CN106380624A - Easily-molded polypropylene foaming bead and preparation method thereof - Google Patents
Easily-molded polypropylene foaming bead and preparation method thereof Download PDFInfo
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- CN106380624A CN106380624A CN201610793448.2A CN201610793448A CN106380624A CN 106380624 A CN106380624 A CN 106380624A CN 201610793448 A CN201610793448 A CN 201610793448A CN 106380624 A CN106380624 A CN 106380624A
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- polypropylene
- polypropylene foaming
- readily molded
- dispersant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-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 physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation method of an easily-molded polypropylene foaming bead. The easily-molded polypropylene foaming bead comprises a dispersant which is inorganic matter particles with the particle size of 0.01-60 [mu]m, a polypropylene polymer which is a propylene and copolymerization monomer copolymer with the propylene mol fraction being not lower than 60%, an aqueous disperse medium, and a physical foaming agent. The preferable dispersant is hydrated aluminosilicate kaolin with the particle size of 0.1-15 [mu]m, and 0.01-5 parts by weight of the hydrated aluminosilicate kaolin are added to every 100 parts by weight of the disperse medium . The dispersant has good suspension performance in water, and can be easily removed from the surface of foaming particles in the cleaning process after foaming completion, inorganic matter barrier on the surface of the foaming particles in the molding process is less, and the foaming particles can be well molten under a low steam pressure, so the energy consumed in the molding of the foaming bead is saved.
Description
Technical field
The present invention relates to a kind of polypropylene foaming beads, specially a kind of polypropylene foaming beads being readily molded into type and
Its preparation method.
Background technology
PP foam material has excellent mechanical property, and is easily recycled, replacement polyphenyl second just progressively
Alkene expanded material, application is more and more extensive.The existing high expansion ratio of polypropylene foaming beads (EPP), but can molded for shape
The product that shape is complicated, dimensional accuracy is high, greatly extends the application of expanded material, and EPP product is in packaging, automobile making
The use in the fields such as industry increasingly increases.
At present, industrial employing batch reactor foaming produces polypropylene foaming beads, then passes through vapor mould
EPP beadlet clinkering is become use product miscellaneous by molded method.Produce expanded bead：Acrylic resin granule, water
Property disperse medium, dispersant, foaming agent be loaded into airtight autoclave together, in the presence of stirring, will by heater
Dispersion in kettle is heated above the temperature of polypropylene softening point, allows foaming agent sufficiently impregnate acrylic resin granule, so
Afterwards dispersion is dumped in air and obtains expanded bead.In foaming process, the effect of dispersant is the resin preventing by thermal softening
Granule mutually bonds, and on the other hand, the expanded bead that release obtains still can adhere to a certain amount of point in its surface after tank washing
Powder, this can hinder expanded particle mutual clinkering in steam moulding process, leads to the molded steam pressure of EPP beadlet more
Height, and clinkering defect in surface easily occurs.
Content of the invention
When the technical problem to be solved in the present invention is to overcome existing EPP beadlet molded, expanded bead is washed through tank
Its surface still can adhere to a certain amount of dispersant afterwards, hinder expanded particle mutual clinkering in steam moulding process, lead to EPP pearl
The molded steam pressure of grain is higher, the problems such as can largely improve product surface defect simultaneously, provide a kind of easily
Production method in molded expanded polypropylene beads.
In order to solve above-mentioned technical problem, the invention provides following technical scheme：
A kind of polypropylene foaming beads being readily molded into type, including following components：
Dispersant, described dispersant particle diameter is 0.01-60 μm of mineral particulates；Including zinc oxide, barium sulfate, carbonic acid
Calcium, aluminosilicate etc., preferably main component are the Kaolin of hydrated aluminosilicate, because suspension in water for the hydrous kaolin
Good, preferably kaolinic a size of 0.1-15 μm of hydrated aluminosilicate；The Kaolin of hydrated aluminosilicate within the specific limits
Particle diameter less, the bigger dispersion effect of its specific surface area can more preferably, and the suspendability in water is more preferably, is more easy to be washed, but
The kaolinic particle diameter too little Yi of hydrated aluminosilicate reunites seriously, instead results in its less efficient dispersal.Preferably it is hydrated kaolinite
Native consumption is the disperse medium of every 100 weight portions, adds Kaolin 0.01-5 weight portion, more preferably 0.05-1 weight portion.Selected
As dispersant, its dispersion mechanism is to form colloid in disperse medium and individually wrap up each and be suspended in dispersion to Kaolin
PP GRANULES in medium, prevents from mutually bondd by the PP GRANULES of thermal softening.
Polyacrylic polymer, described polyacrylic polymer is the copolymer of propylene and one or more comonomer, propylene
Molar fraction >=60%；Preferably at least >=80%, the mixture of two or more copolymers, or homopolymer and copolymer is mixed
Compound.The example of copolymer includes propylene-ethylene block copolymer, Propylene-ethylene random copolymer, propylene-ethylene-butene no
Rule copolymer.
Aqueous dispersion medium；Disperse medium is ethanol, glycerol, any one in water, preferably water, more preferably deionization
Water.
Physical blowing agent；Described physical blowing agent is butane, pentane, vapor, air and CO2In any one.
All double melting peaks structure, wherein high temperature melting in the DSC melting curve of the polypropylene foaming beads obtained by invention
Melt the gas impregnated period that peak occurs being because in foaming process, have the crystal not melted to reset further in resin particle, perfect
And define the crystal structure that melt temperature is higher than polypropylene original melting point；The appearance at watery fusion peak is gas impregnated period tree
The reason of the crystal of thawing recrystallization in the cooling procedure after release of pressure in fat.The molded vapor (steam) temperature of EPP product one
As be selected in temperature between EPP double melting peaks.In molding, the cryocrystal of EPP melts to promote the bonding between beadlet, and high
Warm crystal non-fusible to ensure the cell morphology of expanded bead and the mechanical property of moulding article.The heat enthalpy value one at high-temperature fusion peak
As be preferably 2-20J/g, the energy absorption capacity of the too low expanded bead of its heat content can be deteriorated, and when heat enthalpy value is high, expanded bead is difficult clinkering.
The expanded polypropylene beads being readily molded into type of the present invention are a kind of few (remained on surface of remained on surface inorganic particle
Inorganic matters can largely improve EPP bind particles temperature) and be easy to the molding expanded polypropylene beads of clinkering.Due to
Dispersant suspendability in water is good, and in the cleaning after the completion of foaming, dispersant is more easy to remove from the surface of expanded particle
Go, in forming process, the inorganic matters on expanded particle surface intercept less, and under lower steam pressure, expanded particle can have well
Clinkering, energy consumption when saving expanded bead is molded.
Brief description
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for description, the reality with the present invention
Apply example and be used for explaining the present invention together, be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the polypropylene foaming beads typical double melting peaks curve of the present invention；
Fig. 2 is the expanded polypropylene beads surface SEM picture of embodiment 1；
Fig. 3 is the expanded polypropylene beads surface SEM picture of embodiment 4.
Specific embodiment
Hereinafter the preferred embodiments of the present invention are illustrated it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
A kind of polypropylene foaming beads being readily molded into type, including following components：
Dispersant, dispersant particle diameter is the Kaolin of 20 μm of hydrated aluminosilicate, and consumption is 3kg；
Propylene-ethylene-butene random copolymer resin 500kg, mole fraction >=80%；
Aqueous dispersion medium deionized water 1000kg；
Physical blowing agent CO2.
Embodiment 2
A kind of polypropylene foaming beads being readily molded into type, including following components：
Dispersant, dispersant particle diameter is the Kaolin of 20 μm of hydrated aluminosilicate, and consumption is 2kg；
Propylene-ethylene-butene random copolymer resin 500kg, mole fraction >=80%；
Aqueous dispersion medium deionized water 1000kg；
Physical blowing agent CO2.
Embodiment 3
A kind of polypropylene foaming beads being readily molded into type, including following components：
Dispersant, dispersant particle diameter is the Kaolin of 2 μm of hydrated aluminosilicate, and consumption is 3kg；
Propylene-ethylene-butene random copolymer resin 500kg, mole fraction >=80%；
Aqueous dispersion medium deionized water 1000kg；
Physical blowing agent CO2.
Embodiment 4
A kind of polypropylene foaming beads being readily molded into type, including following components：
Dispersant, dispersant particle diameter is the Kaolin of 2 μm of hydrated aluminosilicate, and consumption is 2kg；
Propylene-ethylene-butene random copolymer resin 500kg, mole fraction >=80%；
Aqueous dispersion medium deionized water 1000kg；
Physical blowing agent CO2.
Embodiment 5
A kind of polypropylene foaming beads being readily molded into type, including following components：
Dispersant, dispersant particle diameter is 5 μm of clay, and consumption is 2kg；
Propylene-ethylene random copolymer or Noblen 500kg, mole fraction >=80%；
Aqueous dispersion medium deionized water 1000kg；
Physical blowing agent CO2.
On the longest edge (120cm) of molded sheet material (120cm × 100cm × 10cm), along one perpendicular to it
Longitudinal bisector, forms the otch of a 2cm depth, and by bending, sample ruptures into two along line of cut, observes section,
On section, the beadlet number of damage abscess accounts for the clinkering degree of the percentage ratio as sample of total beadlet number, and this ratio is higher to be shown
Clinkering is better.Compared by embodiment 1 and embodiment 2, embodiment 3 and embodiment 4, may indicate that in Kaolin particle diameter identical bar
Under part, in foaming process, kaolinic addition is fewer, then under identical briquetting pressure, EPP beadlet embodies more excellent clinkering
Can, basically reach downstream client's molded article clinkering degree requirement.From embodiment 1 and embodiment 3, embodiment 2 and embodiment 4 two
Embodiment compares, it can be shown that in the case of the identical addition of Kaolin, when the less Kaolin of particle diameter makees dispersant, EPP
Beadlet shows lower briquetting pressure and more preferable clinkering degree.By embodiment 2 and 3 contrast it can be shown that with respect to big particle diameter
For Kaolin, even if the little Kaolin of particle diameter is in the case of high addition, still there is relatively low briquetting pressure and preferably
Clinkering degree, the result of above example all demonstrate the less Kaolin of particle diameter because its in water suspension more preferably, in washing
It is more easy in operation remove from EPP surface of beads, contribute to EPP beadlet and there is in relatively low briquetting pressure more excellent clinkering degree.
Fig. 1 is the polypropylene foaming beads typical double melting peaks curve of the present invention；The Crack cause of its double behavior and
Impact to molding is noted above in content of the invention.
Fig. 2 is the expanded polypropylene beads surface SEM picture of embodiment 1；When making dispersant from the big Kaolin of particle diameter,
Kaolin suspension in water is relatively poor, is difficult to be washed off in cleaning, remains in the dispersant of EPP surface of beads relatively
Many, obstruction EPP's is molded.
Fig. 3 is the expanded polypropylene beads surface SEM picture of embodiment 4.When making dispersant from the little Kaolin of particle diameter,
Kaolin suspension in water is good, is easily washed off in cleaning, remains in the dispersant of EPP surface of beads seldom, is beneficial to
EPP is molded.
Finally it should be noted that：The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
To modify to the technical scheme described in foregoing embodiments, or equivalent is carried out to wherein some technical characteristics.
All any modification, equivalent substitution and improvement within the spirit and principles in the present invention, made etc., should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of polypropylene foaming beads being readily molded into type are it is characterised in that include following components：
Dispersant, described dispersant particle diameter is 0.01-60 μm of mineral particulates；
Polyacrylic polymer, described polyacrylic polymer is the copolymer of propylene and comonomer, mole fraction >=60%；
Aqueous dispersion medium；
Physical blowing agent.
2. it is readily molded into the polypropylene foaming beads of type as claimed in claim 1 it is characterised in that described dispersant is oxygen
Change zinc, barium sulfate, Calcium Carbonate, aluminosilicate and hydrated aluminosilicate kaolinic any one or a few.
3. it is readily molded into the polypropylene foaming beads of type as claimed in claim 2 it is characterised in that described dispersant is grain
Footpath is the Kaolin of 0.1-15 μm of hydrated aluminosilicate, the kaolinite of hydrated aluminosilicate in the disperse medium of every 100 weight portions
The addition 0.01-5 weight portion of soil.
4. it is readily molded into the polypropylene foaming beads of type as claimed in claim 3 it is characterised in that every 100 weight portions
The kaolinic addition 0.05-1 weight portion of hydrated aluminosilicate in disperse medium.
5. it is readily molded into the polypropylene foaming beads of type as claimed in claim 1 it is characterised in that described polypropylene gathers
Mole fraction >=80% in compound.
6. it is readily molded into the polypropylene foaming beads of type as claimed in claim 5 it is characterised in that described polypropylene gathers
Compound is propylene-ethylene block copolymer, Propylene-ethylene random copolymer or propylene-ethylene-butene random copolymer.
7. it is readily molded into the polypropylene foaming beads of type as claimed in claim 1 it is characterised in that disperse medium is second
Any one in alcohol, glycerol, water.
8. it is readily molded into the polypropylene foaming beads of type as claimed in claim 1 it is characterised in that described physical blowing agent
For butane, pentane, vapor, air and CO2In any one.
9. it is readily molded into the polypropylene foaming beads of type as claimed in claim 1 it is characterised in that including following components：
Particle diameter is the Kaolin of 0.1-15 μm of hydrated aluminosilicate；
Propylene-ethylene-butene random copolymer, mole fraction >=80%；
Aqueous dispersion medium deionized water；
Physical blowing agent CO2.
10. a kind of preparation method of the polypropylene foaming beads being readily molded into type as claimed in claim 1, its feature exists
In the heat enthalpy value at high-temperature fusion peak is 2-20J/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610793448.2A CN106380624A (en) | 2016-08-31 | 2016-08-31 | Easily-molded polypropylene foaming bead and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610793448.2A CN106380624A (en) | 2016-08-31 | 2016-08-31 | Easily-molded polypropylene foaming bead and preparation method thereof |
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| CN106380624A true CN106380624A (en) | 2017-02-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518576A (en) * | 2001-06-11 | 2004-08-04 | ��ʽ����Jsp | Method for producing polypropylene type resin foamed particle |
| CN102295807A (en) * | 2011-09-05 | 2011-12-28 | 浙江俊尔新材料有限公司 | Extrusion expanded polypropylene beads and preparation method thereof |
| CN102391571A (en) * | 2011-09-05 | 2012-03-28 | 浙江俊尔新材料有限公司 | Extrusion foaming polypropylene particles with lower thermal molding pressure and preparation method thereof |
| CN102391570A (en) * | 2011-09-05 | 2012-03-28 | 浙江俊尔新材料有限公司 | Extrusion foaming polypropylene particles with lower thermal molding temperature and preparation method thereof |
-
2016
- 2016-08-31 CN CN201610793448.2A patent/CN106380624A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518576A (en) * | 2001-06-11 | 2004-08-04 | ��ʽ����Jsp | Method for producing polypropylene type resin foamed particle |
| CN102295807A (en) * | 2011-09-05 | 2011-12-28 | 浙江俊尔新材料有限公司 | Extrusion expanded polypropylene beads and preparation method thereof |
| CN102391571A (en) * | 2011-09-05 | 2012-03-28 | 浙江俊尔新材料有限公司 | Extrusion foaming polypropylene particles with lower thermal molding pressure and preparation method thereof |
| CN102391570A (en) * | 2011-09-05 | 2012-03-28 | 浙江俊尔新材料有限公司 | Extrusion foaming polypropylene particles with lower thermal molding temperature and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘友鹏等: "《聚丙烯发泡珠粒的双熔融峰形成及影响因素》", 《石油化工》 * |
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Application publication date: 20170208 |