CN100575404C - A kind of expandable polypropylene bead and preparation method thereof and expanded bead thereof and molded foam - Google Patents
A kind of expandable polypropylene bead and preparation method thereof and expanded bead thereof and molded foam Download PDFInfo
- Publication number
- CN100575404C CN100575404C CN200610089710A CN200610089710A CN100575404C CN 100575404 C CN100575404 C CN 100575404C CN 200610089710 A CN200610089710 A CN 200610089710A CN 200610089710 A CN200610089710 A CN 200610089710A CN 100575404 C CN100575404 C CN 100575404C
- Authority
- CN
- China
- Prior art keywords
- weight
- bead
- parts
- component
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a kind of expandable polypropylene bead and preparation method thereof, its expanded bead and molded foam also are provided, relate to resin expandable bead field.It is base resin that the present invention adopts atactic copolymerized polypropene, adds high melt strength, propylene and ldpe resin, and melt strength reaches more satisfactory scope when making foaming; And utilize pentane in the closed reactor that does not apply external pressure, to prepare expandable bead as whipping agent.Containing in atactic copolymerized polypropene in the expandable bead is 100 parts by weight, high melt strength, propylene 1～15 parts by weight; New LDPE (film grade) 1～10 parts by weight; Whipping agent 1.0～3.8 parts by weight; Nucleator 0.1～10 parts by weight.This expandable polypropylene bead foaming is easy, and expansion ratio can reach 16 times; Foaming back abscess is even, and foam unit weight is 0.05～0.12g/cm
3About; The preparation method adopts low-pressure process, and is low for equipment requirements, and preparation cost is low, can make difform polypropylene foam goods as required.
Description
Technical field
The present invention relates to the resin expandable bead, say further, relate to expandable polypropylene bead and its preparation method, and expanded bead prepared therefrom and molded foam.
Background technology
Preparing foam materials with expandable bead is the key areas that plastic material is used.Therefore outstanding advantages such as it has that forming method is easy, froth product controllable shapes, dimensional change are easy are used in a large number.
But at present bigger expandable polystyrene bead and the expandability polyetylene beads of usage quantity has following shortcoming: heat resisting temperature is low, modulus is low, it is little, yielding etc. to absorb energy when being hit.
Polypropylene foam has the good heat-resistance characteristic, and the intensity height, absorbs when being hit that energy is big, distortion is little, therefore has purposes and use prospect widely.But because the melt strength of acrylic resin is very low, so the preparation of polypropylene foam has the preparation of very big difficulty, particularly expandable bead just difficult more.
From the patent search result, the expandable polypropylene bead has following several both at home and abroad at present:
One,, can be divided into the whipping agent kind:
1. whipping agent is the haloalkane hydro carbons: this technology is used in the preparation of traditional expandable polystyrene bead more;
2. whipping agent is a straight chain hydrocarbon: expandable polystyrene bead and expandability polyetylene beads adopt this technology more at present;
3. whipping agent is CO
2, N
2With gas such as air: as JP176084, USP6,607,682 etc.;
4. whipping agent is a water: as US4, and 626,555 etc.
Two,, can be divided into the base resin kind:
1. crosslinked polypropylene is understood JP168341 as JSP strain formula;
2. block copolymerization polypropylene
3. modified polypropene is as the Japanese JP190367 of the Idemitsu Kosen Co., Ltd. Japan JP226321 of Kanegafuchi Chemical Industry Co., Ltd.
In addition, see that prior art all adopts high-pressure process usually, as US6797734 etc. with preparation technology's angle.
At present, often there is following problem in polypropylene expandable bead technology in the prior art:
1. adopting halogenated alkane is that the expandable polypropylene bead expansion ratio of whipping agent preparation is higher, and foam materials unit weight is less, but halogenated alkane belong to restriction or forbidding at present environment is had the material of negative impact, do not have good application prospects;
2. adopting straight chain hydrocarbon is that whipping agent prepares the expandable polypropylene bead, generally uses high-pressure process.Than higher, cost is also than higher to the requirement of equipment for preparation technology;
3. adopt CO
2, N
2With gas such as air or water be the expandable polypropylene bead of whipping agent preparation, generally use high-pressure process.Expansion ratio is less, products production cost height.
Summary of the invention
The present invention adopts the method for straight chain hydrocarbon foaming, low-pressure process preparation on to the research basis of the base material compatibility of expandable polypropylene bead, make that expandable polypropylene bead material therefor has environment friendly, expansion ratio height, unit weight is little, preparation technology is easy, cost is low, overcome in the prior art to have problems.
The object of the invention provides a kind of expandable polypropylene bead, by the expansion ratio height of the expanded bead of its gained.
Another object of the present invention provides the preparation method of described expandable polypropylene bead.
A further object of the present invention provides the expanded bead of described expandable polypropylene bead.
A further object of the invention provides the molded foam of described expandable polypropylene bead preparation.
It is base resin that the present invention adopts atactic copolymerized polypropene, adds an amount of high melt strength, propylene and ldpe resin, and as the base-material of preparation expandable polypropylene bead, melt strength reaches more satisfactory scope when making foaming.It includes following component a kind of expandable polypropylene bead provided by the present invention: a. atactic copolymerized polypropene; B. high melt strength, propylene; C. new LDPE (film grade); D. whipping agent; E. nucleator.
If the melt strength of polypropylene matrix resin is low excessively in the polypropylene expanded technology, can cause phenomenons such as abscess caves in, breaks, merging, promptly steep wall can not keep certain intensity, thereby form effective bubble; Melt strength is too high then can make when expanding motivating force too a little less than, cause the bubble wall blocked up, extrudate density raises and the foaming effect that do not reach.Therefore select for use in the expandable polypropylene bead of the present invention melt strength preferably the polypropylene of atactic copolymerized polypropene and high fondant-strength regulate the melt strength of matrix resin, with the foaming effect that obtains and ensure that foam process is smooth.
Above-described expandable polypropylene bead of the present invention, wherein contained component a is the random copolymers of propylene and ethene, promptly a kind of atactic copolymerized polypropene (PPR).The ethene structural unit content of this atactic copolymerized polypropene (recording by infrared [Magna-IR760, Nicolet] and nuclear-magnetism [400M, Switzerland AVANCE]) is 3.5～6.5wt%, is preferably 4.0～5.0wt%; Molecular weight distribution (Mw/Mn) is 3.0～9.0, be preferably 4.2～7.0 (gel chromatograph GPC[150-CALC/GPC, Waters] measure).Its melting index is 0.10～1.2g/10min (testing tool: fusion index instrument code 6942, Italian CDAST manufacturing; Testing standard ASTMD1238; Test condition: 230 ℃, 2.16kg), be preferably 0.13～0.40g/10min; Its melt strength (210 ℃ [Rheotens71.97, German GOTTFERT, 210 ℃]) is 0.75～4.5N, preferred 1.35～3.50N.
Above-described expandable polypropylene bead of the present invention, the high melt strength, propylene of wherein contained components b are that melting index is that 0.05-1.05g/10min, melt strength are the high melt strength, propylene (HMSPP) of 0.5～1.2N (230 ℃ of surveys).Its melting index is preferably 0.07-0.5g/10min, and melt strength is preferably 0.7～0.9N (230 ℃ of surveys).Atactic copolymerized polypropene in component a is 100 parts by weight, and the high melt strength, propylene of components b is 1～15 part of parts by weight, is preferably 5～12 parts by weight.
The high melt strength, propylene of components b can adopt melting index and melt strength in the prior art to meet the polypropylene of above-mentioned condition in the expandable polypropylene bead of the present invention, also can preferably adopt the method preparation that may further comprise the steps:
A. polypropylene and polyfunctional monomer are mixed, obtain mixture;
B. said mixture is fully replaced with nitrogen, and under nitrogen atmosphere irradiation;
C. above-mentioned steps is handled the polypropylene that obtains and mix, obtain high melt strength, propylene through extruding pelletization with oxidation inhibitor.
The more function group monomer is bifunctional or two above monomers in the above method, as: 1,6 hexanediol diacrylate (HDDA), neopentylglycol diacrylate (NPGDA), Vinylstyrene etc.It is 100 parts by weight in polypropylene, and consumption is 0.5～4.0 part.
Compare with raw materials used, the melt polypropylene drawing force value changes delta F that this method obtains is more than or equal to 60cN, and storage modulus G ' is 1.5～2.5 times of blank sample.
Polypropylene and more function group are monomeric among preparation method's step a of said components b high melt strength, propylene is mixed into common mixing, promptly uses common blending meanss such as dipping, stirring to make the more function group monomer fully contact, mix with used polypropylene.The more function group monomer contacts with the polypropylene maximum area in order to make in the method, uniform mixing to be to reach the purpose of effective raising melt strength of polypropylene, preferably selects the powdery polypropylene of (comprising spherical) for use.The polyacrylic melting index of raw material is that 0.5～3g/10min, melt strength are more than the 0.5N, preferred 0.7～0.9N (230 ℃ of surveys).
The irradiation ray of the described irradiation utilization of the preparation method of said components b high melt strength, propylene is selected from electron rays, gamma ray, x-ray or UV-light, is preferably electron rays or gamma ray.Irradiation dose is 0.5～10kGy, is preferably 1.0～4kGy.
Polypropylene material behind the irradiation is also remaining free radical.According to the irradiation technique of routine, the material behind the irradiation need be eliminated free radical, in order to avoid remaining free radical and oxygen effect make degradation of polypropylene.So generally the normal temperature under nitrogen atmosphere of the material behind the irradiation was placed some days, or is placed some hrs down in high temperature.Generally the polypropylene behind the irradiation is handled in 100 ℃ among the present invention and can be eliminated remaining free radical in 2 hours.
Above-described expandable polypropylene bead of the present invention, the new LDPE (film grade) of wherein contained amount of component b can comprise existing various new LDPE (film grade)s or its mixing in the prior art.Atactic copolymerized polypropene in component a is 100 parts by weight, and the new LDPE (film grade) of amount of component b is 1～10 parts by weight, is preferably 3～8 parts by weight.
Above-described expandable polypropylene bead of the present invention, the whipping agent of wherein contained component d is a pentane, can comprise Skellysolve A, iso-pentane, pentamethylene or at least two kinds mixture wherein.Atactic copolymerized polypropene in component a is 100 parts by weight, and the whipping agent of component d is 1.0～3.8 parts by weight, is preferably 1.5～3.2 parts by weight.
Expandable polypropylene bead of the present invention can also include component e nucleator, and it can be so that expandable polypropylene bead of the present invention foaming back abscess uniformity coefficient improves more effective reduction unit weight.Nucleator of the present invention can be selected from a kind of or its mixing in the following material: silicon-dioxide, talcum powder, lime carbonate, magnesium oxide or zinc oxide; Be preferably silicon-dioxide.The nucleator role is extremely important to foaming process as the effect of zeolite in boiling liquid.Say that accurately nucleator forms focus air bubble growth point when foaming, just can form bubble at air bubble growth point when whipping agent decomposes, nucleator plays very important effect for the uniform distribution and the stable growth of abscess.Can control the size of abscess by the consumption of regulating nucleator, the too high weighting agent that then becomes of consumption does not have the effect of focus.Atactic copolymerized polypropene in component a is 100 parts by weight, and nucleator is 0.1～1.0 parts by weight, is preferably 0.1～0.3 parts by weight.
The atactic copolymerized polypropene that expandable polypropylene bead of the present invention can also include in component a is 100 parts by weight, the liquid adjuvants of 0.1～0.5 parts by weight.Liquid adjuvants plays the lubricated effect that reaches abscess adjustment when foaming in extrusion, and its adding helps extruding of foam material, also helps to form abscess uniform and stable, controllable size.Described liquid adjuvants is low molecule straight chain hydrocarbon of liquid or the low molecule silicoorganic compound of liquid, is preferably white oil, whiteruss or silicone oil.
In addition, expandable polypropylene bead of the present invention also can include the usual auxiliaries of polypropylene foam material, as oxidation inhibitor, fire retardant etc.Wherein oxidation inhibitor can adopt tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 168), four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010) etc., and consumption can be conventional amount used.
The preparation method of expandable polypropylene bead provided by the present invention may further comprise the steps:
1. granulation: will include described component a atactic copolymerized polypropene, components b high melt strength, propylene, amount of component b new LDPE (film grade) and component e nucleator etc. and mix by described content, and extrude through melt blending and make pellet in interior component;
2. soak into whipping agent: is 1: 1: 1～1: 1: 5 with above-mentioned gained pellet and water and described component d pentane with the component weight ratio of pellet, water and pentane, the mixing solutions of configuration places closed reactor together, stirred 2～16 hours down in 80～130 ℃, being preferable over 100～110 ℃ stirred 4～8 hours down, making whipping agent and base-material reach preferably soaks into, cool off blowing afterwards, obtain described expandable polypropylene bead.Need not in this step to reactor pressurization, the pressure in the system is low pressure, i.e. the saturated vapor pressure of solvent is generally at 0.3～0.5MPa.
With the expandable polypropylene bead that contains pneumatogen that melt extrudes more than the warp of the present invention, reactor soaked into, promptly can be used as the raw material of expanded bead or foaming product after the clean also drying of clear water.
Preparation method's step of the above expandable polypropylene bead of the present invention 1. in, component a atactic copolymerized polypropene is aforesaid atactic copolymerized polypropene.The ethene structural unit content of this atactic copolymerized polypropene (recording by infrared [Magna-IR760, Nicolet] and nuclear-magnetism [400M, Switzerland AVANCE]) is 3.5～6.5wt%, is preferably 4.0～5.0wt%; Molecular weight distribution (Mw/Mn) is 3.0～9.0, be preferably 4.2～7.0 (gel chromatograph GPC[150-CALC/GPC, Waters] measure).
Preparation method's step of the above expandable polypropylene bead of the present invention 1. in, it is that 0.05～1.05g/10min, melt strength are the high melt strength, propylene (HMSPP) of 0.5～1.2N that the components b high melt strength, propylene adopts melting index.Its melting index is preferably 0.07～0.5g/10min, and melt strength is preferably 0.7～0.9N.This kind polypropylene can adopt melting index and melt strength in the prior art to meet the polypropylene of above-mentioned condition, also can be by above-mentioned method preparation.
Preparation method's step of above-described expandable polypropylene bead of the present invention 1. in, the new LDPE (film grade) of amount of component b can comprise existing various new LDPE (film grade)s or its mixing in the prior art.
Preparation method's step of above-described expandable polypropylene bead of the present invention 1. in, the nucleator of component e can be selected from a kind of or its mixing in the following material: silicon-dioxide, talcum powder, lime carbonate, magnesium oxide or zinc oxide; Be preferably silicon-dioxide.
Preparation method's step of above-described expandable polypropylene bead of the present invention also can comprise above-described liquid adjuvants in 1..The usual auxiliaries that can comprise polypropylene foam material in addition is as oxidation inhibitor, fire retardant etc.
Expandable polypropylene bead preparation method step of the present invention is used in 1. to melt extrude the Processes and apparatus that blend can adopt polypropylene fusion of the prior art to extrude, and is controlled at 200～220 ℃ as blending temperature; Blending equipment can use the general blending equipment in the rubber and plastic processing industry, can comprise mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.For whipping agent is soaked into evenly the pellet of matrix resin, and ensure that again granulation is convenient, step in 1. to its particle diameter of pellet be preferably 1～3mm, 1.5～2mm more preferably; Its particle length is preferably 1～3mm, more preferably 1.5～2mm.
Preparation method's step of the above expandable polypropylene bead of the present invention 2. in, for in impregnation process, do not make pellet because the effect generation of temperature and pressure is even sticking, particle is disperseed, can also add tensio-active agent in the mixing solutions of the water of described configuration and whipping agent pentane.Described tensio-active agent preferred anionic type tensio-active agent and/or nonionic surface active agent.Wherein aniorfic surfactant comprises sulfonate, as the sulfoalkyl ester (Igepon A series) of linear alkylbenzene sulphonic acid (LAS), α-sodium olefin sulfonate (AOS), alkyl sodium sulfonate (SAS), sulphosuccinates, sulfonated lignin, alpha-sulfo fatty acid methyl ester (list) sodium salt (MES), lipid acid and the sulfoalkyl acid amides (Igepon T series) of lipid acid etc.; Carboxylic acid type is as soap etc.; The sulfuric acid type is as fatty alcohol sulphuric acid (ester) salt (FAS), polyoxyethylenated alcohol sodium sulfate (AES) etc.Its consumption is 0.1 ‰～0.1% of water and a pentane gross weight, is preferably 0.1 ‰～0.5 ‰.Wherein nonionic surface active agent comprises polyoxyethylene, as fatty alcohol-polyoxyethylene ether (AEO), polyoxyethylene carboxylate, alkylphenol polyoxyethylene (APEO), polyoxyethylate amide, polyoxyethylene fatty amine, tween (main chemical compositions is the polyoxyethylene sorbitan mono fatty acid ester) etc.; Polyalcohols is as ethylene glycol fatty acid, monoglyceride (mono-glycerides), pentaerythritol fatty ester, sorbitan fatty acid ester, sucrose fatty ester etc.; Polyethers, i.e. oxyethane and propylene oxide block copolymer; The alkylolamide class is as fatty diglycollic amide, fatty monoethanol amide, amine oxide and alkyl polyglycoside (APG) etc.Its consumption is 0.1 ‰～0.1% of water and a pentane gross weight, is preferably 0.1 ‰～0.5 ‰.
A kind of expanded polypropylene bead provided by the present invention makes by above-described expandable polypropylene bead foamable.Its unit weight is 0.05～0.12g/cm
3, pore diameter range is 100～450 μ m, 80% aperture is 150～250 μ m.
The processing condition of above-described foamable are the common foaming process conditions of existing expandable resin bead in the prior art, specifically can comprise: with above-described expandable polypropylene bead of the present invention, be heated to 150～190 ℃, under preferred 160～170 ℃ temperature, 1～5min obtains the expanded polypropylene bead behind preferred 2～3min.
Provided by the present inventionly a kind ofly comprise the expanded polypropylene bead and unit weight is the molded foam of 0.05～0.12g/cm3, wherein the expanded polypropylene bead is by making above expandable polypropylene bead foamable of the present invention.Use common steam heating to get final product: the pre-frothing bead is put into mould, and matched moulds feeds high-temperature steam and makes bead foam, expand, be bonded to foaming product.
Expandable polypropylene bead provided by the invention, foaming is easy, and expansion ratio can reach 11～16 times; Foaming back abscess is even, and foam unit weight is little, is 0.05～0.12g/cm
3About; The employing pentane is a whipping agent, and the preparation raw material is environment-friendly material.The preparation method of expandable polypropylene bead of the present invention adopts low-pressure process, and is low for equipment requirements, and preparation cost is low, can make difform polypropylene foam goods as required.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Below be concrete introduction to raw material in embodiment and the comparative example:
Component a atactic copolymerized polypropene (PPR): Yanshan Petrochemical production, ethene structural unit content is 4.0～5.5%, and molecular weight distribution is 4～5.0, and melting index is 0.2g/10min, and melt strength is 0.3～0.5N, 200 ℃ of surveys;
Components b high melt strength, propylene (HMSPP): get with following method self-control, melting index 0.09g/10min, melt strength survey 1.01N for 190 ℃, survey 0.92N for 210 ℃, survey 0.74N for 230 ℃;
Preparation method: in polypropylene powder (Tianjin second petrochemical plant, melting index 3g/10min, 200 ℃ of surveys of melt strength 0.21N) adding in polypropylene in is 100 weight parts, 0.43 1 of part, 6-hexanediyl ester (commercially available), in high speed agitator (1500rpm), mixed 10 minutes, in the container of packing into.Fully replace and seal with nitrogen then.Use cobalt-60 radiosterilize again, irradiation dose 1.3kGy.Material behind the irradiation was handled 2 hours down at 100 ℃, and take out the cooling back, is described high melt strength, propylene through extruding pelletization.
Its parametric measurement: measure storage modulus G ' on the ARES rotational rheometer, measure 200 ℃ of temperature, shearing rate: 0.01 second/radian, the polyacrylic G ' of raw material was 20Pas, and high melt strength, propylene G ' is 62Pas.On German Geottfert Werkstoff Pruefmaschinen company melt strength instrument, measure melt strength, it is 230 ℃ that melt is measured temperature, recording drawing force value changes delta F is 15.5cN (the drawing force value of pure material was 0.18N before this polypropylene was unmodified, and the drawing force value after the experiment condition modification of present embodiment is 0.74N).
Amount of component b new LDPE (film grade) (LDPE): Yanshan Petrochemical production, trade mark 1I2A, melting index 2.2 ± 0.3g/10min;
Silicon-dioxide (SiO 2 ): U.S. Cabot Cabot company produces, industrial goods;
White oil: Beijing Organic Chemical Plant produces, industrial goods;
Antioxidant 1010, oxidation inhibitor 168: Switzerland gas Ba Jiaji company produces;
Sodium dodecylbenzene sulfonate: belong to aniorfic surfactant, the prosperous great Science and Technology Ltd. that reaches in Tianjin produces;
Nonene phenol polyethenoxy ether (OP-10): belong to nonionic surface active agent, the prosperous great Science and Technology Ltd. that reaches in Tianjin produces;
Component d pentane (comprising Skellysolve A, iso-pentane, pentamethylene): Beijing Yili Fine Chemicals Co., Ltd. produces, industrial goods.
Embodiment 1～12
1. with component a atactic copolymerized polypropene (PPR), components b high melt strength, propylene (HMSPP), amount of component b new LDPE (film grade) (LDPE), silicon-dioxide (SiO
2), white oil, antioxidant 1010, oxidation inhibitor 168, mix by homogenizer, under 200～220 ℃, melt extrude granulation, gained particle diameter 1～2mm, length 1～2mm through twin screw extruder (ZSK-25, German WP company) afterwards.
2. soak into whipping agent: above-mentioned gained pellet is placed closed reactor with the solution that water and described component d pentane, Sodium dodecylbenzene sulfonate and/or OP-10 mix configuration, stirred 8 hours down in 100 ℃, making whipping agent and base-material reach preferably soaks into, cool off blowing afterwards, obtain described expandable polypropylene bead.
With the expandable polypropylene bead of above-mentioned gained, be placed in the electric drying oven with forced convection with the clean also drying of clear water, foamable, 160～170 ℃ of Heating temperatures, time 30s～1min obtains polypropylene foaming beads.
More than each material formula except that tensio-active agent, water, pentane consumption, all be 100 parts and see Table 1 and table 2, wherein antioxidant 1010,168 each 0.2 part in component a atactic copolymerized polypropene parts by weight; White oil is 0.1 part.In addition, water and pentane are that the pellet gross weight that 1. obtains in step respectively is that 100 parts by weight come metered amount; The consumption of tensio-active agent is in the weight percentage of water and pentane gross weight.Properties of sample test result and testing standard see Table 1 and table 2.
Comparative example 1～2
Except that the consumption of LDPE changes scope of the present invention, all the other conditions are all with embodiment 1.
Comparative example 3～4
Except that the consumption of nucleator changes scope of the present invention, all the other conditions are all with embodiment 1.
Comparative example 5～6
Except that the consumption of high melt strength, propylene changes scope of the present invention, all the other conditions are all with embodiment 1.
Comparative example 7
Except that not adding the atactic copolymerized polypropene, all the other conditions are all with embodiment 1.
Comparative example 8
Except that not adding the whipping agent, all the other conditions are all with embodiment 1.
The standard of properties of sample test is as follows in the foregoing description, the comparative example:
Foam unit weight GB/T6343-86
The density after the foaming of expansion ratio material and the ratio of the preceding density of foaming
Flexural strength GB/T8812-88
Size thermostability ISO2796
In addition, in embodiment and the comparative example in the expandable polypropylene bead of gained the content of whipping agent record by the following method: in the preparation method of the described expandable polypropylene bead of embodiment, 2. 1. step finishes the back soaks into the pellet that whipping agent handles and weighs (M) carrying out step, after having finished step processing 2. with the pellet cleaning-drying and weigh again (M ').Then the content of whipping agent is the poor of M ' and M in the bead, and the atactic copolymerized polypropene that also can calculate thus in component a is the parts by weight of the whipping agent of 100 parts by weight.
Table 1
Table 2
Claims (14)
1. expandable polypropylene bead comprises following component:
A. atactic copolymerized polypropene 100 parts by weight
B. high melt strength, propylene 1～15 parts by weight
C. new LDPE (film grade) 1～10 parts by weight
D. whipping agent 1.0～3.8 parts by weight
E. nucleator 0.1～10 parts by weight
The above component a is that ethene structural unit content is 3.5～6.5wt%, molecular weight distribution is 3.0～9.0 atactic copolymerized polypropene, its melting index is a testing standard with ASTM D1238, under 230 ℃ of temperature, load 2.16Kg condition, be measured as 0.10～1.2g/10min, 210 ℃ of melt strengths are 0.75～4.5N; Components b is that 230 ℃ of survey melt strengths are the high melt strength, propylene of 0.5～1.2N, and its melting index is a testing standard with ASTM D1238, under 230 ℃ of temperature, load 2.16Kg condition, is measured as 0.05-1.05g/10min; The whipping agent of described component d is a pentane; Described nucleator is selected from a kind of or its mixing in the following material: silicon-dioxide, talcum powder, lime carbonate, magnesium oxide or zinc oxide.
2. expandable polypropylene bead according to claim 1, it includes following component:
A. atactic copolymerized polypropene 100 parts by weight
B. high melt strength, propylene 5～12 parts by weight
C. new LDPE (film grade) 3～8 parts by weight
D. whipping agent 1.5～3.2 parts by weight
E. nucleator 0.1～0.3 parts by weight.
3. according to the described expandable polypropylene bead of one of claim 1～2, wherein ethene structural unit content is 4.0～5.0wt% in the atactic copolymerized polypropene of component a, and molecular weight distribution is 4.2～7.0.
4. according to the described expandable polypropylene bead of one of claim 1～2, wherein the high melt strength, propylene melting index of components b is a testing standard with ASTM D1238, under 230 ℃ of temperature, load 2.16Kg condition, be measured as 0.07～0.5g/10min, 230 ℃ are surveyed melt strength is 0.7～0.9N.
5. according to the described expandable polypropylene bead of one of claim 1～2, wherein the whipping agent of component d is Skellysolve A, iso-pentane, pentamethylene or its mixing.
6. preparation method according to each described expandable polypropylene bead of claim 1～5 may further comprise the steps:
1. granulation: will include described component a atactic copolymerized polypropene, components b high melt strength, propylene and amount of component b new LDPE (film grade), the e nucleator mixes by described content in interior component, and extrude through melt blending and make pellet;
2. soak into whipping agent: is 1: 1: 1～1: 1: 5 with above-mentioned gained pellet and water and described component d pentane with the component weight ratio of pellet, water and pentane, the mixing solutions of configuration places closed reactor together, stirred 2～16 hours down in 80～130 ℃, cooling back blowing obtains described expandable polypropylene bead.
7. preparation method according to claim 6, wherein step 1. described in component extrude through melt blending and make pellet, its particle diameter is 1～3mm, length is 1～3mm.
8. preparation method according to claim 6, wherein add tensio-active agent in the mixing solutions of step described in 2., wherein tensio-active agent is selected from aniorfic surfactant and/or nonionic surface active agent, and its consumption is 0.1 ‰～0.1% of water and a pentane gross weight.
9. preparation method according to claim 8, wherein the 2. middle dosage of surfactant of step is 0.1 ‰-0.5 ‰ of water and a pentane gross weight.
10. preparation method according to claim 8, wherein said aniorfic surfactant is selected from sulfonate, carboxylate salt and sulfuric acid; Wherein said nonionic surface active agent is selected from polyoxyethylene, polyalcohols, polyethers, alkylolamide class.
11. preparation method according to claim 6, wherein the 2. middle whipping temp of step is 100～110 ℃; Churning time is 4～8 hours.
12. expanded polypropylene bead that makes by each described expandable polypropylene bead foamable with claim 1～5.
13. expanded polypropylene bead according to claim 12, its unit weight are 0.05～0.12g/cm
3
14. one kind comprises the expanded polypropylene bead and unit weight is 0.05～0.12g/cm
3, molded foam, wherein the expanded polypropylene bead makes by each the described expandable polypropylene bead foamable with claim 1～5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610089710A CN100575404C (en) | 2006-07-13 | 2006-07-13 | A kind of expandable polypropylene bead and preparation method thereof and expanded bead thereof and molded foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610089710A CN100575404C (en) | 2006-07-13 | 2006-07-13 | A kind of expandable polypropylene bead and preparation method thereof and expanded bead thereof and molded foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101104716A CN101104716A (en) | 2008-01-16 |
| CN100575404C true CN100575404C (en) | 2009-12-30 |
Family
ID=38998803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610089710A Active CN100575404C (en) | 2006-07-13 | 2006-07-13 | A kind of expandable polypropylene bead and preparation method thereof and expanded bead thereof and molded foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100575404C (en) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353460B (en) * | 2008-09-11 | 2011-11-16 | 丹阳市华东工程塑料有限公司 | Environment-friendly type micro-foaming polypropylene sheet and preparation thereof |
| WO2010049371A1 (en) * | 2008-10-27 | 2010-05-06 | Borealis Ag | Extrusion blown molded bottles with high stiffness and transparency |
| CN102115561B (en) * | 2009-12-30 | 2013-02-20 | 李晓丽 | Physical foaming polypropylene sheet material |
| CN101866717B (en) * | 2010-05-12 | 2011-08-31 | 深圳市穗榕同轴电缆科技有限公司 | High-temperature resistant fire-retardant co-axial cable |
| CN102285171B (en) * | 2011-05-27 | 2014-03-26 | 常州市华星新材料科技有限公司 | Non-natural continuous filament fabric reinforced low-density pre-foamed plastic sheet |
| US9067705B2 (en) | 2011-06-17 | 2015-06-30 | Berry Plastics Corporation | Process for forming an insulated container having artwork |
| BR112013032423A2 (en) | 2011-06-17 | 2017-01-17 | Berry Plastics Corp | insulating glove for a cup |
| CN103717500B (en) | 2011-06-17 | 2016-02-03 | 比瑞塑料公司 | Thermally insulated container |
| WO2012174422A2 (en) | 2011-06-17 | 2012-12-20 | Berry Plastics Corporation | Insulated container with molded brim |
| CN102888053B (en) * | 2011-07-21 | 2014-08-27 | 中国石油化工股份有限公司 | Halogen-free flame-retardant polypropylene foam material and preparation method thereof |
| KR20140059255A (en) | 2011-08-31 | 2014-05-15 | 베리 플라스틱스 코포레이션 | Polymeric material for an insulated container |
| CN102295807B (en) * | 2011-09-05 | 2013-11-20 | 浙江俊尔新材料有限公司 | Extrusion expanded polypropylene beads and preparation method thereof |
| CN102391571B (en) * | 2011-09-05 | 2013-04-24 | 浙江俊尔新材料有限公司 | Extrusion foaming polypropylene particles with lower thermal molding pressure and preparation method thereof |
| CN103665582B (en) * | 2012-09-04 | 2016-02-24 | 中国石油化工股份有限公司 | Propylene and ethylene butylene high melt strength, propylene foaming plate or sheet material and preparation method thereof |
| CN103665567B (en) * | 2012-09-04 | 2015-09-16 | 中国石油化工股份有限公司 | Co-polymer foamed bead of propylene butene and preparation method thereof |
| SG11201503336VA (en) * | 2012-10-26 | 2015-06-29 | Berry Plastics Corp | Polymeric material for an insulated container |
| CA2905085A1 (en) | 2013-03-14 | 2014-09-25 | Berry Plastics Corporation | Container |
| CN103131087B (en) * | 2013-03-21 | 2015-09-23 | 合肥汇邦高分子材料有限责任公司 | A kind of injection molding process of microporous foam PP plastics |
| EP3033208A4 (en) | 2013-08-16 | 2017-07-05 | Berry Plastics Corp. | Polymeric material for an insulated container |
| CN104448575B (en) * | 2014-12-04 | 2017-02-01 | 联塑市政管道（河北）有限公司 | Low-temperature resistant PP-R pipe and preparation method thereof |
| WO2016118838A1 (en) | 2015-01-23 | 2016-07-28 | Berry Plastics Corporation | Polymeric material for an insulated container |
| CN104725724A (en) * | 2015-03-24 | 2015-06-24 | 合肥创新轻质材料有限公司 | Smell removing master batch as well as preparation method and application thereof |
| CN106084453A (en) * | 2016-06-08 | 2016-11-09 | 上海光大高科技股份有限公司 | A kind of automobile fretting map enhancing modified polypropylene and preparation method thereof |
| CN106317642A (en) * | 2016-08-31 | 2017-01-11 | 无锡会通轻质材料股份有限公司 | Preparation method of silver-grey antistatic type bubbling polypropylene beads |
| CN106397977A (en) * | 2016-08-31 | 2017-02-15 | 无锡会通轻质材料股份有限公司 | Novel conductive type expanded polypropylene beads and preparation method thereof |
| CA3013585A1 (en) | 2017-08-08 | 2019-02-08 | Berry Global, Inc. | Insulated container |
| CN109705470A (en) * | 2019-01-16 | 2019-05-03 | 广西云亭烯技术有限公司 | A kind of preparation method of graphene EPP |
| CN110256765B (en) * | 2019-06-30 | 2020-11-13 | 浙江大学 | Biaxially oriented foamed polypropylene film and preparation method thereof |
| CN110437380A (en) * | 2019-07-10 | 2019-11-12 | 青岛青迈高能电子辐照有限公司 | A kind of method of irradiation grafting preparation high-performance polybutene expanded bead (EPB) |
| CN112280089A (en) * | 2019-07-24 | 2021-01-29 | 安踏（中国）有限公司 | Middle sole formed by mould pressing physical foaming and preparation method thereof |
| CN110483829A (en) * | 2019-08-22 | 2019-11-22 | 中国科学院青岛生物能源与过程研究所 | A kind of low irradiation intensity prepares the preparation method of high-strength polypropylene expanded bead (EPP) |
| CN111138705A (en) * | 2020-01-09 | 2020-05-12 | 宁波铭瑞中兴电子科技有限公司 | Preparation method of foaming floating ball |
| CN112409684A (en) * | 2020-11-03 | 2021-02-26 | 临沂利方塑胶制品有限公司 | Processing method of high-strength toy plastic |
| CN114573915B (en) * | 2022-03-08 | 2023-12-01 | 广东新亚光电缆股份有限公司 | Low-energy-consumption pipe production process |
| CN115926030A (en) * | 2022-12-16 | 2023-04-07 | 东莞巨正源科技有限公司 | High-permeability high-toughness low-isotacticity polypropylene thermal forming resin and preparation process thereof |
-
2006
- 2006-07-13 CN CN200610089710A patent/CN100575404C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 高发泡倍率聚丙烯泡沫材料的研制. 刘涛，张薇，张师军.合成树脂及塑料，第22卷第6期. 2005 |
| 高发泡倍率聚丙烯泡沫材料的研制. 刘涛，张薇，张师军.合成树脂及塑料，第22卷第6期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101104716A (en) | 2008-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100575404C (en) | A kind of expandable polypropylene bead and preparation method thereof and expanded bead thereof and molded foam | |
| KR100679552B1 (en) | Abs complex material manufacturing method and abs complex material thereby | |
| CN101538387B (en) | Polypropylene foaming material and production method thereof | |
| CN102218879B (en) | Waste polypropylene-modified foaming plate and manufacturing method thereof | |
| CN105504498B (en) | A kind of injection grade polypropylene microporous foam composite material and preparation method thereof | |
| CN103834097B (en) | A kind of polypropylene microparticle and method for making and the method being prepared polypropylene foaming beads by it and product | |
| CN102070841A (en) | Polypropylene foam sheet prepared from composite foaming agent and production method thereof | |
| CN102604216B (en) | Laser-marked glass-fiber reinforced polypropylene composite as well as preparation method and application thereof | |
| CN106715553B (en) | Composite resin particle, its manufacturing method, foaminess particle, expanded beads, foam molding and automotive interior trim part | |
| CN110591309B (en) | Biodegradable foamed plastic composite material and preparation method and application thereof | |
| CN104350118B (en) | The method preparing flowable amorphous poly alhpa olefin binding agent pellet | |
| CN104327369A (en) | Polypropylene composition and polypropylene pellet | |
| CN103665583A (en) | Propylene-ethylene high-melt-strength polypropylene foamed bead and preparation method thereof | |
| CN103788502A (en) | Polypropylene foaming bead formed body and preparation method thereof | |
| CN105563684A (en) | Process for making thermoplastic polymer pellets | |
| CN107108937A (en) | The auxiliary material that foams and foam forming method | |
| CN102079841A (en) | High-flowability impact-resistant polypropylene composite and preparation method thereof | |
| CN114773722B (en) | Polypropylene material and preparation method and application thereof | |
| CN103951866B (en) | Expanded polyolefin composition and polyolefin foam and its preparation method and the goods prepared by said composition | |
| CN100389150C (en) | Polypropylene foaming premix and its preparation method | |
| CN110627959A (en) | Preparation method of high-strength high-toughness microporous polybutylene foam beads (EPB) | |
| JP2002105442A (en) | Heat storage material composition | |
| CN106117814A (en) | A kind of automotive upholstery microporous foam PP composite material and preparation method thereof | |
| CN103665420A (en) | Propylene-ethylene-butylene high-melt-strength polypropylene foamed bead and preparation method thereof | |
| CN1270968A (en) | Process for preparing foam resin product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |