CN101157776A - High-strength high-toughness polypropylene blending composite material and preparation method thereof - Google Patents
High-strength high-toughness polypropylene blending composite material and preparation method thereof Download PDFInfo
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- CN101157776A CN101157776A CNA2007100504910A CN200710050491A CN101157776A CN 101157776 A CN101157776 A CN 101157776A CN A2007100504910 A CNA2007100504910 A CN A2007100504910A CN 200710050491 A CN200710050491 A CN 200710050491A CN 101157776 A CN101157776 A CN 101157776A
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Abstract
The invention discloses a blending compound material with high strength and toughness and the preparation method thereof and is characterized in that: (1) the preparation of PP graft: 100 parts of PP are added into an internal mixer to be melted. After that, 0.1 to 1 part of dicumyl peroxide (DCP) as initiator, 3 to 8 parts of grafting monomer (BPA) or (2A) are in sequence added to conduct grafting modification. The PP graft can be obtained under the temperature of 170-200 DEG C, 30-60 rmp of rotational speed and 5 minutes of reaction. (2) The preparation of PP blending compound material: 100 parts of PP, 5 to 30 parts of PC, 5 to 50 parts of toughening elastomer, 1 to 30 parts of bulking agents and 0.1 to 0.5 part of antioxidant are added into a high blending machine to conduct primary blending. Then the primary blending materials are put into a twin screw extruder to be blended and to realize extrusion pelletization under 230 DEG C to 270 DEG C temperature of extruder charging barrel and 50 to 150 rmp of rotational speed. Thereafter, the material obtained after the extrusion pelletization is dried under the temperature of 80 DEG C to 100 DEG C for 2 hours to 4 hours; finally, the blending compound material with high strength and toughness is made.
Description
Technical field
The present invention relates to a kind of high-strength high-toughness polypropylene blending composite material and preparation method thereof, belong to polymer processing field.
Background technology
Polypropylene (PP) is one of five big general-purpose plastics, because the source is abundant, low price is easy to machine-shaping, the product high comprehensive performance, and purposes is very extensive, has become kind with fastest developing speed in the resins for universal use.But also there is some deficiency in its performance, and is low as notched Izod impact strength, fragile under low temperature disconnected, shrinking percentage is big, and creep resistance is poor, the product size poor stability, easily produce flexural deformation, shortcoming such as weathering resistance, fast light, heat-resisting and resistance to deterioration are relatively poor has greatly limited its engineering and has used.For this reason, PP is carried out the high performance modification, especially toughening modifying research has crucial meaning.
People have carried out extensive work PP have been carried out toughening modifying research.Usually adopt various thermoplastic elastic bodies and PP blend, form the blend of resistance to impact shock and excellent in low temperature toughness, all obtained widespread use as polypropylene/styrene-butadiene-styrene thermoplastic elastomer (PP/SBS), polypropylene/cis-1,4-polybutadiene rubber (PP/BR), polypropylene/emulsion polymerized styrene butadiene rubber (PP/SBR), polypropylene/ethylene propylene rubber (PP/EPR), polypropylene/terpolymer EP rubber (PP/EPDM), polypropylene/polyisobutylene rubber (PP/IBR) etc.But the mechanical strength of PP and rigidity have bigger reduction and loss.The extensive various mineral fillers of employing (lime carbonate, talcum powder, mica and wollastonite etc.) are at present filled, reinforcement, thereby improve dimensional stability, thermotolerance, the rigidity of material, reduce material cost simultaneously, but gained material scratch resistance trace are relatively poor.Adopt plastics such as ethylene-vinyl acetate copolymer (EVA), new LDPE (film grade) (LDPE), high density polyethylene(HDPE) (HDPE), polyamide (PA), polyethylene terephthalate (PET), polyphenylene oxide (PPO), acrylonitrile-butadiene-styrene copolymer (ABS) etc. as the toughness reinforcing properties-correcting agent of PP, can make system when toughness increases, reduce the inflexible loss, the physical propertiess such as wear resistance, dyeability of material are improved.But its toughening effect can not show a candle to rubber and thermoplastic elastomer, and because poor with the consistency of PP, make system reach high toughness often needs to strengthen the properties-correcting agent consumption or add compatilizer.
Chinese patent CN1640926A discloses a kind of preparation method of flexibilized polypropylene material, and selecting PP/EPDM for use is raw material, and 180-210 ℃ of blend, by gammairradiation, the notched Izod impact strength that makes material is 20-40KJ/m then
2, but undeclared tensile strength of material index.Tang Longxiang etc., J.Appl.Polym.Sci.2004,92 (5), described in molten state under the situation of photosensitizers double as linking agent, PP/EPDM (mass ratio 70/30) is exposed to makes photo-crosslinking PP/EPDM elastomerics under the UV-light, compare with uncrosslinked blend, degree of crosslinking is that its notched Izod impact strength of material of 30% is by 35KJ/m
2Bring up to 48KJ/m
2, but tensile strength only is 17Mpa, the material preparation process is complicated.Zhao Juan etc., plastics industry 2007,35 (6) adopts the expanding material of polypropylene grafted maleic anhydride (PP-g-MAH) as the PP/PA intermingling material, and its tensile strength of the material for preparing remains on higher level, but notched Izod impact strength is all less than 10KJ/m
2
Summary of the invention
The objective of the invention is provides a kind of high-strength high-toughness polypropylene blending composite material and preparation method thereof at the deficiencies in the prior art, is characterized in selecting for use polycarbonate (PC) and toughening elastic body coordination plasticizing to strengthen PP.Prepare the novel compatibilized dose of consistency of improving system, obtain the PP intermingling material of strong and unyielding balance, excellent combination property.
Purpose of the present invention is realized that by following technical measures wherein said raw material mark is parts by weight except that specified otherwise.
The starting raw material recipe ingredient of high-strength high-toughness polypropylene blending composite material is:
100 parts of polypropylene
5～30 parts of polycarbonate
5～50 parts of toughening elastic bodies
1～30 part of expanding material
0.1～0.5 part in oxidation inhibitor
Wherein, toughening elastic body is hydrogenated styrene-butadiene-styrene block copolymers (SEBS) or ethylene-octene polyolefin elastomer (POE).
Expanding material is styrene-ethylene-propylene-styrene segmented copolymer (SEPS), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), at least a in polypropylene grafted 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (PP-g-BPA) and the polypropylene grafted 2-allyl group dihydroxyphenyl propane (PP-g-2A).
Oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol esters, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester or N, any among the N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide).
The preparation method of high-strength high-toughness polypropylene blending composite material
1.PP the preparation of grafts
100 parts of PP are added in the Banbury mixeies after the fusion, add 0.1～1 part of initiator dicumyl peroxide (DCP), 3～8 parts of grafted monomer BPA or 2A successively and carry out graft modification; In temperature 170-200 ℃, 30～60 rev/mins of rotating speeds, reaction 5～10min obtains the PP grafts.
2.PP the preparation of blended compound material
Add in the high mixer 100 parts of PP, 5～30 parts of PC, 5～50 parts of toughening elastic bodies, 1～30 part of expanding material, 0.1～0.5 part of oxidation inhibitor just mixed, to just mix material then and put into the twin screw extruder blend, extruding pelletization, 230-270 ℃ of extruder barrel temperature, screw speed 50-150 rev/min, again with pellet in 80～100 ℃ of drying 2～4h of temperature, obtain high-strength high-toughness polypropylene blending composite material.
The high-strength high-toughness polypropylene blending composite material performance
As shown in Figure 1, under identical PC consumption, the shock strength of blend increases with the increase of SEBS consumption, is because the SEBS particle deforms as toughner or forms the cavity and absorbed a large amount of impact energys, has reduced the tensile strength of material inevitably.Under identical SEBS consumption, the shock strength of blend obviously increases with the increase of PC consumption.The adding of a small amount of PC reduces the tensile strength of blend to some extent, but when PC content surpassed 10wt%, with the increase of PC consumption, the tensile strength of blend obviously increased.The molecular structure of SEBS is given the effect of its increase-volume, and above-mentioned phenomenon is more obvious with the increase of SEBS consumption, and the consistency of system improves, and makes the obdurability of PC obtain performance, has obtained strong and unyielding equilibrated high-performance PP intermingling material.The shock strength and the tensile strength of PP/PC/SEBS (55/20/25) system reach 70KJ/m respectively
2And 21MPa, to compare with pure PP, its notched Izod impact strength has improved 35 times, and tensile strength can also remain on higher level.But the SEBS of too high consumption reunites easily in system and reduces the probability that the hole produces; When the PC too high levels, when reaching 30wt%, the system phase-splitting seriously causes the shock strength of blend to drop to a low value.
As shown in Figure 2, novel compatibilized dose advantage highly significant.Do not use under the situation of expanding material at 10 parts of POE content, the shock strength of PP co-mixing system is less than 4KJ/m
2, the adding of expanding material makes its shock strength obtain significant raising, even 20wt% expanding material shock strength reaches 20KJ/m
2, but very little to the influence of tensile strength, the explanation system can keep its rigidity well in toughness reinforcing.When higher POE consumption, increase the expanding material consumption, the shock strength of intermingling material has obtained more significantly improving, even 20wt% expanding material shock strength reaches 70KJ/m
2, to compare with pure PP, its notched Izod impact strength has improved 35 times, and tensile strength can also remain on higher level.
The present invention has following advantage
Traditional elastic body toughening PP, material is when toughness is improved, the mechanical strength of PP also declines to a great extent, can not use as structured material, the present invention is according to the notion of " rigid-rigid polymer toughening ", develop strong and unyielding equilibrated PP material, in toughness reinforcing its higher intensity and rigidity that keep simultaneously.
Firm and the tool toughness of polycarbonate (PC), shock strength is particularly outstanding, and heat-resisting winter hardiness, creep resistant, electrical insulating property and resistance to weathering are good.The present invention is PP and PC blend, by compound system interface capacity increasing technique, makes the PC obdurability be brought into play in the PP matrix and embody.SEBS, SEPS all belong to the SBS based block copolymer, and in molecular structure, the EB section can be dissolved each other with nonpolar PP, and the benzene ring structure of S section and PC is similar, are class ideal macromole expanding materials of PP/PC co-mixing system.The network structure that hard and strong S section is scattered among soft section of the elasticity EB has given SEBS the elasticity similar to traditional vulcanized rubber, can further improve toughening effect.SEPS and SEBS have obvious difference, do not play toughening effect in system, but the good expanding material of PP/PC system.Novel compatibilized dose of PP-g-BPA, PP-g-2A, its molecule have the similar molecular structure with PC, can interact by the intermolecular physics of intensive to improve the consistency of PP and PC; BPA also has remarkable stabilization, can be under anaerobic or anoxybiotic state the cancellation free radical, thereby reach the purpose that improves the heat-resisting processing stability of polymkeric substance.The notched Izod impact strength of the strong and unyielding balance intermingling material of PP of preparation can reach 70KJ/m
2More than, improve than the shock strength of pure PP and to reach 30-40 doubly, and tensile strength still can remain on about 21MPa.
Description of drawings
Fig. 1 be PP/PC/SEBS blend (a) tensile strength and (b) notched Izod impact strength with PC and SEBS content curve.
Fig. 2 is PP/PC/POE/ expanding material system tensile strength and the shock strength change curve with the compatilizer consumption.(a) 10 parts of POE; (b) 20 parts of POE
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
With PP 200g in Banbury mixer after the fusion, add dicumyl peroxide (DCP) 0.2g, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (BPA) 6g successively, 190 ℃ of temperature of reaction, rotating speed 60rpm is reaction 10min down, obtains expanding material PP-g-BPA.
With PP 10Kg, PC 500g, PP-g-BPA 100g, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 10g mixes, adopt the twin screw extruder melting mixing, the extruder barrel temperature is 230-270 ℃, screw speed is 50 rev/mins, extruding pelletization at 90 ℃ of dry 3h of temperature, has obtained high-strength high-toughness polypropylene blending composite material.
Embodiment 2
PP 200g after the fusion, is added dicumyl peroxide (DCP) 2g, 2-allyl group dihydroxyphenyl propane (2A) 16g successively in Banbury mixer, 170 ℃ of temperature of reaction, rotating speed 30rpm is reaction 5min down, obtains expanding material PP-g-2A.
[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol ester 30g mixes with PP 10Kg, PC 1.5Kg, SEBS 2Kg, PP-g-2A 300g, two, adopt the twin screw extruder melting mixing, the extruder barrel temperature is 230-270 ℃, screw speed is 100 rev/mins, extruding pelletization, at 80 ℃ of dry 4h of temperature, obtained high-strength high-toughness polypropylene blending composite material.
Embodiment 3
With PP 10Kg, PC 3Kg, SEBS 5Kg, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester 50g mixes, adopt the twin screw extruder melting mixing, the extruder barrel temperature is 230-270 ℃, and screw speed is 150 rev/mins, extruding pelletization, at 100 ℃ of dry 2h of temperature, obtained high-strength high-toughness polypropylene blending composite material.
Embodiment 4
With PP 10Kg, PC 1Kg, POE 500g, SEPS 200g, N, N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide) 40g mixes, adopt the twin screw extruder melting mixing, the extruder barrel temperature is 230-270 ℃, and screw speed is 70 rev/mins, extruding pelletization, at 90 ℃ of dry 3h of temperature, obtained high-strength high-toughness polypropylene blending composite material.
Claims (5)
1. high-strength high-toughness polypropylene blending composite material.The starting raw material that it is characterized in that this blended compound material is joined
Fang Zufen is by weight:
100 parts of polypropylene
5～30 parts of polycarbonate
5～50 parts of toughening elastic bodies
1～30 part of expanding material
0.1～0.5 part in oxidation inhibitor
2. high-strength high-toughness polypropylene blending composite material according to claim 1 is characterized in that toughening elastic body is hydrogenated styrene-butadiene-styrene block copolymers or ethylene-octene polyolefin elastomer.
3. high-strength high-toughness polypropylene blending composite material according to claim 1, it is characterized in that expanding material is styrene-ethylene-propylene-styrene segmented copolymer, hydrogenated styrene-butadiene-styrene block copolymers, at least a in polypropylene grafted 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate and the polypropylene grafted 2-allyl group dihydroxyphenyl propane.
4. high-strength high-toughness polypropylene blending composite material according to claim 1, it is characterized in that oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol esters, two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester or N, among the N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide) any.
5. as the preparation method of high-strength high-toughness polypropylene blending composite material as described in one of claim 1～4.It is characterized in that this method may further comprise the steps:
(1) preparation of PP grafts
After fusion in 100 parts of PP adding Banbury mixeies, add 0.1～1 part of initiator dicumyl peroxide, 3～8 parts of grafted monomer 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate or 2-allyl group dihydroxyphenyl propane successively and carry out graft modification; In 170～200 ℃ of temperature, 30～60 rev/mins of rotating speeds, reaction 5～10min obtains the PP grafts.
(2) preparation of PP blended compound material
Add in the high mixer 100 parts of PP, 5～30 parts of PC, 5～50 parts of toughening elastic bodies, 1～30 part of expanding material, 0.1～0.5 part of oxidation inhibitor just mixed, to just mix material then and put into the twin screw extruder blend, extruding pelletization, 230～270 ℃ of extruder barrel temperature, 50～150 rev/mins of screw speeds, again with pellet in 80～100 ℃ of drying 2～4h of temperature, obtain high-strength high-toughness polypropylene blending composite material.
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| CN105037778A (en) * | 2015-08-07 | 2015-11-11 | 东华大学 | Preparing method for environment-friendly composite material for sanitary product |
| CN105086154A (en) * | 2015-09-07 | 2015-11-25 | 太仓金昊达新材料有限公司 | Polyethylene composite plastic particles |
| CN107250269A (en) * | 2014-12-18 | 2017-10-13 | Sabic环球技术有限责任公司 | The composition of makrolon and propylene blends |
| CN110591216A (en) * | 2019-09-25 | 2019-12-20 | 中广核高新核材科技（苏州）有限公司 | Shielding material for conductive polypropylene power cable |
| CN111234378A (en) * | 2020-03-12 | 2020-06-05 | 美瑞新材料股份有限公司 | PP/TPU composite material with core-shell structure and preparation method thereof |
| CN111944307A (en) * | 2019-05-17 | 2020-11-17 | 朴哲范 | Nano elastomer fiber toughened polymer material |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568723A (en) * | 1984-11-08 | 1986-02-04 | Mobil Oil Company | Blends of polypropylene, polycarbonate and a saturated styrene-ethylene-butylene-styrene rubber |
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2007
- 2007-11-14 CN CN200710050491A patent/CN101157776B/en not_active Expired - Fee Related
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| CN107250269A (en) * | 2014-12-18 | 2017-10-13 | Sabic环球技术有限责任公司 | The composition of makrolon and propylene blends |
| CN105037778A (en) * | 2015-08-07 | 2015-11-11 | 东华大学 | Preparing method for environment-friendly composite material for sanitary product |
| CN105086154A (en) * | 2015-09-07 | 2015-11-25 | 太仓金昊达新材料有限公司 | Polyethylene composite plastic particles |
| CN111944307A (en) * | 2019-05-17 | 2020-11-17 | 朴哲范 | Nano elastomer fiber toughened polymer material |
| CN110591216A (en) * | 2019-09-25 | 2019-12-20 | 中广核高新核材科技（苏州）有限公司 | Shielding material for conductive polypropylene power cable |
| CN111234378A (en) * | 2020-03-12 | 2020-06-05 | 美瑞新材料股份有限公司 | PP/TPU composite material with core-shell structure and preparation method thereof |
| CN112920363A (en) * | 2021-01-12 | 2021-06-08 | 华南理工大学 | Thermoplastic polyurethane elastomer compatibilizer and preparation method and application thereof |
| CN115352156A (en) * | 2022-09-02 | 2022-11-18 | 上海紫华薄膜科技有限公司 | Low-gram-weight high-strength cast film and preparation method thereof |
| CN117417595A (en) * | 2023-09-13 | 2024-01-19 | 吉林盛大电缆有限公司 | Temperature-resistant cable and modified polypropylene cable protective sleeve material |
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Assignee: Guangxi Xinshen Science and Technology Co., Ltd. Assignor: Sichuan University Contract record no.: 2012450000003 Denomination of invention: High-strength high-toughness polypropylene blending composite material and preparation method thereof Granted publication date: 20100519 License type: Exclusive License Open date: 20080409 Record date: 20120309 |
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