CN109988362A - A kind of micro-foaming polypropylene material and preparation method thereof - Google Patents

A kind of micro-foaming polypropylene material and preparation method thereof Download PDF

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Publication number
CN109988362A
CN109988362A CN201910310992.0A CN201910310992A CN109988362A CN 109988362 A CN109988362 A CN 109988362A CN 201910310992 A CN201910310992 A CN 201910310992A CN 109988362 A CN109988362 A CN 109988362A
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foaming
micro
foaming agent
agent
polypropylene material
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CN109988362B (en
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张诗妍
盖东海
汤文立
盖国胜
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Zibo Qingda Powder Material Engineering Co ltd
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Qingda Aloin (zibo) New Materials Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102Azo-compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102Azo-compounds
    • C08J9/103Azodicarbonamide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/108Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond in a heterocyclic ring containing at least one carbon atom
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/02CO2-releasing, e.g. NaHCO3 and citric acid
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/04N2 releasing, ex azodicarbonamide or nitroso compound
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/18Binary blends of expanding agents
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    • C08J2205/00Foams characterised by their properties
    • C08J2205/04Foams characterised by their properties characterised by the foam pores
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/12Polypropene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds

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Abstract

The present invention relates to the field of polymers more particularly to a kind of micro-foaming polypropylene material and preparation method thereof.The present invention provides one kind and has a low-density, high foamability, abscess uniform pore diameter and is concentrated mainly on material internal, and surface has the micro-foaming polypropylene material of excellent appearance and the preparation method of this kind of micro-foaming polypropylene material without trace.Foaming agent composite powder of the particle diameter distribution D50 value at 1-10 microns is prepared by blapharoplast and composite foamable agent, make foaming agent uniform load on blapharoplast, micro-foaming polypropylene material is prepared with acrylic resin mixing extruding pelletization, injection molding in foaming agent composite powder.Compared with traditional fretting map mode, cost of the present invention is lower, and the requirement to special equipment is less, and can maximum possible reservation virgin pp itself good characteristic.

Description

A kind of micro-foaming polypropylene material and preparation method thereof
Technical field
The present invention relates to the field of polymers more particularly to a kind of micro-foaming polypropylene material and preparation method thereof.
Background technique
It is compared with common plastics, Foamex is because its density is low, good heat build-up performance, and high thermal stability is good Mechanical property, such as the advantages that impact strength, toughness, endurance, in packaging material, auto-parts, adsorbent, mechanical support dress It is standby that places is waited to have many applications.Wherein, polypropylene, since its is at low cost, high-melting-point, high stretch modulus, low-density, well Chemical stability, be widely used Foamex industry.According to the difference of foaming aperture size, expanded polypropylene can divide For the PP and fretting map PP that commonly foams.The common usual abscess naked eyes of expanded polypropylene, can as it can be seen that cell diameter is higher than 100 microns It is used to prepare packaging material.When cell diameter is lower than 100 microns, then referred to as micro-foaming polypropylene, can be used for the part of car body The weight of car body is effectively reduced in injection moulded fittings.But preparing micro-foaming polypropylene has two big difficult points, a big difficulty is foaming The control of size, because comparing with materials such as polyurethane, polystyrene, polyacrylic melt strength is lower, so that foaming It is extremely difficult, easily there is the problems such as fusion steeped and rupture and generate the bulla of irregular distribution, the second largest difficult point is foaming ruler Very little homogeneity is difficult to control, and other than being influenced by polypropylene melt strength itself, the homogeneity of polypropylene expanded size is controlled More difficult mainly to have 2 reasons, reason one is that polypropylene itself is a kind of half hitch polycrystalline macromolecule, whole during forming spherocrystal A macromolecule internal physical structure is no longer uniform, leads into bubble homogeneity and goes wrong, second reason is foaming agent, microvesicle nucleation Agent and the mixing of acrylic resin not enough uniformly lead to the size difference that foams.And foaming agent, microvesicle nucleating agent and polypropylene The mixing of resin is there is also two problems, one is the reunion of foaming agent itself, the second is foaming agent, microvesicle nucleating agent etc. are inorganic Mixing between particle and acrylic resin.
Currently, difficult for the above foaming of polypropylene fusing point, the bad problem of foaming size distribution uniformity, mainly Technology path be to improve polyacrylic melt strength, polyacrylic polarity is modified, or use physics supercritical foaming It is prepared by method.In order to improve polyacrylic melt strength, the first normal method is to use high melt strength, propylene HMSPP such as introduces a small amount of long chain branched polypropylene using new catalyst or reactor, but it is very high to be generally prepared as this;The Why the polyolefin (such as polyethylene) of other high fondant-strengths is blended two kinds of modes, but other polyolefin, which are added, to be reduced The advantages such as the heat resistance of polypropylene itself and good mechanical property;The third mode is to introduce certain cross-linked structure, such as logical Overshoot crosslinking or chemical cross-linking agent are crosslinked polypropylene segment, but the control of the degree of cross linking is more difficult, and easily deposit In chemical residual, preparation process is more difficult to control, in some instances it may even be possible to which there are certain risk of explosion.In order to improve polypropylene and inorganic The mixing of filler, normal method are that use maleic anhydride to modify polypropylene compatible between inorganic filler to improve it Property, but maleic anhydride higher cost, and it is also unsatisfactory for the control of cell size.In addition, using the overcritical hair of physics Prepared by bubble method, be to utilize with polymer-gas homogeneous system existing for types of supercritical fluid, using rapidly changing temperature The mode of degree makes gas solubility change dramatically in the polymer and prepares microvesicle, but supercritical fluid hair method usually needs Special equipment is wanted, complex process, control of product quality is difficult, and higher cost.
Based on this, inventing one kind can be used for common Melt strength polypropylene resin, without special supercritical fluid Equipment can be realized polypropylene fretting map, and foaming homogeneity is good, foaming agent soilless sticking and the material technology that cost can be effectively controlled Become extremely important.
Summary of the invention
The purpose of the present invention is to provide one kind to have low-density, high foamability, abscess uniform pore diameter and main concentration In material internal, surface has the micro-foaming polypropylene material of excellent appearance and the system of this kind of micro-foaming polypropylene material without trace Preparation Method.
The present invention is compound in 1-10 microns of foaming agent by blapharoplast and composite foamable agent preparation particle diameter distribution D50 value Powder makes foaming agent uniform load on blapharoplast, foaming agent composite powder is made with acrylic resin mixing extruding pelletization, injection molding It is standby to obtain micro-foaming polypropylene material.The micro-foaming polypropylene surfacing being prepared without trace, inside there are uniform pore diameter, Average-size is the compound microbubble structure that 50-250 microns of the small bubble of microvesicle and aperture less than 10 microns collectively constitutes, or The ultra micro bubble structure of small bubble of the aperture less than 20 microns.Density of material is 0.8-0.95g/cm3, melt flow rate 2.5- 50g/10min, tensile strength > 8Mpa, elongation at break are higher than 500%, Izod notched impact strength > 5kJ/m2.The present invention Compared with the preparation process of traditional micro-foaming polypropylene, by preparing NEW TYPE OF COMPOSITE foam powder, without special overcritical The pore size of polypropylene fretting map and the control of homogeneity can be realized with common Melt strength polypropylene resin in fluid device System, and solve the problems, such as foaming agent reunion simultaneously.
The present invention provides a kind of micro-foaming polypropylene material, acrylic resin and 0.5- including 50-99.5wt% The particle diameter distribution D50 value of 50wt% is in 1-10 microns of foaming agent composite powder, and wherein foaming agent composite powder includes following quality hundred Divide the component of content: blapharoplast 10-95%, composite foamable agent 5-90%, promoter for blowing agent 0-10%.
Wherein, blapharoplast includes but is not limited to: wood powder, diatomite, flyash, dolomite, calcium carbonate, calcium silicates, glass Glass microballon, titanium dioxide titanium dioxide, sepiolite, concave convex rod, zeolite, quartz, kaolin, silica, bentonite or perlite One of or it is a variety of.
Composite foamable agent includes the first phase foaming agent of 50-100wt% and the second phase foaming agent of 0-50wt%, wherein One phase foaming agent is one of p-toluene sulfonylsemicarbazide, azodicarbonamide, Barium azodicarboxylate or 5- phenyl tetrazole Or it is a variety of, the second phase foaming agent is bicarbonate, such as one of sodium bicarbonate, calcium bicarbonate or calcium bicarbonate or a variety of.
Promoter for blowing agent is sodium bicarbonate, sodium citrate, urea, lactic acid, one of malic acid or a variety of.
The present invention provides a kind of preparation method of micro-foaming polypropylene material, prepares foaming agent composite powder first, by 10- 95wt% blapharoplast, 5-90wt% composite foamable agent, the mixing of 0-10wt% promoter for blowing agent;Again by the poly- of 50-99.5wt% The foaming agent composite powder of allyl resin and matter 0.5-50wt%, which mix and carries out extruding pelletization, obtains modified polypropene pellet;Finally Modified polypropene pellet is sent into injection molding machine, injection molding under conditions of injection temperature is 210-250 DEG C is prepared poly- Propylene micro-foaming material.
Wherein raw material acrylic resin is the acrylic resin particle that melt flow rate is 2-45g/10min.
Wherein being granulated is that melting extrusion granulation is carried out by double screw extruder, and extrusion temperature is 140-180 DEG C, is changed Property polypropylene granules.
Wherein, blapharoplast includes but is not limited to: wood powder, diatomite, flyash, dolomite, calcium carbonate, calcium silicates, glass Glass microballon, titanium dioxide titanium dioxide, sepiolite, concave convex rod, zeolite, quartz, kaolin, silica, bentonite or perlite One of or it is a variety of.
Wherein, composite foamable agent includes the first phase foaming agent of 50-100wt% and the second phase foaming agent of 0-50wt%, Wherein the first phase foaming agent is p-toluene sulfonylsemicarbazide, azodicarbonamide, Barium azodicarboxylate, in 5- phenyl tetrazole One or more, the second phase foaming agent is bicarbonate, such as sodium bicarbonate, calcium bicarbonate, one of calcium bicarbonate or a variety of.
Wherein, promoter for blowing agent is sodium bicarbonate, sodium citrate, urea, lactic acid, one of malic acid or a variety of.
Wherein, hybrid mode uses mixed at high speed blender, vibromill, sand mill, air-flow when prepared by foaming agent composite powder Mill, Ball-stirring mill, honeycomb mill, Raymond mill, ring roll mill, omnipotent impact grinding, high-speed impact airslide disintegrating mill, wet process or dry ball milling Machine it is one or more, the foaming agent composite powder being prepared is coated on blapharoplast by composite foamable agent, particle diameter distribution D50 Value is at 1-10 microns.
The micro-foaming polypropylene surfacing being prepared is without trace, and there are uniform pore diameters, average-size 50- for inside The compound microbubble structure that 250 microns of the small bubble of microvesicle and aperture less than 10 microns collectively constitutes, exemplary diagram such as attached drawing 1, Or the ultra micro bubble structure of small bubble of the aperture less than 20 microns, exemplary diagram such as attached drawing 2.
By the way that composite foamable agent is supported on blapharoplast in advance, asked it is possible to prevente effectively from conventional foaming agents powder ball is poly- Topic, and can be realized the control of effective dispersibility and foaming dimensional homogeneity of the foaming agent in polypropylene simultaneously, it avoids the occurrence of Bulla is randomly distributed due to caused by the fusion of bubble, rupture.Further, the aperture of material can be by adjusting foaming agent composite powder The parameters such as ingredient, constituent mass score, particle diameter distribution be adjusted.The density that material is made is 0.8-0.95g/cm3, melt Flowing velocity is 2.5-50g/10min, and has good mechanical characteristic, and tensile strength > 8Mpa, elongation at break is higher than 500%, Izod notched impact strength > 5kJ/m2.Compared with traditional fretting map mode, cost of the present invention is lower, sets to special type Standby requirement is less, and can maximum possible reservation virgin pp itself good characteristic.
Detailed description of the invention
Attached drawing 1 is the compound microbubble structure Fracture scan electron microscope that the present invention is prepared;
Attached drawing 2 is the ultra micro bubble structure Fracture scan electron microscope that the present invention is prepared;
Attached drawing 3 is the scanning electron microscope (SEM) photograph of comparative example.
Specific embodiment
Comparative example
By melt flow rate (MFR) be 38g/min acrylic resin and pure azodicarbonamide according to mass ratio 10:1 most Carry out extruding pelletization at a temperature of 180 DEG C of high temperature, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, product is made Density is 0.88g/cm3, there is aperture in 500 microns or more of macroscopical bulla in some areas, and some areas are still, do not steep Hole aperture seriously affects the mechanical property of material, Izod notched impact strength < 4kJ/m in 10 microns of ultra micro bubbles below2, Abscess microstructure is as shown in Fig. 3.
Embodiment 1
Using high-speed impact airslide disintegrating mill by mass percent be 95% talcum powder and mass percent be 5% The compound obtained foaming agent composite powder of composite foamable agent, wherein composite foamable agent selects the first phase foaming agent azodicarbonamide, the Two-phase foaming agent sodium acid, made foaming agent composite powder particle diameter distribution D50 value are 8.5 microns.It is 2.5 by melt flow rate (MFR) Acrylic resin and modified foaming agent composite powder according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of squeeze out and make Grain, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, be made product density be 0.88g/cm3.Made sample surfaces Smooth no trace, inside is there are uniform pore diameter, the small bubble of microvesicle and aperture less than 10 microns that average-size is 150 microns The compound microbubble structure collectively constituted, material melt flowing velocity are 2.5-50g/10min, tensile strength 8.1Mpa, and fracture stretches Long rate is higher than 500%, Izod notched impact strength 6kJ/m2.Abscess microstructure is as shown in Fig. 1, the foam structure of material It there are the equally distributed average pore size in bubble aperture is 150-200 microns micro- in 100 micron dimensions mainly in material internal Pore structure, and there are uniform pore diameter distribution in 1 micron dimension, the micro hole that average pore size is 2 microns.
Embodiment 2
The foaming agent composite powder in acrylic resin and above-described embodiment 1 for being 20 by melt flow rate (MFR) is according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, It is 0.91g/cm that product density, which is made,3
Embodiment 3
The foaming agent composite powder in acrylic resin and above-described embodiment 1 for being 20 by melt flow rate (MFR) is according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, It is 0.92g/cm that product density, which is made,3
Embodiment 4
The foaming agent composite powder in acrylic resin and above-described embodiment 1 for being 38 by melt flow rate (MFR) is according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, It is 0.94g/cm that product density, which is made,3
Embodiment 5
Using high-speed impact airslide disintegrating mill by mass percent be 95% talcum powder and mass percent be 5% The compound obtained foaming agent composite powder of composite foamable agent, wherein the first phase foaming agent toluene sulfonyl semicarbazide of composite foamable agent selection, Second phase foaming agent sodium acid, made foaming agent composite powder particle diameter distribution D50 value are 8.5 microns.It is by melt flow rate (MFR) 2.5 acrylic resin and foaming agent composite powder according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, And 230 DEG C of maximum temperature at a temperature of carry out injection molding, be made product density be 0.92g/cm3.Abscess microstructure is such as Shown in attached drawing 2.
Embodiment 6
The foaming agent composite powder in acrylic resin and above-described embodiment 5 for being 20 by melt flow rate (MFR) is according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, It is 0.94g/cm that product density, which is made,3
Embodiment 7
Using high-speed impact airslide disintegrating mill by mass percent be 95% talcum powder and mass percent be 5% The compound obtained foaming agent composite powder of composite foamable agent, wherein composite foamable agent selects the first phase foaming agent Barium azodicarboxylate, the Two-phase foaming agent sodium acid, made foaming agent composite powder particle diameter distribution D50 value are 8.5 microns.It is 2.5 by melt flow rate (MFR) Acrylic resin and foaming agent composite powder according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, be made product density be 0.85g/cm3
Embodiment 8
The foaming agent composite powder in acrylic resin and above-described embodiment 7 for being 20 by melt flow rate (MFR) is according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, It is 0.92g/cm that product density, which is made,3
Embodiment 9
Using high-speed impact airslide disintegrating mill by mass percent be 95% talcum powder and mass percent be 5% The compound obtained foaming agent composite powder of composite foamable agent, wherein composite foamable agent select the first phase foaming agent for 5- phenyl tetrazole, Second phase foaming agent sodium acid, made foaming agent composite powder particle diameter distribution D50 value are 8.5 microns.It is by melt flow rate (MFR) 2.5 acrylic resin and foaming agent composite powder according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, And 230 DEG C of maximum temperature at a temperature of carry out injection molding, be made product density be 0.84g/cm3
Embodiment 10
The foaming agent composite powder in acrylic resin and above-described embodiment 9 for being 20 by melt flow rate (MFR) is according to mass ratio 10:1 180 DEG C of the highest temperature at a temperature of carry out extruding pelletization, and 230 DEG C of maximum temperature at a temperature of carry out injection molding, It is 0.90g/cm that product density, which is made,3
The foregoing is merely better embodiment of the invention, protection scope of the present invention is not with above embodiment Limit, as long as those of ordinary skill in the art's equivalent modification or variation made by disclosure according to the present invention, should all be included in power In the protection scope recorded in sharp claim.

Claims (10)

1. a kind of micro-foaming polypropylene material, it is characterised in that: surfacing is without trace, and there are uniform pore diameters, average ruler for inside The compound microbubble structure or aperture that very little microvesicle and aperture for 50-250 microns is collectively constituted less than 10 microns of small bubble are equal The ultra micro bubble structure of small bubble of the even, average-size less than 20 microns;Density of material is 0.8-0.95g/cm3, melt flows speed Degree is 2.5-50g/10min, and tensile strength > 8Mpa, elongation at break is higher than 500%, Izod notched impact strength > 5kJ/ m2
2. a kind of micro-foaming polypropylene material as described in claim 1, it is characterised in that: poly- third including 50-99.5wt% The particle diameter distribution D50 value of olefine resin and 0.5-50wt% are in 1-10 microns of foaming agent composite powder, wherein foaming agent composite powder packet Include the component of following mass percentage: blapharoplast 10-95%, composite foamable agent 5-90%, promoter for blowing agent 0-10%.
3. a kind of micro-foaming polypropylene material as claimed in claim 2, it is characterised in that: blapharoplast be wood powder, diatomite, Flyash, dolomite, calcium carbonate, calcium silicates, glass microballoon, titanium dioxide titanium dioxide, sepiolite, concave convex rod, zeolite, quartz, One of kaolin, silica, bentonite or perlite are a variety of.
4. a kind of micro-foaming polypropylene material as claimed in claim 2, it is characterised in that: composite foamable agent includes 50- The first phase foaming agent of 100wt% and the second phase foaming agent of 0-50wt%, wherein the first phase foaming agent is tolysulfonyl ammonia One of base urea, azodicarbonamide, Barium azodicarboxylate or 5- phenyl tetrazole are a variety of, and the second phase foaming agent is carbonic acid One of hydrogen salt, such as sodium bicarbonate, calcium bicarbonate or calcium bicarbonate are a variety of.
5. a kind of micro-foaming polypropylene material as claimed in claim 2, it is characterised in that: promoter for blowing agent be sodium bicarbonate, One of sodium citrate, urea, lactic acid or malic acid are a variety of.
6. a kind of preparation method of micro-foaming polypropylene material, it is characterised in that: foaming agent composite powder is prepared first, by 10- 95wt% blapharoplast, 5-90wt% composite foamable agent, the mixing of 0-10wt% promoter for blowing agent;Again by the poly- of 50-99.5wt% The foaming agent composite powder of allyl resin and 0.5-50wt%, which mix and carries out extruding pelletization, obtains modified polypropene pellet;Finally will Modified polypropene pellet is sent into injection molding machine, and injection molding under conditions of injection temperature is 210-250 DEG C is prepared poly- third Alkene micro-foaming material.
7. a kind of preparation method of micro-foaming polypropylene material as claimed in claim 6, it is characterised in that: raw material polypropylene tree Rouge is the acrylic resin particle that melt flow rate is 2-45g/10min;Preferably, granulation be by double screw extruder into Row melting extrusion is granulated, and extrusion temperature is 140-180 DEG C, obtains modified polypropene pellet.
8. a kind of preparation method of micro-foaming polypropylene material as claimed in claim 6, it is characterised in that: blapharoplast is wood Powder, diatomite, flyash, dolomite, calcium carbonate, calcium silicates, glass microballoon, titanium dioxide titanium dioxide, sepiolite, concave convex rod, One of zeolite, quartz, kaolin, silica, bentonite or perlite are a variety of.
9. a kind of preparation method of micro-foaming polypropylene material as claimed in claim 6, it is characterised in that: composite foamable agent packet The first phase foaming agent of 50-100wt% and the second phase foaming agent of 0-50wt% are included, wherein the first phase foaming agent is to toluene sulphur One of semicarbazides, azodicarbonamide, Barium azodicarboxylate or 5- phenyl tetrazole are a variety of, and the second phase foaming agent is One of bicarbonate, such as sodium bicarbonate, calcium bicarbonate or calcium bicarbonate are a variety of;Promoter for blowing agent is sodium bicarbonate, lemon One of lemon acid sodium, urea, lactic acid or malic acid are a variety of.
10. a kind of preparation method of micro-foaming polypropylene material as claimed in claim 6, it is characterised in that: foaming agent is compound Powder prepare when hybrid mode using mixed at high speed blender, vibromill, sand mill, airflow milling, Ball-stirring mill, honeycomb mill, Raymond mill, Ring roll mill, omnipotent impact grinding, high-speed impact airslide disintegrating mill, wet process or dry method ball mill it is one or more, be prepared Foaming agent composite powder be coated on blapharoplast by composite foamable agent, particle diameter distribution D50 value is at 1-10 microns.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111205503A (en) * 2020-02-21 2020-05-29 中化石化销售有限公司 Foaming agent material, foaming agent master batch and preparation method thereof
CN111592703A (en) * 2020-05-18 2020-08-28 广德祥源新材科技有限公司 Environment-friendly cross-linked polyolefin foam material and preparation method thereof
CN112063029A (en) * 2020-09-01 2020-12-11 广东工业大学 Micro-foaming polyethylene wood-plastic composite material and preparation method thereof
CN112080069A (en) * 2020-09-01 2020-12-15 广东工业大学 Foamed polypropylene wood-plastic material and preparation method thereof
CN112608555A (en) * 2020-12-14 2021-04-06 金发科技股份有限公司 Foaming agent master batch and preparation method thereof
CN116837488A (en) * 2023-07-01 2023-10-03 东莞市威骏不织布有限公司 High-permeability durable reflective cloth and preparation method thereof
CN116855183A (en) * 2023-07-12 2023-10-10 湖北祥源高新科技有限公司 Polyolefin-based cushioning foam sheet, adhesive tape, display module, and electronic product

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977458A (en) * 2012-12-11 2013-03-20 苏州工业园区润佳工程塑料有限公司 Micropore foaming agent for polypropylene, microcellular foamed polypropylene composite material and methods for preparing micropore foaming agent for polypropylene and microcellular foamed polypropylene composite material
CN105885240A (en) * 2016-04-25 2016-08-24 中山诗兰姆汽车零部件有限公司 Microcellular foaming composite material and preparation method thereof
CN107033381A (en) * 2017-03-20 2017-08-11 北京化工大学 Nanocomposite foaming agent, foaming product and its preparation method and application
US20180057651A1 (en) * 2016-08-30 2018-03-01 LCY Chemical Corp. Polypropylene foams and processes of making

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977458A (en) * 2012-12-11 2013-03-20 苏州工业园区润佳工程塑料有限公司 Micropore foaming agent for polypropylene, microcellular foamed polypropylene composite material and methods for preparing micropore foaming agent for polypropylene and microcellular foamed polypropylene composite material
CN105885240A (en) * 2016-04-25 2016-08-24 中山诗兰姆汽车零部件有限公司 Microcellular foaming composite material and preparation method thereof
US20180057651A1 (en) * 2016-08-30 2018-03-01 LCY Chemical Corp. Polypropylene foams and processes of making
CN107033381A (en) * 2017-03-20 2017-08-11 北京化工大学 Nanocomposite foaming agent, foaming product and its preparation method and application

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111205503A (en) * 2020-02-21 2020-05-29 中化石化销售有限公司 Foaming agent material, foaming agent master batch and preparation method thereof
CN111592703A (en) * 2020-05-18 2020-08-28 广德祥源新材科技有限公司 Environment-friendly cross-linked polyolefin foam material and preparation method thereof
CN111592703B (en) * 2020-05-18 2022-08-16 广德祥源新材科技有限公司 Environment-friendly cross-linked polyolefin foam material and preparation method thereof
CN112063029A (en) * 2020-09-01 2020-12-11 广东工业大学 Micro-foaming polyethylene wood-plastic composite material and preparation method thereof
CN112080069A (en) * 2020-09-01 2020-12-15 广东工业大学 Foamed polypropylene wood-plastic material and preparation method thereof
CN112608555A (en) * 2020-12-14 2021-04-06 金发科技股份有限公司 Foaming agent master batch and preparation method thereof
CN112608555B (en) * 2020-12-14 2022-05-10 金发科技股份有限公司 Foaming agent master batch and preparation method thereof
CN116837488A (en) * 2023-07-01 2023-10-03 东莞市威骏不织布有限公司 High-permeability durable reflective cloth and preparation method thereof
CN116855183A (en) * 2023-07-12 2023-10-10 湖北祥源高新科技有限公司 Polyolefin-based cushioning foam sheet, adhesive tape, display module, and electronic product
CN116855183B (en) * 2023-07-12 2024-08-02 湖北祥源高新科技有限公司 Polyolefin-based cushioning foam sheet, adhesive tape, display module, and electronic product

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