CN1400240A - Preparation method of polyethylene material with high strength, high toughness and high density - Google Patents

Preparation method of polyethylene material with high strength, high toughness and high density Download PDF

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Publication number
CN1400240A
CN1400240A CN 01108690 CN01108690A CN1400240A CN 1400240 A CN1400240 A CN 1400240A CN 01108690 CN01108690 CN 01108690 CN 01108690 A CN01108690 A CN 01108690A CN 1400240 A CN1400240 A CN 1400240A
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China
Prior art keywords
hdpe
preparation
irradiation
polyethylene material
density polyethylene
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CN 01108690
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CN1160403C (en
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范萍
徐闻
刘鹏波
徐僖
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Sichuan University
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Sichuan University
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Publication of CN1160403C publication Critical patent/CN1160403C/en
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Abstract

The preparation method of high-strength, high-toughness and high-density polyethylene material is characterized by that under the action of ultrasonic wave the inorganic particles of juanying powder, white mica, calcium carbonate and titanium dioxide are better deagglomerated and dispersed, their surfaces can be better covered by bifunctional group reagents, such as gamma-aminopropyl triethoxysilicane, N-beta-(aminoethyl)-gamma-aminopropyl triethoxysilicane and N-beta-(aminomethyl)-gamma-aminopropylmethyl diethoxysilicane, so that they can obtained good dispersion and stronger interfacial interaction in irradiation HDPE base body, and the extension rate at break and notched impact strength of the comixed system can be obviously raised.

Description

A kind of preparation method of high strength, high toughness and high density polyethylene material
The present invention relates to a kind of polyolefine through engineering approaches new technology, belong to polymer processing field.
For HDPE/ mineral filler co-mixing system, dispersion and the interfacial interaction of mineral filler in matrix has very big influence to the mechanical property of system.The filler grain particle diameter is more little, and work in-process is easy more reunites, and is difficult to obtain in matrix good dispersion more.The patent ZL971075228 of the power of having patented such as China person Xu happy, be entitled as employing " irradiation technique prepares the method for high strength, high toughness and high density polyethylene material ", method by the irradiation increase-volume, though improved inorganic particulate dispersed in polyethylene and the interfacial interaction of system strengthened, reached and strengthened toughness reinforcing effect, but for some ultrafine particles, the reunion situation of particle in matrix still exists.
The objective of the invention is to provide a kind of preparation method of high strength, high toughness and high density polyethylene material at the deficiencies in the prior art, be characterized in adopting ultrasonic wave that inorganic particulate is carried out pre-treatment, utilize hyperacoustic dispersion and cleanup action to make interface modifier in the single particle coated with uniform, reduce the surface energy of particle filled composite, promote the dispersion of inorganic particulate in resin matrix, strengthen interfacial interaction, thereby increase substantially the mechanical property of co-mixing system.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the supersound process of inorganic particulate
Add 20~50 parts of inorganic particulates in 100 parts of water and/or ethanol medium, particle diameter is 1~10 micron, and adds 0.2~2.5 part of interface modifier, is made into slimy suspension, with 5~10 minutes after-filtration and dry of 20kHz ultrasonication,
2. the gamma-radiation irradiation HDPE (preparation method of γ-HDPE) and electron beam irradiation HDPE (e-HDPE)
Adopt 60Co gamma-radiation source or electron electrostatic accelerator at room temperature carry out irradiation to HDPE in the air, and irradiation dose is 10~60kGy, and on its molecular chain, introduce C=O etc. and contain the oxygen polar group,
3. the preparation method of high strength, high toughness and high density polyethylene material
The inorganic particulate of irradiation HDPE90~50 part and 10~50 parts of supersound process is adopted two roller mills under 140-170 ℃ of temperature mixing 8~15 minutes.
Inorganic particulate is that sericite-tridymite-cristobalite, white mica, lime carbonate and/or titanium dioxide are at least a.
Interface modifier is that MALEIC ANHYDRIDE, ω-hexanolactam, γ-An Bingjisanyiyangjiguiwan, N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ aminopropyl methyl dimethoxysilane, γ-(many ethylenes amino) propyl trimethoxy silicane and/or γ-(2, the 3-glycidoxy) propyl trimethoxy silicane is at least a.
Experimental result shows, the powerful divergent function of ultrasonic wave can agglomerated inorganic particulate obtain good reunion, dispersion and the Surface Renewal of separating, its surface can effectively be coated by interface modifier, thereby in irradiation HDPE matrix, obtain good dispersion, make co-mixing system elongation at break and notched Izod impact strength all be significantly improved, see for details shown in the table one.
The present invention has following advantage:
Technology is simple, cleaning, pollution-free, and the intermingling material that makes has excellent mechanical property, and cost is lower, is expected to be applied at aspects such as pipeline, material of construction and automobile component.
Embodiment:
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples can only be 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 according to the content of the invention described above.
1. in 100 gram water mediums, add 20 gram median sizes and be 1.6 microns sericite-tridymite-cristobalite and 0.6 gram γ-An Bingjisanyiyangjiguiwan, be made into slimy suspension, adopt the 20kHz ultra-sonic generator to handle after 7 minutes sericite-tridymite-cristobalite filtered and dry.It is mixing to adopt two roller mills to carry out supersound process sericite-tridymite-cristobalite 40 grams and γ-HDPE (irradiation dose is 10kGy) 60 grams, 150 ℃ of melting temperatures, mixing time 15 minutes.
2. in 80 gram water, 20 gram ethanol mediums, add 30 gram median sizes and be titanium dioxide and 1.5 gram N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwans of 2 microns, be made into slimy suspension, adopt the 20kHz ultra-sonic generator to handle after 5 minutes titanium dioxide filter and dry.It is mixing to adopt two roller mills to carry out supersound process titanium dioxide 30 grams and e-HDPE (50kGy) 70 grams, 160 ℃ of melting temperatures, mixing time 12 minutes.
3. in 90 gram water, 10 gram ethanol mediums, add 40 gram median sizes and be 2 microns white mica and 1.6 gram γ-An Bingjisanyiyangjiguiwans, be made into slimy suspension, adopt the 20kHz ultra-sonic generator to handle after 8 minutes white mica filtered and dry.It is mixing to adopt two roller mills to carry out supersound process white mica 40 grams and γ-HDPE (30kGy) 60 grams, 155 ℃ of melting temperatures, mixing time 10 minutes.
4. in 70 gram water, 30 gram ethanol mediums, add 25 gram median sizes and be lime carbonate and 0.8 gram γ-(many ethylenes amino) propyl trimethoxy silicane of 1 micron, be made into slimy suspension, adopt the 20kHz ultra-sonic generator to handle after 10 minutes lime carbonate is filtered and drying.It is mixing to adopt two roller mills to carry out supersound process lime carbonate 30 grams and e-HDPE (40kGy) 70 grams, 165 ℃ of melting temperatures, mixing time 15 minutes.
The mechanical property of the inorganic particle blended system of table 1 irradiation HDPE/ supersound process
Tensile strength notched Izod impact strength elongation at break sample inorganic particulate
(MPa) (J/m) (%) irradiation HDPE-1 29.3 543 384 sericite-tridymite-cristobalites, 30% irradiation/ultrasonic HDPE-1 29.1 665 552 sericite-tridymite-cristobalites, 30% irradiation HDPE-2,27.4 581 128 sericite-tridymite-cristobalites, 40% irradiation/ultrasonic HDPE-2 29.4 745 340 sericite-tridymite-cristobalites, 40% irradiation HDPE-3,30.4 575 49 sericite-tridymite-cristobalites, 50% irradiation/ultrasonic HDPE-3 30.3 695 130 sericite-tridymite-cristobalites, 50% irradiation HDPE-4,28.9 184 49 white micas, 30% irradiation/ultrasonic HDPE-4 29.1 468 328 white micas, 30%

Claims (3)

1. the preparation method of a high strength, high toughness and high density polyethylene material is characterized in that:
A. the supersound process of inorganic particulate
Add 20~50 parts of inorganic particulates in 100 parts of water and/or ethanol medium, median size is 1~10 micron, and adds 0.2~2.5 part of interface modifier, is made into slimy suspension, with 5~10 minutes after-filtration and dry of 20kHz ultrasonication,
B. the gamma-radiation irradiation HDPE (preparation method of γ-HDPE) and electron beam irradiation HDPE (e-HDPE)
Adopt 60Co gamma-radiation source or electron electrostatic accelerator at room temperature carry out irradiation to HDPE in the air, and irradiation dose is 10~60kGy, and on its molecular chain, introduce C=O etc. and contain the oxygen polar group,
C. the preparation method of high strength, high toughness and high density polyethylene material
The inorganic particulate of irradiation HDPE90~50 part and 10~50 parts of supersound process is adopted two roller mills under 140-170 ℃ of temperature mixing 8~15 minutes.
2. according to the preparation method of the described a kind of high strength, high toughness and high density polyethylene material of claim 1, it is characterized in that inorganic particulate is that sericite-tridymite-cristobalite, white mica, lime carbonate and/or titanium dioxide are at least a.
3. according to the preparation method of the described a kind of high strength, high toughness and high density polyethylene material of claim 1, it is characterized in that interface modifier is that MALEIC ANHYDRIDE, ω-hexanolactam, γ-An Bingjisanyiyangjiguiwan, N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ aminopropyl methyl dimethoxysilane, γ-(many ethylenes amino) propyl trimethoxy silicane and/or γ-(2, the 3-glycidoxy) propyl trimethoxy silicane is at least a.
CNB011086904A 2001-07-31 2001-07-31 Preparation method of polyethylene material with high strength, high toughness and high density Expired - Fee Related CN1160403C (en)

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CNB011086904A CN1160403C (en) 2001-07-31 2001-07-31 Preparation method of polyethylene material with high strength, high toughness and high density

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325550C (en) * 2005-04-13 2007-07-11 四川大学 Heat conducting composite material of polyethylene in high density, rpeparation method and application thereof
CN101263257B (en) * 2005-09-15 2013-03-27 阿力泽有限公司 Method for attachment of silicon-containing compounds to a surface and for the synthesis of hypervalent silicon compounds
CN105925029A (en) * 2016-06-07 2016-09-07 平顶山市美伊金属制品有限公司 Non-stick pan spray coating containing absorbable iron element
CN105925043A (en) * 2016-06-07 2016-09-07 平顶山市美伊金属制品有限公司 Non-stick pan spray coating containing absorbable zinc element
CN106065212A (en) * 2016-06-07 2016-11-02 平顶山市美伊金属制品有限公司 A kind of non-stick pan spray paint containing acceptable calcium element

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325550C (en) * 2005-04-13 2007-07-11 四川大学 Heat conducting composite material of polyethylene in high density, rpeparation method and application thereof
CN101263257B (en) * 2005-09-15 2013-03-27 阿力泽有限公司 Method for attachment of silicon-containing compounds to a surface and for the synthesis of hypervalent silicon compounds
CN105925029A (en) * 2016-06-07 2016-09-07 平顶山市美伊金属制品有限公司 Non-stick pan spray coating containing absorbable iron element
CN105925043A (en) * 2016-06-07 2016-09-07 平顶山市美伊金属制品有限公司 Non-stick pan spray coating containing absorbable zinc element
CN106065212A (en) * 2016-06-07 2016-11-02 平顶山市美伊金属制品有限公司 A kind of non-stick pan spray paint containing acceptable calcium element

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