CN100478394C - Nano attapulgite clay composition for modified engineered plastic - Google Patents

Nano attapulgite clay composition for modified engineered plastic Download PDF

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Publication number
CN100478394C
CN100478394C CNB2006101186802A CN200610118680A CN100478394C CN 100478394 C CN100478394 C CN 100478394C CN B2006101186802 A CNB2006101186802 A CN B2006101186802A CN 200610118680 A CN200610118680 A CN 200610118680A CN 100478394 C CN100478394 C CN 100478394C
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China
Prior art keywords
attapulgite clay
nano attapulgite
clay composition
composition
nano
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CNB2006101186802A
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Chinese (zh)
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CN1962756A (en
Inventor
邵佳敏
王海洋
樊晓烨
唐颂超
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East China University of Science and Technology
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East China University of Science and Technology
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Priority to CNB2006101186802A priority Critical patent/CN100478394C/en
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Publication of CN100478394C publication Critical patent/CN100478394C/en
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Abstract

The invention discloses a nanometer concave-convex bar clay composition of fused modified engineering plastic, which is characterized by the following: allocating the composition with 50-60% nanometer concave-convex bar clay, 15-20% epoxy radical compound, 15-20% low-fusing point adjuvant and 8-20% carrier resin as raw material; fusing together at 130-180 Deg C; solidifying; grinding to obtain the product; possessing excellent dispersing property and compatibility with modified engineering plastic.

Description

The nano attapulgite clay composition that is used for modified engineered plastic
Technical field
The present invention relates to a kind of nano attapulgite clay composition, specifically, relate to a kind of nano attapulgite clay composition that is used for the melt modification engineering plastics.
Background technology
Nano attapulgite clay is to be refined by attapulgite clay (having another name called polygorskite or Palygorskite) to form, and its experience molecular formula is: (Mg, Al, Fe) 5Si 8O 20(HO) 2(OH 2) 44H 2O.
Nano attapulgite clay has that specific surface area is big, surfactivity is high and the surperficial characteristics such as polar hydroxyl that contain, and this is just indicating it when being used for modification organic polymer (particularly engineering plastics), should have the potential of structural strengthening and Chemical bond usefulness.Yet because nano attapulgite clay self and organic polymer (particularly nonpolar organic polymer) affinity are relatively poor, cause it in product of rubber and plastic, only to be taken as inert filler at present and use, bring into play its due effect far away.
CN 1664004 has reported the Attapulgite that will have the 1-dimention nano dimensional structure, and sepiolite directly is scattered in polyester monocase after treatment and carries out in-situ polymerization, to improve the nucleation performance of polyester, improves its processing characteristics and mechanical property; CN1687184 directly is scattered in the monomer of polyamide after having reported the nano material processing that will have one-dimentional structure, and is reactor with the screw extrusion press, and hybrid reaction is synthetic carries out simultaneously, becomes the high performance composite nylon resin of high molecular at last.And make the report that composition is used for melt modification organic polymer (particularly engineering plastics) and do not see as yet nano attapulgite clay is composite.
Summary of the invention
The objective of the invention is to, a kind of nano attapulgite clay composition that is used for melt modification organic polymer (particularly engineering plastics) is provided, give full play to the potential of nano attapulgite clay.
The present invention organises by the surface to nano attapulgite clay and handles and the surface of low molecular material coats, and reaches to improve its consistency in organic high polymers and the purpose of dispersiveness.In addition, finely disseminated nano attapulgite clay embodies the nano composite material effect with property by the principle of crystallization nucleation.
The said nano attapulgite clay composition that is used for melt modification organic polymer (particularly engineering plastics) of the present invention, it is characterized in that, said nano attapulgite clay composition, by mass percentage, mixing and solidify to pulverize and obtain 130 ℃～180 ℃ temperature by following raw materials according;
Nano attapulgite clay 50%～60%
Contain epoxy compounds 15%～20%
Low melting point auxiliary agent 15%～20%
Vector resin 8%～20%
Wherein: the said epoxy compounds that contains is the organic compound that bisphenol A epoxide resin, linear phenolic epoxy resin or end group contain epoxide group;
Said low melting point auxiliary agent is that fusing point is lower than 150 ℃ polyethylene wax or oxidized polyethlene wax;
Said vector resin is one or more in acid anhydride-grafted polyolefine, ethylene-vinyl acetate copolymer, polymeric amide, polyester or the acrylonitrile-butadiene-styrene copolymer (ABS).
Above-mentioned raw materials is commercially available product.
In optimized technical scheme of the present invention, the said epoxy compounds that contains is that average oxirane value (Ev) is 12～20 Resins, epoxy.
In another optimal technical scheme of the present invention, said vector resin is a melting index (MI) greater than 20 acid anhydride-grafted polyolefine, solution solvent viscosity ratio (η) less than 0.7 polyester or solution solvent viscosity ratio (η) less than 2.5 polymeric amide.
The said nano attapulgite clay composition of the present invention can be used for the melt modification of polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS) or nylon 6 engineering plastics such as (PA6), its key step is: with said nano attapulgite clay composition of the present invention and polymkeric substance (matrix resin) blend such as PE, PET, PP, ABS, PS or PA6, and to make the content of nano attapulgite clay composition in the blend be 2wt%～10wt%.The processing temperature that is warming up to matrix used resin carry out the melting mixing modification get final product the polymkeric substance of nano attapulgite clay modification.By as can be known to the polymer-modified SEM/TEM fractograph analysis of gained, nano attapulgite clay said polymer-modified in good dispersion.
The invention provides a kind of nano attapulgite clay composition that is used for engineering plastics such as melt modification PE, PET, PP, ABS, PS or PA6, said composition can make nano attapulgite clay be dispersed in well in the engineering plastics that are modified, and with the engineering plastics of modification good consistency is arranged, for the potential of giving full play to nano attapulgite clay is laid a good foundation.
Description of drawings
The Electronic Speculum figure of the nano attapulgite clay composition that Fig. 1 embodiment 1 makes.
Fig. 2 is pressed the Electronic Speculum figure of embodiment 6 method modified PET resulting polymers by nano attapulgite clay composition.
Embodiment
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention.
The used nano attapulgite clay of following examples is purchased in Changzhou monodimension nanometer material company limited; E-20 Resins, epoxy (by the name of GB GB/T1630-1989 Resins, epoxy nomenclature, down together) and E-12 Resins, epoxy are all purchased in Shanghai Resin Factory.
The preparation of nano attapulgite clay composition:
Embodiment 1
The raw material and the content of preparation nano attapulgite clay composition are as follows, and wherein content is in weight %:
Nano attapulgite clay 50%
E-20 Resins, epoxy 20%
Polyethylene wax (fusing point is lower than 150 ℃) 20%
Polypropylene grafted maleic anhydride 10%
With nano attapulgite clay, E-20 Resins, epoxy and fusing point be lower than 150 ℃ of polyethylene waxs with above-mentioned mixed evenly after, join surface temperature and be in two roller mills of 130 ℃～150 ℃, mixing 10～15 minutes, the piece flaky mixture that obtains is together added extruding pelletization in the twin screw extruder (processing temperature is 150 ℃～180 ℃) with polypropylene grafted maleic anhydride after fragmentation, obtain nano attapulgite clay composition.Its Electronic Speculum figure as shown in Figure 1.
Embodiment 2
The raw material and the content of preparation nano attapulgite clay composition are as follows, and wherein content is in weight %:
Nano attapulgite clay 55%
E-20 Resins, epoxy 15%
Oxidized polyethlene wax (fusing point is lower than 150 ℃) 15%
Ethylene-vinyl acetate copolymer grafted maleic anhydride 15%
With nano attapulgite clay, E-20 Resins, epoxy and fusing point be lower than 150 ℃ of oxidized polyethlene wax with above-mentioned mixed evenly after, join surface temperature and be in two roller mills of 130 ℃～150 ℃, mixing 10～15 minutes, the piece flaky mixture that obtains is together added extruding pelletization in the twin screw extruder (processing temperature is 140 ℃～160 ℃) with ethylene-vinyl acetate copolymer after fragmentation, obtain nano attapulgite clay composition.
Embodiment 3
The raw material and the content of preparation nano attapulgite clay composition are as follows, and wherein content is in weight %:
Nano attapulgite clay 50%
E-12 Resins, epoxy 30%
Oxidized polyethlene wax (fusing point is lower than 150 ℃) 10%
Polypropylene grafted maleic anhydride 10%
With nano attapulgite clay, E-12 Resins, epoxy and fusing point be lower than 150 ℃ of oxidized polyethlene wax with above-mentioned mixed evenly after, join surface temperature and be in two roller mills of 130 ℃～140 ℃, mixing 10～15 minutes, the piece flaky mixture that obtains is together added extruding pelletization in the twin screw extruder (processing temperature is 150 ℃～180 ℃) with polypropylene grafted maleic anhydride after fragmentation, obtain nano attapulgite clay composition.
Embodiment 4
The raw material and the content of preparation nano attapulgite clay composition are as follows, and wherein content is in weight %:
Nano attapulgite clay 55%
E-12 Resins, epoxy 25%
Polyethylene wax (fusing point is lower than 150 ℃) 10%
Polypropylene grafted maleic anhydride 10%
With nano attapulgite clay, E-12 Resins, epoxy and fusing point be lower than 150 ℃ of polyethylene waxs with above-mentioned mixed evenly after, join surface temperature and be in two roller mills of 130 ℃～140 ℃, powerful mixing 10～15 minutes, the piece flaky mixture that obtains is together added extruding pelletization in the twin screw extruder (processing temperature is 150 ℃～180 ℃) with polypropylene grafted maleic anhydride after fragmentation, obtain nano attapulgite clay composition.
Nano attapulgite clay composition is used for the melt modification of engineering plastics:
Embodiment 5～16
Will by the nano attapulgite clay composition of embodiment 1～4 preparation respectively with polyethylene terephthalate (PET), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS) and nylon 6 (PA6) polymkeric substance (matrix resin) blend, and the processing temperature that is warming up to matrix used resin is carried out the melting mixing modification and is got final product through the polymkeric substance of nano attapulgite clay modification.Carry out performance test to nano attapulgite clay is polymer-modified, the results are shown in Table 1.
In the table 1:
Composition concentration (wt%) is meant nano attapulgite clay composition concentration, and calculates acquisition by following formula:
Composition concentration=nano attapulgite clay composition weight/(nano attapulgite clay composition weight+matrix resin weight) x100%;
The composition that composition therefor makes for embodiment 1 among embodiment 6 and the embodiment 7;
The composition that composition therefor makes for embodiment 2 among embodiment 9 and the embodiment 10;
The composition that composition therefor makes for embodiment 3 among embodiment 12 and the embodiment 13;
The composition that composition therefor makes for embodiment 4 among embodiment 15 and the embodiment 16;
Embodiment 5, embodiment 11 and embodiment 14 are the blank example.

Claims (3)

1, a kind of nano attapulgite clay composition that is used for the melt modification engineering plastics is characterized in that, said nano attapulgite clay composition is by mass percentage, mixing and solidify to pulverize and obtain 130 ℃～180 ℃ temperature by following raw materials according;
Nano attapulgite clay 50%～60%
Contain epoxy compounds 15%～20%
Low melting point auxiliary agent 15%～20%
Vector resin 8%～20%
Wherein: the said epoxy compounds that contains is bisphenol A epoxide resin or linear phenolic epoxy resin;
Said low melting point auxiliary agent is that fusing point is lower than 150 ℃ polyethylene wax or oxidized polyethlene wax;
Said vector resin is that acid anhydride-grafted polyolefine, ethylene-vinyl acetate copolymer, polymeric amide, polyester are or/and acrylonitrile-butadiene-styrene copolymer.
As the said nano attapulgite clay composition of claim 1, it is characterized in that 2, wherein said vector resin is a melting index greater than 20 acid anhydride-grafted polyolefine, solution solvent viscosity ratio less than 0.7 polyester or solution solvent viscosity ratio less than 2.5 polymeric amide.
As the said nano attapulgite clay composition of claim 1, it is characterized in that 3, wherein said engineering plastics are: polyethylene terephthalate, polypropylene, acrylonitrile-butadiene-styrene copolymer or nylon 6.
CNB2006101186802A 2006-11-23 2006-11-23 Nano attapulgite clay composition for modified engineered plastic Expired - Fee Related CN100478394C (en)

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Application Number Priority Date Filing Date Title
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CN100478394C true CN100478394C (en) 2009-04-15

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760010B (en) * 2008-12-26 2013-09-18 上海普利特复合材料股份有限公司 Low odor and emission nylon 6 composition and preparation method thereof
CN102179357A (en) * 2011-02-28 2011-09-14 盱眙博图凹土高新技术开发有限公司 Method for preparing water-based attapulgite conductive coating
CN102382396B (en) * 2011-09-29 2013-07-17 芜湖海杉型材有限公司 Novel plastic pipe and preparation method thereof
CN103756265B (en) * 2013-12-20 2016-02-03 安徽国星生物化学有限公司 A kind of PET composite material containing attapulgite
CN104877294A (en) * 2015-06-09 2015-09-02 苏州圣谱拉新材料科技有限公司 Attapulgite-PEN-PET composite material and preparing method

Non-Patent Citations (8)

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Title
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环氧树脂/凹凸棒土复合材料的分散和力学性能研究. 康文韬等.中国塑料，第16卷第10期. 2002
环氧树脂/凹凸棒土复合材料的分散和力学性能研究. 康文韬等.中国塑料，第16卷第10期. 2002 *
聚丙烯/凹凸棒土纳米复合材料的制备、结构与性能. 王平华，徐国永.高分子材料科学与工程，第21卷第2期. 2005
聚丙烯/凹凸棒土纳米复合材料的制备、结构与性能. 王平华，徐国永.高分子材料科学与工程，第21卷第2期. 2005 *
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