CN1094496C - Process for preparing nm particles reinforced and toughened polyethylene composition - Google Patents
Process for preparing nm particles reinforced and toughened polyethylene composition Download PDFInfo
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- CN1094496C CN1094496C CN99115068A CN99115068A CN1094496C CN 1094496 C CN1094496 C CN 1094496C CN 99115068 A CN99115068 A CN 99115068A CN 99115068 A CN99115068 A CN 99115068A CN 1094496 C CN1094496 C CN 1094496C
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Abstract
The present invention relates to a preparation method for an nm particle reinforced and toughened polyethylene composite material. The preparation method is characterized in that nm particles, a solvent and a surface dispersing agent are added to an oscillation type stirrer or a stirrer with an ultrasonic oscillator and are ground by a ball mill in the presence of a small quantity of solvent to make the dispersing agent and the nm particles homogeneously dispersed. The preparation method aims to make surface dispersing treatment carried out on the nm particles, the nm particles bearing the surface treatment are dried and then are mixed with polyethylene in a mill or a double-screw extruder, and the mixture is prepared into a parent material; the parent material and the polyethylene are extruded by the double-screw extruder for granulation to be prepared into the reinforced and toughened polyethylene composite material.
Description
The present invention relates to a kind of preparation method of nm particles reinforced and toughened polyethylene composition, belong to the polymer composite preparation field.
Polyethylene is a kind of purposes general-purpose plastics extremely widely, but because modulus is low, the notched Izod impact strength sensitivity has limited the application of polyethylene as structured material.Adopt rubber, the toughness reinforcing composite polyethylene material of micron order rigid particles, its toughness is increased substantially, but weak point is: rigidity, the modulus of rubber toughened composite polyethylene material descend significantly (Wu Peixi, Zhang Liucheng, polymer blending modification, the Chinese light industry society 1996 of setting out; QiZongNeng, Zhu Xiaoguang, investigation of materials journal 1997,6:623), the modulus of micron rigid particles toughening composition increases, tensile strength descend significantly (Fu Qiang, Shen Jiusi, Wang Guiheng, high score Materials Science and Engineering 1992,1:107), these two kinds of technological lines all can not make the mechanical property of the composite polyethylene material of preparation improve comprehensively and improve at present.
The objective of the invention is to provide a kind of preparation method of nm particles reinforced and toughened polyethylene composition at the deficiencies in the prior art, be characterized in nanoparticle, solvent and surface dispersant add and have ultra-sonic oscillation producer or vibration whipping appts and utilize ball mill grinding in the presence of a small amount of solvent, make dispersion agent and nanoparticle homodisperse, purpose is that nanoparticle is carried out surperficial dispersion treatment, then surface treated nanoparticle is carried out drying back and polyethylene mixing preparation masterbatch on mill or twin screw extruder, compound preparation strengthens toughness reinforcing composite polyethylene material in twin screw extruder again.The comprehensive mechanical property of this composite polyethylene material is good, and shock strength improves about 1 times, and tensile strength and modulus all have raising in various degree.
Purpose of the present invention goes out following technical measures realization, and wherein, described raw material portion rate is ratio of weight and number except that specified otherwise.
The preparation method of nm particles reinforced and toughened polyethylene composition
1. nanoparticle surface dispersion treatment
With nanoparticle, solvent and surface dispersant, be 1.0: 0.1～2.0 by the ratio of nanoparticle and solvent; Nanoparticle is 1: 0.01～0.05 with the ratio of surface dispersant, adds to have ultra-sonic oscillation producer or vibration whipping appts and utilize ball mill grinding in the presence of a small amount of solvent, makes dispersion agent and nanoparticle homodisperse.
2. the compound preparation masterbatch of nanoparticle and polyethylene
Nanoparticle after surperficial dispersion treatment again with dried nanoparticle and polyethylene, adds in mills or twin screw extruder mixing preparation masterbatch by 0.8～3.0: 1.0 in 60～80 ℃ of dryings of temperature 40～70 hours.
3. the compound preparation composite polyethylene material of masterbatch and polyethylene
With the masterbatch and the polyethylene of mixing preparation, by mixing in 0.06～0.10: the 1.00 adding twin screw extruders, temperature is 130～210 ℃, rotating speed 60～150r/min, and extruding pelletization makes nm particles reinforced and toughened polyethylene composition.
Nanoparticle is a lime carbonate, and the mixture of silicon-dioxide and/or silicon nitride and silicon carbide is at least a, and median size is 50～80nm.
Solvent is that Virahol, acetone, toluene, dimethylbenzene or whiteruss are at least a.
Surface dispersant is a titanic acid ester, aluminic acid ester, acrylate, phosphoric acid ester and/or alkyl hydrochlorate.
Nano particle reinforced tenacity increased composite polyethylene material, has good chemical property, the purer polyethylene of shock strength has improved 1 times, tensile strength and modulus all have raising in various degree, as when using high density polyethylene(HDPE), its yield strength 28～30MPa, elongation at break 300～400%, shock strength 58～65KJ/m
2
The present invention has following advantage:
1. the preparation method is simple, and equipment loss is little, is easy to suitability for industrialized production.
2. the nanoparticle consumption is few, is applicable to the goods that performance requriements is high, as Turnover Box, and bucket etc., because the raising of plastics performance, corresponding quantity of plastics reduces, i.e. the suitable attenuate of the wall thickness of plastics, thus reduced cost.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are 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 invention described above content.
1. with nano-calcium carbonate 50 grams, Virahol 100 grams and titanic acid ester 1 gram add and have in the reaction vessel of ultrasonic oscillator, handled 0.5 hour for 25 ℃ in temperature, nano-calcium carbonate after the processing placed the baking oven of 60 ℃ of temperature dry 48 hours, dried nano-calcium carbonate and high density polyethylene(HDPE) add in the mill mixing by 0.8: 1 ratio, 155 ℃ of temperature, 10 minutes time, make masterbatch, again masterbatch and high density polyethylene(HDPE) are made nano-calcium carbonate enhancing toughened polyethylene composition by extruding pelletization in 1: 9.5 the ratio adding twin screw extruder.
2. with nano silicon 50 grams, dimethylbenzene 100 grams and aluminic acid ester 1 gram add and have in the reaction vessel of the whipping appts that vibrates, handled 1 hour for 20 ℃ in temperature, nano silicon after the processing placed the baking oven of 70 ℃ of temperature dry 48 hours, dried nano silicon and new LDPE (film grade) add in the mill mixing by 1: 1 ratio, 150 ℃ of temperature, time 10min, make masterbatch, again masterbatch and new LDPE (film grade) are made nano silicon enhancing toughened polyethylene composition by extruding pelletization in 1: 9 the ratio adding twin screw extruder.
3. the mixture 50 with nano-silicon nitride and silicon carbide restrains, acetone 100 grams and acrylate 1.5 grams add and have in the reaction vessel of ultrasonic oscillator, handled 1.5 hours for 20 ℃ in temperature, nano-silicon nitride after the processing and carborundum particle placed the baking oven of 70 ℃ of temperature dry 48 hours, dried nanoparticle and LLDPE added in the mill mixing by 2: 1,150 ℃ of temperature, time 15min, make masterbatch, masterbatch and linear polyethylene are made nm particles reinforced and toughened polyethylene composition by extruding pelletization in 0.65: 9.35 the ratio adding twin screw extruder.
4. with nano-calcium carbonate 1000 grams, whiteruss 15 grams and titanic acid ester 15 grams add in the ball mill in 60～100 ℃ of grindings of temperature 6 hours, nano-calcium carbonate after the processing and high density polyethylene(HDPE) added to extrude in twin screw extruder or the single screw extrusion machine by 1: 1 and make masterbatch, again masterbatch were added the interior extruding pelletization of twin screw extruder with high density polyethylene(HDPE) by 1: 9 and made nano-calcium carbonate enhancing toughened polyethylene composition.
Claims (4)
1, the preparation method of nm particles reinforced and toughened polyethylene composition is characterized in that:
(1) nanoparticle surface dispersion treatment
With nanoparticle, solvent and surface dispersant, weight ratio by nanoparticle and solvent is 1.0: 0.1～2.0, the weight ratio of nanoparticle and surface dispersant is 1: 0.01～0.05, adding has ultra-sonic oscillation producer or vibration whipping appts and utilize ball mill grinding in the presence of a small amount of solvent, makes dispersion agent and nanoparticle homodisperse;
(2) the compound preparation masterbatch of nanoparticle and polyethylene
Nanoparticle after surperficial dispersion treatment, in 60～80 ℃ of dryings of temperature 40～70 hours, again with dried nanoparticle and polyethylene, be added in the mill by weight 0.8～3.0: 1.0, in 150 ℃ of temperature, in 10～15 minutes time or the twin screw extruder, in 130～210 ℃ of mixing preparation masterbatch of temperature;
(3) the compound preparation composite polyethylene material of masterbatch and polyethylene
With the masterbatch and the polyethylene of above-mentioned preparation, interior mixing by weight 0.06～0.10: 1.00 adding twin screw extruders, temperature is 130～210 ℃, rotating speed 60～150r.p.m, and extruding pelletization makes nm particles reinforced and toughened polyethylene composition.
2,, it is characterized in that nanoparticle is a lime carbonate, at least a in silicon-dioxide and/or silicon nitride and the silicon carbide mixture according to the preparation method of the described nm particles reinforced and toughened polyethylene composition of claim 1.
3,, it is characterized in that solvent is at least a in Virahol, acetone, toluene, dimethylbenzene and/or the whiteruss according to the preparation method of the described nm particles reinforced and toughened polyethylene composition of claim 1.
4,, it is characterized in that surface dispersant is at least a in titanic acid ester, aluminic acid ester, acrylate, phosphoric acid ester and/or the alkyl hydrochlorate according to the preparation method of the described nm particles reinforced and toughened polyethylene composition of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115068A CN1094496C (en) | 1999-08-10 | 1999-08-10 | Process for preparing nm particles reinforced and toughened polyethylene composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN99115068A CN1094496C (en) | 1999-08-10 | 1999-08-10 | Process for preparing nm particles reinforced and toughened polyethylene composition |
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| CN1283650A CN1283650A (en) | 2001-02-14 |
| CN1094496C true CN1094496C (en) | 2002-11-20 |
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| CN99115068A Expired - Fee Related CN1094496C (en) | 1999-08-10 | 1999-08-10 | Process for preparing nm particles reinforced and toughened polyethylene composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390335C (en) * | 2005-03-10 | 2008-05-28 | 中国科学院化学研究所 | Polymer compounding fiber composed by surface-modified, inorganic filler and polymer |
| CN100410312C (en) * | 2003-05-28 | 2008-08-13 | 新疆天业节水灌溉股份有限公司 | Nanometer material modified water delivering flexible pipe |
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| CN103524860B (en) * | 2012-07-05 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of ultrasonication graphite-made is for heat conduction polyethylene master batch method and composition thereof |
| CN103132171B (en) * | 2013-03-19 | 2014-08-27 | 中国水产科学研究院东海水产研究所 | Method for manufacturing polyethylene fiber for fishing |
| CN104194146B (en) * | 2014-08-06 | 2016-09-28 | 惠州市沃特新材料有限公司 | Polypropene composition and preparation method thereof |
| CN108892849A (en) * | 2018-07-18 | 2018-11-27 | 广西南宁荣威德新能源科技有限公司 | A kind of high density polyethylene (HDPE) bilayer feed pipe and preparation method thereof |
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|---|---|---|---|---|
| JPS63113052A (en) * | 1986-10-31 | 1988-05-18 | Kao Corp | Antistatic master pellet composition |
| CN87102663A (en) * | 1987-04-07 | 1988-11-02 | 徐升秀 | Plastic filler parent granule |
| JPH0820766A (en) * | 1994-07-07 | 1996-01-23 | Kao Corp | Granular antistatic agent mixture and method for using the same |
| CN1147033A (en) * | 1996-08-16 | 1997-04-09 | 刘明然 | Ultraviolet screening mother granule and fiber |
| CN1216515A (en) * | 1996-02-21 | 1999-05-12 | 花王株式会社 | Ultraviolet-screening composite particulate and process for the production thereof |
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1999
- 1999-08-10 CN CN99115068A patent/CN1094496C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63113052A (en) * | 1986-10-31 | 1988-05-18 | Kao Corp | Antistatic master pellet composition |
| CN87102663A (en) * | 1987-04-07 | 1988-11-02 | 徐升秀 | Plastic filler parent granule |
| JPH0820766A (en) * | 1994-07-07 | 1996-01-23 | Kao Corp | Granular antistatic agent mixture and method for using the same |
| CN1216515A (en) * | 1996-02-21 | 1999-05-12 | 花王株式会社 | Ultraviolet-screening composite particulate and process for the production thereof |
| CN1147033A (en) * | 1996-08-16 | 1997-04-09 | 刘明然 | Ultraviolet screening mother granule and fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410312C (en) * | 2003-05-28 | 2008-08-13 | 新疆天业节水灌溉股份有限公司 | Nanometer material modified water delivering flexible pipe |
| CN100390335C (en) * | 2005-03-10 | 2008-05-28 | 中国科学院化学研究所 | Polymer compounding fiber composed by surface-modified, inorganic filler and polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1283650A (en) | 2001-02-14 |
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