparative example 3 adds 50 parts of conducting masterbatch one.
Comparative example 4, it is essentially identical with comparative example 2, the difference is that, comparative example 2 adds 60 parts of conducting masterbatch two.
Comparative example 5 is substantially the same manner as Example 11, the difference is that, step E will first gather before carrying out air precompressed
Propylene expanded bead is heated to 50 DEG C.
Comparative example 6 is substantially the same manner as Example 11, the difference is that, step E will first gather before carrying out air precompressed
Propylene expanded bead is heated to 90 DEG C.
Fig. 1 is the conductive network structural schematic diagram of conductivity type polypropylene foaming beads prepared by embodiment 1, wherein 1 is
Polypropylene foaming beads, 2 be carbon nanotube, and 3 be conductive black, it can be seen that inside polypropylene foaming beads and surface is uniform
Conductive black and carbon nanotube are filled, and carbon nanotube connects each self-dispersed conductive black to form network structure.
Detailed test method and test result such as table 2 for properties in above-described embodiment 1-13 and comparative example 1-6
It is shown.
Table 2
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of preparation method of high magnification conductivity type polypropylene foaming beads, it is characterised in that: the following steps are included:
A. it after being mixed in a certain ratio acrylic resin and conductive black uniformly, processes to obtain conductive mother by twin-screw extrusion
Material one；
B. it after being mixed in a certain ratio acrylic resin and conductive filler uniformly, processes to obtain conductive mother by twin-screw extrusion
Material two；
C. it is micro- acrylic resin, stabilizer, nucleating agent, conducting masterbatch one and two melt blending of conducting masterbatch to be obtained into polypropylene
Grain；
D. polypropylene microparticle made from step C is put into foamable reaction kettle together with decentralized medium, dispersing agent and surfactant
In, it is then continually fed into foaming agent into foamable reaction kettle and heats pressurization, when reaching set temperature and pressure, rapid pressure release,
Obtain conductivity type polypropylene foaming beads；
E. conductivity type polypropylene foaming beads made from step D are subjected to air precompressed, make bead internal reservoir pressure-air, so
After carry out second time of foaming, obtain high magnification conductivity type polypropylene foaming beads；
Conductive filler the preparation method comprises the following steps: by 55-95 parts of polyethylene powders, 10-40 parts of carbon nanotubes and 0.5-5 in the step B
It is made after ultrasonic disperse, blending and stirring, being heated to reflux after ethyl alcohol mixing；
Acrylic resin in the step A-C is same acrylic resin, and acrylic resin is mole percentage
>=50% polypropylene homopolymer and/or propylene and the copolymer of one or more comonomers.
2. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: the step
The weight percent of each component in rapid A are as follows: acrylic resin 80-95%, conductive black 5-20%；Each component in the step B
Weight percent are as follows: acrylic resin 90-99%, conductive filler 1-10%.
3. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: the step
The weight percent of each component in rapid C are as follows: acrylic resin 60-70%, stabilizer 0.5-2%, nucleating agent 0.1-3.0%, lead
The goddess of lightning expect a 10-20% and two 10-20% of conducting masterbatch, the nucleating agent be calcium carbonate, magnesium sulfate, talcum powder, aluminium hydroxide,
One or more of silica, zinc borate.
4. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: the step
Foaming agent in rapid D is one or more of carbon dioxide, nitrogen, air, pentane and oxygen, and decentralized medium is deionization
Water, dispersing agent are in kaolin, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, silica and zinc borate
One or more, preferably kaolin；The decentralized medium dosage and the weight ratio of polypropylene microparticle are 1-3:1, dispersant dosage
The weight percent for accounting for polypropylene microparticle is 0.02-2%, preferably 0.1-1%.
5. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: the step
Surfactant is one or more of stearic acid, neopelex, glycine betaine and fatty glyceride in rapid D,
It is preferred that neopelex；The weight percent that the dosage of surfactant accounts for polypropylene microparticle is 0.002-2%, excellent
Select 0.1-0.3%.
6. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: the step
In rapid D after rapid pressure release, the polypropylene foaming beads of acquisition are kept the temperature into 20-30min under the conditions of 70-80 DEG C.
7. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: described to lead
Electric particle size carbon black is 1-150nm, and the carbon nanotube is single-walled carbon nanotube, and dibutyl phthalate oil factor is 100-
600ml/100g。
8. the preparation method of high magnification conductivity type polypropylene foaming beads as described in claim 1, it is characterised in that: described to lead
Electric carbon black is silane coupler modified conductive black；The carbon nanotube is silane coupler modified carbon nanotube.
9. the preparation method of high magnification conductivity type polypropylene foaming beads as claimed in claim 8, it is characterised in that: the silicon
Alkane coupling agent is Silane coupling agent KH550.
10. the preparation method of high magnification conductivity type polypropylene foaming beads as claimed in claim 8, it is characterised in that: described
Silane coupling agent are as follows:
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| CN115073848A (en) * | 2022-07-25 | 2022-09-20 | 上海科进生物技术有限公司 | Composition for preparing conductive polypropylene resin, preparation method and conductive suction head |
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