CN100460459C - Method for preparing hybridization material of polypropylene group through cross blending fusion - Google Patents
Method for preparing hybridization material of polypropylene group through cross blending fusion Download PDFInfo
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- CN100460459C CN100460459C CNB2006100671660A CN200610067166A CN100460459C CN 100460459 C CN100460459 C CN 100460459C CN B2006100671660 A CNB2006100671660 A CN B2006100671660A CN 200610067166 A CN200610067166 A CN 200610067166A CN 100460459 C CN100460459 C CN 100460459C
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- polypropylene
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- -1 polypropylene group Polymers 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims description 38
- 230000004927 fusion Effects 0.000 title claims description 6
- 238000009396 hybridization Methods 0.000 title claims description 6
- 239000004743 Polypropylene Substances 0.000 claims abstract description 43
- 229920001155 polypropylene Polymers 0.000 claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000004793 Polystyrene Substances 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 26
- 229910000019 calcium carbonate Inorganic materials 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 11
- 239000008188 pellet Substances 0.000 description 10
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KHWQFISNNNRGLV-UHFFFAOYSA-N 2,4,6-tributylphenol Chemical compound CCCCC1=CC(CCCC)=C(O)C(CCCC)=C1 KHWQFISNNNRGLV-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
This invention relates to a method for preparing polypropylene-based hybrid by melt blending. The polypropylene-based hybrid is inorganic nanoparticles/elastomer/polypropylene hybrid, and has such advantages as uniform dispersion of inorganic phase and high impact strength.
Description
Technical field:
The present invention relates to a kind of method of preparing hybridization material of polypropylene group through cross blending fusion, be a kind of employing step by step the dispersive melt-mixing method prepare the method for inorganic nano-particle/elastomerics/polypropylene hybrid material.
Background technology:
The preparation method of inorganic/organic nano hybrid material has sol-gel method, situ aggregation method, melt-blending process etc.Wherein, melt-blending process is a kind of method that is easy to realize industrial applications.With inorganic nano-particle and plastics and elastomer blended, make inorganic/organic nano hybrid material, can bring into play inorganic nano-particle and elastomeric coordination plasticizing effect, significantly improve the shock strength of plastics.Nano-calcium carbonate is in inorganic/organic nano hybrid material research one of inorganic nano-particle of application prospect to be arranged most.In addition, the inorganic nano-particle that is applied to inorganic/organic nano hybrid material also has nano silicon, layered silicate (if you would take off soil) etc.
Polypropylene is the lower brittle plastic of a kind of shock strength, need carry out toughening modifying.In polyacrylic toughening modifying, traditional method is to adopt the elastic body toughening agent, and used elastomerics has styrene-butadiene block copolymer (SBS), terpolymer EP rubber (EPDM), ethene-1-octene copolymer (POE) etc.In recent years, the application of POE in polypropylene toughening is comparatively general.Though the elastic body toughening method can obtain toughness preferably, the rigidity of material (bending elastic modulus) can descend.Inorganic nano-particles such as nano-calcium carbonate have significant toughening effect to polypropylene, with inorganic nano-particle and polypropylene and elastomer blended, make inorganic nano-particle/elastomerics/polypropylene hybrid material, can bring into play inorganic nano-particle and elastomeric coordination plasticizing effect, significantly improve shock strength, and can improve rigidity (bending elastic modulus) simultaneously; Compare with independent employing elastic body toughening, considerable advantage is arranged.
Prepare at blending method inorganic/during the organic nano hybrid material, a major issue that solve is the dispersion of inorganic nano-particle in polymeric matrix.The method that adopts is a mother material at present.The patent that the inventor has " toughness reinforced mother material for nanometer calcium carbonate plastics " (patent No. 00129696.5) is exactly the patent about a kind of nano-calcium carbonate masterbatch formula system.Adopting mother material to prepare inorganic/organic nano hybrid material, is that inorganic nano-particle is prepared into masterbatch with polymer support and auxiliary agent blend earlier, then with masterbatch once with polymer blending, be prepared into nano-hybrid material.Because in this method, masterbatch be once with polymer blending, so the dispersion of inorganic nano-particle in polymkeric substance, and the raising degree of associated polymer performance just has been subjected to influence.
Summary of the invention:
The novel method that the purpose of this invention is to provide a kind of preparing hybridization material of polypropylene group through cross blending fusion, inorganic nano-particle is mixed with elastomerics, employing twin screw extruder dispersive melt-mixing method step by step prepares inorganic nano-particle/elastomerics/polypropylene hybrid material, make inorganic nano-particle more even, thereby improve the performance of material in the dispersion of organic phase.
The present invention is a kind of method of preparing hybridization material of polypropylene group through cross blending fusion, concrete step and method are: at first inorganic nano-particle is mixed with the mass ratio of elastomerics with 2:3 to 3:2, make inorganic nano-particle one-level masterbatch with twin screw extruder, then, the part of the total consumption of polypropylene is mixed with the one-level masterbatch earlier, with twin screw extruder blend granulation, make the secondary masterbatch; In the secondary masterbatch, add a part of polypropylene, granulation more again; Repeated 2-6 this dispersion step by step, up to polyacrylic prescription consumption is all added.
The each polypropylene amount of adding and the mass ratio of this grade masterbatch are 1: 4 to 2: 3 in disperseing step by step.
The said inorganic nano-particle of the present invention is lime carbonate, aluminium hydroxide, silicon-dioxide or titanium dioxide, and the grain diameter of particle is less than or equal to 100 nanometers;
Said elastomerics is ethene-1-octene copolymer (POE) or terpolymer EP rubber (EPDM);
Also add the 1-5% low-molecular-weight polystyrene in the said one-level masterbatch, 0.1-0.3% oxidation inhibitor, as: four (3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid) pentaerythritol ester (being antioxidant 1010) or 2,4,6-tri-butyl-phenol (being oxidation inhibitor 246).
Method of the present invention, the dispersive number of times is too much unsuitable step by step, too much can cause polyacrylic degraded, and is unfavorable to material property.The very few aim of even dispersion that do not reach.
Adopt the inorganic nano-particle/elastomerics/polypropylene hybrid material of method preparation of the present invention, compare with the masterbatch blending method of common employing, not only the dispersion of inorganic particulate between organic phase is more even, the performance of material, as shock strength etc., also has raising by a larger margin.
Embodiment:
Embodiment 1
Nano-calcium carbonate (particle diameter is the 30-40 nanometer) is mixed with ethene-1-octene copolymer (POE), with prepared in twin-screw extruder one-level masterbatch, the prescription of one-level masterbatch (mass percent) is: nano-calcium carbonate 50%, POE 48%, low-molecular-weight polystyrene 1.8%, oxidation inhibitor (model 1010) 0.2%.By the one-level masterbatch: polypropylene is that 70: 30 mass ratio adds polypropylene, through the twin screw extruder granulation, makes the secondary masterbatch; Again by the secondary masterbatch: polypropylene is that 70: 30 mass ratio adds polypropylene, granulation once more; So repeat 4 times (promptly the dispersive number of times is 4 times step by step).The pellet of the nano-calcium carbonate of making/POE/ polypropylene hybrid material contains polypropylene 76% in the composition, nano-calcium carbonate 12%, and POE 11.5%, low-molecular-weight polystyrene 0.45%, oxidation inhibitor (model 1010) 0.05%.Adopt injection moulding to make batten the pellet of the nano-calcium carbonate/POE/ polypropylene hybrid material of present embodiment preparation, the simply supported beam notched Izod impact strength of mensuration is 64.2KJ/m
2
Embodiment 2
Dispersion multiplicity step by step among the embodiment 1 is 5 times, and other conditions are with embodiment 1.The pellet of the nano-calcium carbonate of making/POE/ polypropylene hybrid material contains polypropylene 83.2% in the composition, nano-calcium carbonate 8.4%, and POE 8.05%, low-molecular-weight polystyrene 0.32%, oxidation inhibitor (model 1010) 0.03%.Adopt injection moulding to make batten the pellet of the nano-calcium carbonate/POE/ polypropylene hybrid material of present embodiment preparation, the simply supported beam notched Izod impact strength of mensuration is 60.6KJ/m
2
Embodiment 3
Dispersion multiplicity step by step among the embodiment 1 is 6 times, and ethene-1-octene copolymer (POE) changes terpolymer EP rubber (EPDM) into, and other preparation conditions are with embodiment 1.The nano-calcium carbonate of making/EPDM/ polypropylene hybrid material pellet contains polypropylene 88.2% in the composition, nano-calcium carbonate 5.9%, EPDM5.68%, low-molecular-weight polystyrene 0.2%, oxidation inhibitor (model 1010) 0.02%.
Embodiment 4
Dispersion multiplicity step by step among the embodiment 1 is changed into 2 times, and nano-calcium carbonate changes nano-aluminum hydroxide (particle diameter is the 80-100 nanometer) into, and masterbatch at different levels: polyacrylic ratio changes 80: 20 into, and other preparation conditions are with embodiment 1.The nano-aluminum hydroxide of making/POE/ polypropylene hybrid material pellet contains polypropylene 52% in the composition, nano-aluminum hydroxide 24%, and POE 23.12%, low-molecular-weight polystyrene 0.8%, oxidation inhibitor (model 1010) 0.08%.
Embodiment 5
Change the nano-calcium carbonate among the embodiment 1 into nano silicon (particle diameter is the 20-30 nanometer), the prescription of one-level masterbatch (mass percent) changes into: nano silicon 40%, POE 58%, low-molecular-weight polystyrene 1.8%, oxidation inhibitor (model 246) 0.2% disperses multiplicity to change into step by step 2 times.All the other preparation conditions are identical with embodiment 1.The nano silicon of making/POE/ polypropylene hybrid material pellet contains polypropylene 51% in the composition, nano silicon 19.6%, and POE 28.3%, low-molecular-weight polystyrene 1%, oxidation inhibitor (model 1010) 0.1%.
Embodiment 6
Change the nano-calcium carbonate of implementing in 1 into nano titanium oxide (particle diameter is the 30-40 nanometer), the prescription of one-level masterbatch (mass percent) changes into: nano titanium oxide 60%, POE 35%, low-molecular-weight polystyrene 4.8%, oxidation inhibitor (model 1010) 0.2% disperses multiplicity to change into step by step 3 times.All the other preparation conditions are identical with embodiment 1.The nano titanium oxide of making/POE/ polypropylene hybrid material pellet contains polypropylene 65.7% in the composition, nano titanium oxide 20.6%, and POE 12.03%, low-molecular-weight polystyrene 1.7%, oxidation inhibitor (model 1010) 0.07%.
Embodiment 7
To implement one-level masterbatch in 1: polyacrylic ratio changes 80: 20 into, disperses multiplicity to change into step by step 4 times.All the other preparation conditions are identical with embodiment 1.The pellet of the nano-calcium carbonate of making/POE/ polypropylene hybrid material contains polypropylene 67.2% in the composition, nano-calcium carbonate 16.4%, and POE 15.85%, low-molecular-weight polystyrene 0.5%, oxidation inhibitor (model 1010) 0.05%.
Comparative Examples 1
Following material is prepared into nano-calcium carbonate/POE/ polypropylene hybrid material by common masterbatch blending method, and its composition is: polypropylene 76%, nano-calcium carbonate 12%, POE 11.5%, low-molecular-weight polystyrene 0.45%, oxidation inhibitor (model 1010) 0.05% is identical with embodiment 1.The preparation method becomes masterbatch with prepared in twin-screw extruder earlier according to the above ratio with nano-calcium carbonate, POE, low-molecular-weight polystyrene, oxidation inhibitor (model 1010), mix according to the above ratio with polypropylene once then, become the pellet of nano-calcium carbonate/POE/ polypropylene hybrid material with prepared in twin-screw extruder, adopt injection moulding to make batten again, the simply supported beam notched Izod impact strength of mensuration is 58.5KJ/m
2Compare with embodiment 1, the notched Izod impact strength of Comparative Examples 1 is starkly lower than embodiment 1.
Comparative Examples 2
Following material is prepared into nano-calcium carbonate/POE/ polypropylene hybrid material by common masterbatch blending method, and its composition is: polypropylene 83.2%, nano-calcium carbonate 8.4%, POE 8.05%, low-molecular-weight polystyrene 0.32%, oxidation inhibitor (model 1010) 0.03% is identical with embodiment 2.The preparation method in proportion 1.The notched Izod impact strength of measuring is 57.4KJ/m
2Compare with embodiment 2, the notched Izod impact strength of Comparative Examples 2 is starkly lower than embodiment 2.
Claims (2)
1. the method for a preparing hybridization material of polypropylene group through cross blending fusion, concrete step and method are: at first inorganic nano-particle is mixed with the mass ratio of elastomerics with 2:3 to 3:2, make inorganic nano-particle one-level masterbatch with twin screw extruder, then, the part of the total consumption of polypropylene is mixed with the one-level masterbatch earlier, with twin screw extruder blend granulation, make the secondary masterbatch; In the secondary masterbatch, add a part of polypropylene, granulation more again; Repeated 2-6 this dispersion step by step, and up to polyacrylic prescription consumption is all added, the each polypropylene amount of adding and the mass ratio of this grade masterbatch are 1: 4 to 2: 3 in disperseing step by step;
Said inorganic nano-particle is lime carbonate, aluminium hydroxide, silicon-dioxide or titanium dioxide, and the grain diameter of particle is less than or equal to 100 nanometers;
Said elastomerics is ethene-1-octene copolymer or terpolymer EP rubber.
2. according to the method for claim 1, it is characterized in that: add the low-molecular-weight polystyrene of mass percent 1-5% and the oxidation inhibitor of 0.1-0.3% in the said one-level masterbatch.
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| CNB2006100671660A CN100460459C (en) | 2006-04-06 | 2006-04-06 | Method for preparing hybridization material of polypropylene group through cross blending fusion |
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| CN100460459C true CN100460459C (en) | 2009-02-11 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102008054967A1 (en) * | 2008-12-19 | 2010-06-24 | Evonik Degussa Gmbh | Silatran-containing particles |
| CN102634111A (en) * | 2011-02-10 | 2012-08-15 | 黑龙江鑫达企业集团有限公司 | High-toughness polymer composite material and preparation method thereof |
| TWI490108B (en) | 2013-12-20 | 2015-07-01 | Ind Tech Res Inst | Composite and method for preparing the same |
| CN104945744A (en) * | 2014-03-27 | 2015-09-30 | 苏州欣港神工贸有限公司 | High-polymer thermoplastic elastomer roller and manufacturing technique thereof |
| JP6713095B2 (en) * | 2016-08-12 | 2020-06-24 | 株式会社Ｔｂｍ | Method for producing resin molded body, method for producing resin molding pellets and method for improving smoothness |
| CN107903494A (en) * | 2017-11-22 | 2018-04-13 | 西安交通大学 | A kind of polypropylene-base blending type nanocomposite and preparation method thereof |
| KR20220061447A (en) * | 2020-11-06 | 2022-05-13 | 한국전기연구원 | Method for manufacturing thermoplastic elastomer nanocomposites by wet process, thermoplastic elastomer nanocomposites manufactured therefrom |
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|---|---|---|---|---|
| CN1285365A (en) * | 2000-10-16 | 2001-02-28 | 北京化工大学 | Toughness reinforced mother material for nanometer calcium carbonate plastics |
| KR20010100279A (en) * | 2000-04-07 | 2001-11-14 | 박찬구 | Process for preparing intercalated nanocomposites |
| CN1631960A (en) * | 2004-11-30 | 2005-06-29 | 上海普利特复合材料有限公司 | Talc powder filled polypropylene with high rigidity, high toughness and high scratch resistance and method for preparing same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010100279A (en) * | 2000-04-07 | 2001-11-14 | 박찬구 | Process for preparing intercalated nanocomposites |
| CN1285365A (en) * | 2000-10-16 | 2001-02-28 | 北京化工大学 | Toughness reinforced mother material for nanometer calcium carbonate plastics |
| CN1631960A (en) * | 2004-11-30 | 2005-06-29 | 上海普利特复合材料有限公司 | Talc powder filled polypropylene with high rigidity, high toughness and high scratch resistance and method for preparing same |
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Assignee: TAIAN MODERN PLASTIC Co.,Ltd. Assignor: Beijing University of Chemical Technology Contract record no.: 2010370000415 Denomination of invention: Method for preparing hybridization material of polypropylene group through cross blending fusion Granted publication date: 20090211 License type: Exclusive License Open date: 20071010 Record date: 20100730 |
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