CN102217465A - Preparation method for nano-composite beta-crystal co-polypropylene (NFbetaPP) material - Google Patents
Preparation method for nano-composite beta-crystal co-polypropylene (NFbetaPP) material Download PDFInfo
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Abstract
The invention relates to a preparation method for a nano-composite beta-crystal co-polypropylene (NFbetaPP) material, belonging to the field of modified polypropylene materials, which mainly uses nano calcium carbonate and a beta-crystal nucleating agent to form a polynuclear complex high-efficacy beta-crystal nucleating agent to produce betaPPR (beta-crystal polypropylene random copolymer) (H/B), uses a certain amount of nanomaterial to modify the overall performance of beta-PP (beta-crystal polypropylene), and uses a melting, mixing, polymerizing and granulating technique with a twin-screw extruder to synthesize the NFbetaPP material for volume production. After adding 0.1-3% of the beta-crystal complex nucleating agent, the notched impact strength at room temperature of beta-PP is improved by 20-90%, the compressive strength is increased by 30-50% and the heat-resistant temperature is increased by 20 DEG C, compared with PP. When the use amount of nano calcium carbonate is 4%, the impact strength of the NFbetaPP material is increased by 33% compared with beta-PP and is 3 times that of pure PP, the tensile modulus and flexural modulus are respectively increased by 10% and 15% compared with beta-PP, and the content of beta-crystal is about 6% higher than that of beta-PP.
Description
Technical field:
Modified polypropylene material
Technical background:
Polypropylene (PP) has that density is little, good mechanical performance, electrical insulating property is good, dielectric constant is less, proof stress is drawn up and advantages such as chemical resistance corrosion, and easily processing, heat distortion temperature height, good heat resistance, the stress performance of anti-the ring are good, inexpensive etc., are widely used in every field such as pipeline, film, sheet material.But PP also has, and anti-notched Izod impact strength is low, black brittleness is big, shortcomings such as creep is big under the HTHP.Therefore, modification toughness reinforcing to PP, that strengthen is very active.Can adopt elastomer blended modifier to come Toughened PP generally speaking, but the method has been sacrificed intensity and the heat resistance of PP.Though the blend rigid particles can improve intensity, rigidity and the warm tolerance of PP, can reduce its impact strength and cryogenic property.Realizing improving its compressive resistance, heat resisting temperature and high-temperature creep resistance toughness reinforcing the time with the common MODIFIED PP of beta nucleater with the nano grade inorganic material, is very effective method in.
Polypropylene (PP) is a semicrystalline polymeric, and the structural form of its degree of crystallinity, crystal formation and crystal plays a crucial role to its performance.PP can generate five kinds of crystalline structures such as α, β, γ, δ and plan hexagonal crystal usually because of the crystallization condition difference.Wherein, the basic alpha-crystal form that generates under general processing conditions, alpha-crystal form be modal also be the best crystal formation of stability; Beta crystal takes second place, and adds beta nucleater fusion copolymerization method exactly in the most effective industrial processing method.Beta crystal PP short texture, crystallization is incomplete, and the structure of radial layer and axially layer cross arrangement seldom mainly exists with simple layer shape harness shape in the crystal.The extended pattern segment that in the porous crystalline zone of β crystalline substance, exists a large amount of continuous strands to be connected to form, this makes the PP material of β crystalline substance can absorb more energy when being damaged, demonstrate toughness and ductility preferably, the structure of this layer shape harness shape has improved the high temperature and creep resistance and the antioxygenic property of PP material, and has greatly improved withstand voltage, the heat-resisting and service life of product.In addition, do not have tangible combination interface between the brilliant PP spherocrystal of β, at adjacent spherocrystal boundary, platelet intermeshes, and this structure is difficult for greatly having been improved corrosion such as the acid and alkali resistance of PP product, salt by corrosion such as chemicalss.A certain amount of beta nucleater is added in the PP material, with the fusion copolymerization method produce the brilliant PP of β be the most effective also be one of the simplest method.At present, commercially available beta nucleater has: 1 condensed ring compounds with planar structure is as triphen dithiazine, phenothiazine etc.; 2 bi-component binary acid types such as stearic acid and pimelic acid are composite by a certain percentage; 3 aromatic amines are as 2,6-phthalic acid Cyclohexamide (DCTH) or 2,6-naphthalenedicarboxylic acid Cyclohexamide, TBM4, TBM5; 4 terres rares are by calcium and rare earth element mixed matching such as WBG etc., and wherein the terres rares effect is best.
It is fairly obvious to PP notched Izod impact strength and unnotched impact strength toughening effect to add nano material, two aspects of having traced it to its cause: the one, material is under the impact stress effect, nano particle can produce with matrix on every side and peel off and form the cavity, stress state around the existence in this cavity can change, make matrix produce the shearing surrender and absorb a large amount of impact energys, therefore improved the impact strength of material; The 2nd, the existence of nano particle makes the PP material play the nucleus effect in crystallization process, and the effect of heterogeneous nucleation has improved crystalline rate, refinement crystallite dimension, improved the toughness of PP material and the shock resistance of product greatly.。At present, adding commercially available nano-calcium carbonate, silica, titanium dioxide, alundum (Al etc. polymer-modified is one of effective, the most most economical material.
Summary of the invention: major technique of the present invention just has been to use the brilliant nucleator of nano-calcium carbonate and terres rares and aromatic amine β to be re-dubbed " polynuclear complex " brilliant composite nucleator of β efficiently, this highly efficiency compositional nucleator especially has special crystal transfer effect and effect to PP-R, compare with independent use nucleator, beta crystal content can exceed more than 30% among the β PP-R.Test shows, interpolation certain amount of nano calcium carbonate can improve the combination property of the brilliant PP of β, as being 4% o'clock at the nano-calcium carbonate consumption, impact strength has improved 33% than β-PP-H, be 3 times of pure PP-H, stretch modulus, bending modulus have improved 10% and 15% than β-PP-H respectively, and the content of β crystalline substance exceeds about 6% than β-PP.
The tubing that the technology of the present invention β PP-R/ nano composite material modifying PP-R (NF β PP-R) is made, has high heat-resisting, high withstand voltage, high tenacity and anti-low temperature by advantages such as, long-lives, trace it to its cause one is exactly that the brilliant unique spiral growth fasciculation aggregation of β grows up to mutually with the edge of peripheral crystal in the crystal growth process that overlaying state is dried mutually scratches, permeates, between each grain boundary, collide, overlap to form layer structure, fine and close and stable no tangible interface between the crystal edge with the flakes form.The layer structure crystalline material of this spiral growth pencil aggregation has that heat distortion temperature height, oxidation resistance are strong, molecular link factors such as easy fracture of being heated not between grain boundary, has greatly improved heat-resisting, the high withstand voltage performance of product height; Its reason two can cause a large amount of crackles when being subjected to impacting, thereby absorbs a large amount of impact energys.Simultaneously because the interfering with each other of stress field between a large amount of crackles can stop further developing of crackle again, thereby improved material toughness; The effect of nano material, but refinement the crystal grain of β PP-R, the reducing of crystallite dimension overcome between the coarse grain interface stress and concentrated breakable defective, when being subjected to external impacts, stress disperseed, thereby improved the impact property of material.This shows the result of the comprehensive function that reduces of the above-mentioned just surrender mechanism of the raising of β-PP-/nano composite material impact property, beta-crystalline form one-tenth and crystallite dimension.
The present invention is realized by following technology:
Employing is put into kneader through stearic acid surface-treated nano-calcium carbonate with the brilliant nucleator of β and was mixed 30 minutes down for 100 rev/mins at 80～100 ℃, rotating speed, and the cooling back is stand-by with thin-film package under vacuum state.With nano material, antioxidant, compatilizer, dispersant, PP material after ultrahigh speed intensive mixer high speed stirs, through double screw extruder melt blending polymerization granulation (each section of machine barrel temperature is 170～225 ℃).One of major technique of the present invention is to have adopted the brilliant nucleator of " polynuclear complex " combination β of kneading technology synthesizing efficient, and the brilliant nucleator of this combination β is that PE is had significant beta crystal nucleation Modification effect with the random segment COPP PP-R of branch in PP.
Two of major technique of the present invention is to have adopted double screw extruder melt blending polymerization technique to realize scale volume production β-PP.
Three of major technique of the present invention is with modification β-PP such as nano-calcium carbonates, has improved the nucleation rate of β-PP, refinement the crystal grain of β-PP, improved the toughness and the low temperature resistivity of material.
Four of major technique of the present invention is to have adopted ultrahigh speed powerful mixing technology, has realized the even branch of nano material ecosystem in polymer.The brilliant nucleator of the β of indication of the present invention is commercially available terres rares WBG, aromatic amine, enanthic acid and stearic compound, calcium salt etc.
The nanometer of indication of the present invention is that particle diameter is 20～80nm nano-calcium carbonate or alundum (Al etc.
The antioxidant of indication of the present invention is 1010,168 commercially available combination antioxidant.
The compatilizer of indication of the present invention is commercially available maleic anhydride inoculated polypropylene.
The dispersant of indication of the present invention is commercially available ethylene group bis-stearamides (E B S).
The PP of indication of the present invention is PP-H, PP-B, PP-R.
Embodiment: be illustrated below in conjunction with instantiation
Example 1
Take by weighing prescription raw material material:
Make the combination beta nucleater:
WBG is put into kneader with TBM4, and mixing is after 30 minutes down at 60 ℃, and interpolation 1Kg nano-calcium carbonate continuation mixing was taken out with special-purpose sealed bag and encapsulated in 30 minutes.
Even ecosystem distribution nano material:
Take by weighing 10KgPP-R raw material and remaining nano-calcium carbonate, dispersant and put into ultrahigh speed intensive mixer high speed stirring taking-up after 10 minutes.Material evenly mixes:
To make up beta nucleater, ecosystem distribution nano material, combination antioxidant, maleic anhydride inoculated polypropylene, remaining PP-R etc. and put into the mixing of homogenizer high speed together.
The melt blending polymerization granulation:
The prescription raw material that mixed are put into the polymerization of double screw extruder melt blending, and each section of extruder temperature is 178 ℃, 180 ℃, 210 ℃, 260 ℃; The raw material of extruding is through pelleter pelletizing, dehydration, homogenizing, metering, packing, warehouse-in.
Example 2 takes by weighing prescription raw material material:
Make the combination beta nucleater:
WBG is put into kneader with TBM4, and mixing is after 30 minutes down at 60 ℃, and interpolation 1Kg nano-aluminium oxide continuation mixing was taken out with special-purpose sealed bag and encapsulated in 30 minutes.
Homogenizing ecosystem distribution nano material:
Take by weighing 10KgPP-R raw material and remaining nano-aluminium oxide, dispersant and put into ultrahigh speed intensive mixer high speed stirring taking-up after 10 minutes.
Material evenly mixes:
To make up beta nucleater, ecosystem distribution nano material, combination antioxidant, maleic anhydride inoculated polypropylene, remaining PP-R etc. and put into the mixing of homogenizer high speed together.
The melt blending polymerization granulation:
The prescription raw material that mixed are put into the polymerization of double screw extruder melt blending, and each section of extruder temperature is 170 ℃, 180 ℃, 210 ℃, 220 ℃; The raw material of extruding is through pelleter pelletizing, dehydration, homogenizing, metering, packing, warehouse-in.
Example 3
Take by weighing prescription raw material material:
Make the combination beta nucleater:
WBG is put into kneader with TBM4, and mixing is after 30 minutes down at 60 ℃, and interpolation 1Kg nano-calcium carbonate continuation mixing was taken out with special-purpose sealed bag and encapsulated in 30 minutes.
Even ecosystem distribution nano material:
Take by weighing 10KgPP-R raw material and remaining nano-calcium carbonate and put into ultrahigh speed intensive mixer high speed stirring taking-up after 10 minutes.
Material evenly mixes:
To make up beta nucleater, ecosystem distribution nano material, combination antioxidant, maleic anhydride inoculated polypropylene, remaining PP-H etc. and put into the mixing of homogenizer high speed together.
The melt blending polymerization granulation:
The prescription raw material that mixed are put into the polymerization of double screw extruder melt blending, and each section of extruder temperature is 170 ℃, 180 ℃, 210 ℃, 230 ℃; The raw material of extruding is through pelleter pelletizing, dehydration, homogenizing, metering, packing, warehouse-in.
Claims (7)
1. brilliant COPP NF β PP-R (H, B) the material preparation method of nano combined β is characterized in that by β combination nucleator MODIFIED PP
Be transformed into beta crystal PP (β-PP) and improve the performance of β-PP with nano material, antioxidant, compatilizer, dispersant;
2. described according to claims 1, the beta nucleater that it is characterized in that indication is the wherein a kind of of terres rares, aromatic amine, enanthic acid and stearic compound, calcium salt etc., its consumption is 0.1%～3%;
3. described according to claims 1, the β combination nucleator that it is characterized in that indication are that calcium salt, terres rares, aromatic amine are re-dubbed efficiently " polynuclear complex " β combination nucleator, and each nucleator content is 0.05%～4%;
4. described according to claims 1, the nano material that it is characterized in that indication are wherein a kind of such as nano-calcium carbonate, nano aluminium oxide, and its consumption is 1%～6%;
5. described according to claims 1, the antioxidant that it is characterized in that indication is 1010,168 compound, its consumption is 0.6%～2%;
6. described according to claims 1, the compatilizer that it is characterized in that indication is a maleic anhydride inoculated polypropylene, its consumption is 1%～3%;
7. described according to claims 1, the dispersant that it is characterized in that indication is ethylene group bis-stearamides (E B S), its consumption is 0.6%～3%.
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| CN 201010125785 CN102217465A (en) | 2010-03-17 | 2010-03-17 | Preparation method for nano-composite beta-crystal co-polypropylene (NFbetaPP) material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102558683A (en) * | 2011-12-31 | 2012-07-11 | 广州呈和科技有限公司 | Polypropylene beta crystal form nucleating agent composition and application thereof |
| CN105860275A (en) * | 2016-03-31 | 2016-08-17 | 日丰科技有限公司 | Beta-PPR tube and preparation method thereof |
| CN114605743A (en) * | 2022-04-07 | 2022-06-10 | 涿州市隽诚化工有限公司 | Preparation method and application of nucleation auxiliary agent for anti-reflection polypropylene |
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| US4806770A (en) * | 1987-02-02 | 1989-02-21 | William M. Hylton | Germicidal toothbrush holder |
| CN1267682A (en) * | 2000-03-17 | 2000-09-27 | 中国石油天然气股份有限公司兰州石化分公司 | Composite nanometer-level polypropylene/montmorillonoid material and its preparation |
| CN101085846A (en) * | 2006-06-07 | 2007-12-12 | 林世平 | Preparation and production for beta-PP material |
| CN101608035A (en) * | 2008-06-17 | 2009-12-23 | 林世平 | The preparation of structure nano material six sides (β) crystal polypropylene NMPP-R (H) CT material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4806770A (en) * | 1987-02-02 | 1989-02-21 | William M. Hylton | Germicidal toothbrush holder |
| CN1267682A (en) * | 2000-03-17 | 2000-09-27 | 中国石油天然气股份有限公司兰州石化分公司 | Composite nanometer-level polypropylene/montmorillonoid material and its preparation |
| CN101085846A (en) * | 2006-06-07 | 2007-12-12 | 林世平 | Preparation and production for beta-PP material |
| CN101608035A (en) * | 2008-06-17 | 2009-12-23 | 林世平 | The preparation of structure nano material six sides (β) crystal polypropylene NMPP-R (H) CT material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558683A (en) * | 2011-12-31 | 2012-07-11 | 广州呈和科技有限公司 | Polypropylene beta crystal form nucleating agent composition and application thereof |
| CN102558683B (en) * | 2011-12-31 | 2014-01-22 | 广州呈和科技有限公司 | Polypropylene beta crystal form nucleating agent composition and application thereof |
| TWI461472B (en) * | 2011-12-31 | 2014-11-21 | Gch Technology Co Ltd | Β-nucleating agent composite for polypropylene and the use of the same |
| CN105860275A (en) * | 2016-03-31 | 2016-08-17 | 日丰科技有限公司 | Beta-PPR tube and preparation method thereof |
| CN105860275B (en) * | 2016-03-31 | 2018-11-06 | 日丰科技有限公司 | β-PPR pipe and preparation method thereof |
| CN114605743A (en) * | 2022-04-07 | 2022-06-10 | 涿州市隽诚化工有限公司 | Preparation method and application of nucleation auxiliary agent for anti-reflection polypropylene |
| CN114605743B (en) * | 2022-04-07 | 2023-11-28 | 涿州市隽诚化工有限公司 | Preparation method and application of nucleation auxiliary agent for anti-reflection polypropylene |
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Application publication date: 20111019 |