CN1869123A - Polyurethanel clay nanometer composite material and its preparation method - Google Patents
Polyurethanel clay nanometer composite material and its preparation method Download PDFInfo
- Publication number
- CN1869123A CN1869123A CN 200510011817 CN200510011817A CN1869123A CN 1869123 A CN1869123 A CN 1869123A CN 200510011817 CN200510011817 CN 200510011817 CN 200510011817 A CN200510011817 A CN 200510011817A CN 1869123 A CN1869123 A CN 1869123A
- Authority
- CN
- China
- Prior art keywords
- polymeric amide
- parts
- weight
- clay
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
A nano-class polyamide-clay composition with anisotropy is prepared from polyamide (100 Wt portions) and the chain-laminar magnesium silicate clay (0.5-20) through dual-screw extruding out. It has high mechanical performance and refractory nature.
Description
Technical field
The present invention relates to a kind of polyamide nano-composite, be specifically related to a kind of anisotropic nanoparticle and be dispersed in the polymeric amide/clay nano composite material in the polyamide substrate and the preparation method of polymeric amide/clay nano composite material.
Background technology
Polymeric amide claims nylon again, mainly comprises polyamide 6 and polyamide 66 etc., is a kind of widely used engineering plastics, is widely used in aspects such as automobile component, electrical part, fiber and packaging film.But because the existence of acid amides polar group, also there are shortcomings such as water-intake rate height, heat-drawn wire are low in polymeric amide, has limited its Application Areas.Early stage method of modifying is to adopt the Inorganic Fillers Filled polymeric amide, improve its intensity, rigidity and dimensional stability, as use filling polymeric amide such as glass fibre, lime carbonate, talcum or mica can improve intensity, modulus and the thermotolerance of material, but, make the density of matrix material increase because addition is big.Another approach that improves performance is to adopt superfine Inorganic Fillers Filled polyamide substrate, but when packing material size reaches nano level, the surface energy that particle is bigger makes that interparticle self aggregation effect is very big, use traditional blend method, be difficult to make the homodisperse on the filler acquisition nanometer level, and only belong to the microcosmic matrix material, influenced the improvement of reinforcing effect and resistance toheat.
A kind of novel method of Chu Xianing is to use layered silicate to prepare polymer nanocomposites in recent years, what wherein widely use is a kind of natural sheet silicate minerals---montmorillonite clay, its structural unit is that thickness is about 1 nanometer, and length and width are tens of silicate lamellas to hundreds of nanometers.Chinese patent publication number CN 1206028 for example, CN 1288023, and CN 1396211, and world patent WO 9304117 and U.S. Pat 5385776 have reported that all the method for utilizing melt blending prepares the method for polymeric amide/montmorillonite nano-composite material.But these preparations all require to layered silicate the mineral filler processing that organises, complex process.
Sepiolite-polygorskite type clay is the aqueous chain layered magnesium of a class silicate minerals, has 2: 1 type structures.Different with the montmorillonite that 2: 1 type structures are equally also arranged is, the top, angle of the tetrahedral sheet of montmorillonite all facing one direction, thereby form simple laminate structure, and in sepiolite-polygorskite type clay, do 180 ° of upsets along top, the angle in the Y direction tetrahedron every certain cycle, thereby formed chain and the passage that is parallel to X-axis.The desirable chemical formula of sepiolite and polygorskite is respectively: [Mg
8(Si
12O
30) (OH)
4(OH
2)
4] 8H
2O and [Mg
5(Si
8O
20) (OH)
4(OH
2)
4] 4H
2O, Mg element wherein can partly be substituted (referring to " clay mineral material and environment remediation ", Wu Pingxiao writes, Chemical Industry Press, 2004 years) by elements such as Al.The microlitic structure of natural sepiolite-polygorskite type clay mineral is fibrous, bar-shaped or needle-like, and diameter is between 10 to 100nm, and length can reach several microns to tens microns.Sepiolite can occur with two kinds of forms, comprises fibrous sepiolite and clay shape sepiolite.
The resource of China's sepiolite and polygorskite is all abundanter, and use is also very extensive.The composite fire retardant fire-proof lining paper made from sepiolite is disclosed as Chinese patent publication number CN 1352337, CN 1354076 discloses the manufacture method of the composite silicate hard heat-insulating plate that contains sepiolite, and CN 1255510 and CN1334289 then disclose with the polyolefine of situ aggregation method preparation and the nano composite material of sepiolite-polygorskite type clay.And Chinese patent publication number CN 1511865 discloses a kind of nano fiber reinforcing agent with sepiolite-polygorskite type clay preparation, be used to prepare polymer nanocomposites, but need to use multiple organic components such as surface active properties-correcting agent and surperficial separant, therefore complex process, shortcoming that processing cost is high are also arranged.
Summary of the invention
One of purpose of the present invention is to provide a kind of polymeric amide/clay nano composite material, and this matrix material has excellent mechanical property and resistance toheat, and particularly rigidity is higher.
Two of purpose of the present invention is to provide a kind of preparation method of polymeric amide/clay nano composite material, and the clay that is adopted needn't be through organising processing.
Contain the polymeric amide of 100 parts by weight and the chain layered magnesium silicate minerals clay of 0.5～20 parts by weight in polymeric amide/clay nano composite material of the present invention.
Polymeric amide used in the present invention is polyamide 6 or polyamide 66.
Chain layered magnesium silicate minerals clay used in the present invention is sepiolite or polygorskite.
Sepiolite used in the present invention can be fibrous sepiolite or clay shape sepiolite.
In polymeric amide/clay nano composite material of the present invention, can also contain antioxidant and/or lubricant.
The add-on of antioxidant is 0.05～2 parts by weight of relative 100 parts by weight polymeric amide; The add-on of lubricant is 0.1～2 parts by weight of relative 100 parts by weight polymeric amide.
Employed antioxidant is the antioxidant at polymeric amide in polymeric amide/clay nano composite material of the present invention, and purpose is in order to be reduced in the oxidative degradation of polymeric amide in the preparation composite material.Used antioxidant comprises four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (commercial disignation antioxidant 1010); (3; 5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester (commercial disignation 1076) or N; N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine (commercial disignation oxidation inhibitor 1098) etc.
Employed lubricant is the lubricant at polymeric amide in polymeric amide/clay nano composite material of the present invention, and its effect is to improve the surface property of polymeric amide and melt the body viscosity, reduce and the friction of processing units and improve release property in the post-treatment process.Used lubricant comprises whiteruss or ethylene bis stearamide (EBS) etc.
The preparation method of polymeric amide/clay nano composite material of the present invention, more easier than the method for reporting in the past for preparing polymeric amide/clay nano composite material, this method is:
With the polymeric amide of 100 parts by weight, after the chain layered magnesium silicate minerals clay of 0.5～20 parts by weight thorough mixing in high-speed mixer is even, melt extrude granulation with twin screw extruder, can make polymeric amide/clay nano composite material.Twin screw rotating speed, screw configuration and barrel zone temperature are suitable with the conventional composite polyamide of filling, and wherein the barrel zone temperature scope is 210 ℃～250 ℃ for polyamide 6, is 260 ℃～300 ℃ for polyamide 66.This method does not need the clay processing that organises, and weak point consuming time is simple to operate, thereby cost of manufacture is lower.
With polymeric amide and chain layered magnesium silicate minerals clay when high-speed mixer mixes, can further add the antioxidant of 0.05～2 parts by weight of relative 100 parts by weight polymeric amide, and/or add the lubricant of 0.1～2 parts by weight of relative 100 parts by weight polymeric amide.
In order to guarantee the performance of gained polymeric amide/clay nano composite material, before compound with polymeric amide, can carry out purifying to used chain layered magnesium silicate minerals clay in case of necessity, its objective is the impurity of removing non-chain layered magnesium silicate minerals clay, as quartz, lime carbonate etc.Purifying can carry out in the described method of Journal of Membrane Science (calendar year 2001s 182 volume the 41st～50 page) or other appropriate method according to Weir etc.
Polymeric amide/clay nano composite material provided by the present invention, because the clay that is adopted has fibrous texture, length-to-diameter ratio is higher, thereby product has higher rigidity and excellent heat resisting, can be widely used in a plurality of industries such as automobile, machinery and electronic apparatus.
Description of drawings
The TEM photo of the polyamide 6 of Fig. 1 embodiment of the invention 1/fibrous sepiolite nano composite material.
The TEM photo of the polyamide 6 of Fig. 2 embodiment of the invention 2/clay shape sepiolite nano composite material.
Embodiment
Below in conjunction with embodiment technical characterictic of the present invention is described, need to prove that these just part descriptions for example do not constitute the restriction to content of the present invention.
Embodiment 1
The method purifying of the aforementioned Weir of fibrous sepiolite powder (Yi County, Hebei sepiolite company limited product) reference etc.With 100 parts of polyamide 6s (U.S. Honeywell company product), 2 parts of purifying fibrous sepiolites, 0.2 part of 1098 antioxidant, 0.2 part of whiteruss adopt twin screw extruder to melt extrude and obtain polyamide 6/clay nano composite material after high-speed mixer mixes.Screw rod parameter and processing conditions following (table 1):
Table 1. screw rod parameter and processing conditions
| The screw rod parameter | Processing conditions | |||||
| Screw diameter (mm) | Length-to-diameter ratio | First section (℃) | Second section (℃) | The 3rd section (℃) | The 4th section (℃) | Screw speed (rpm) |
| 30 | 23 | 210 | 220 | 230 | 230 | 200 |
Gained polyamide 6/clay nano composite material extrudate is through granulation, drying.Transmission electron microscope photo (as shown in Figure 1) show sepiolite in this matrix material with the nanoscale homodisperse.The mechanical property of material is listed in table 2.
Embodiment 2
With 100 parts of polyamide 6s (with embodiment 1), 2 parts in clay shape sepiolite powder (liuyang hunan sepiolite company limited product), 0.2 part of 1098 antioxidant, 0.2 part of whiteruss adopts the method identical with embodiment 1 to process and makes polyamide 6/clay nano composite material.Transmission electron microscope photo (as shown in Figure 2) show sepiolite in this matrix material with the nanoscale homodisperse, the mechanical property of material is listed in table 2.
Comparative Examples 1
With 100 parts of polyamide 6s (with embodiment 1), 2.5 parts of na-montmorillonites (chemical plant, Qinghe, Zhangjiakou product), 0.2 part of 1098 antioxidant, 0.2 part of whiteruss adopts the method identical with embodiment 1 to process and makes product.X-ray diffraction and this material of transmission electron microscope test shows are intercalation type nano composite material.The mechanical property of material is listed in table 2.
Comparative Examples 2
With 100 parts of polyamide 6s (with embodiment 1), 3 parts of the montmorillonites that organises (interlamellar spacing 2.1nm, press Chinese patent CN 1081207C preparation), 0.2 part of 1098 antioxidant, 0.2 part of whiteruss adopts the method identical with embodiment 1 to process and makes product.X-ray diffraction and this material of transmission electron microscope test shows are exfoliated nano-composite.The mechanical property of material is listed in table 2.
Comparative Examples 3
With 100 parts of polyamide 6s (with embodiment 1), 0.2 part of 1098 antioxidant, 0.2 part of whiteruss adopts the method identical with embodiment 1 to process and makes product.The mechanical property of material the results are shown in table 2.
The performance of table 2 polyamide 6 nano composite material
Every test data of comparison sheet 2, as seen compare with base polyamide 6 (Comparative Examples 3), tensile modulus, modulus in flexure and the thermal denaturation temperature that contains the polyamide 6 composite material (embodiment 1 and 2) of sepiolite filler all obtains raising in various degree, particularly Young's modulus has surpassed the intercalation type nano composite material (Comparative Examples 1) that contains na-montmorillonite, improve even surpassed the exfoliated nano-composite (Comparative Examples 2) that contains organic montmorillonite, material has high rigidity.
Embodiment 3
With 100 parts of polyamide 6s (with embodiment 1), 2 parts in clay shape sepiolite powder (with embodiment 2) adopts the method identical with embodiment 1 to process and makes polyamide 6/clay nano composite material.The mechanical property of material is similar to embodiment 2.
Embodiment 4
With 100 parts of polyamide 66s (Liaoyang petro-chemical fiber company), 2 parts in polygorskite powder (Jiangsu Autbang Nonmetal Co., Ltd's product), 0.2 part of 1098 antioxidant, 0.2 part of EBS lubricant is after high-speed mixer mixes, adopt twin screw extruder to melt extrude and obtain polyamide 66/clay nano composite material, screw rod parameter and processing conditions following (table 3):
Table 3. screw rod parameter and processing conditions
| The screw rod parameter | Processing conditions | |||||
| Screw diameter (mm) | Length-to-diameter ratio | First section (℃) | Second section (℃) | The 3rd section (℃) | The 4th section (℃) | Screw speed (rpm) |
| 30 | 23 | 265 | 275 | 275 | 275 | 200 |
Gained polyamide 66/clay nano composite material extrudate is through granulation, drying.Compare with the polyamide 66 raw material, the mechanical property of matrix material improves a lot.
Claims (10)
1. a polymeric amide/clay nano composite material is characterized in that: contain the polymeric amide of 100 parts by weight and the chain layered magnesium silicate minerals clay of 0.5～20 parts by weight in polymeric amide/clay nano composite material.
2. matrix material according to claim 1 is characterized in that: described polymeric amide is polyamide 6 or polyamide 66.
3. matrix material according to claim 1 is characterized in that: described chain layered magnesium silicate minerals clay is sepiolite or polygorskite.
4. matrix material according to claim 3 is characterized in that: described sepiolite is fibrous sepiolite or clay shape sepiolite.
5. matrix material according to claim 1 is characterized in that: further contain antioxidant and/or lubricant in described polymeric amide/clay nano composite material.
6. matrix material according to claim 5 is characterized in that: the add-on of described antioxidant is 0.05～2 parts by weight of relative 100 parts by weight polymeric amide; The add-on of lubricant is 0.1～2 parts by weight of relative 100 parts by weight polymeric amide.
7. according to claim 5 or 6 described matrix materials; it is characterized in that: described antioxidant is four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; (3; 5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester or N; N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine.
8. according to claim 5 or 6 described matrix materials, it is characterized in that: described lubricant is whiteruss or ethylene bis stearamide.
9. preparation method according to each described matrix material of claim 1～8, it is characterized in that: with the polymeric amide of 100 parts by weight, after 0.5 the chain layered magnesium silicate minerals clay of～20 parts by weight thorough mixing in high-speed mixer is even, melt extrude granulation with twin screw extruder, can make polymeric amide/clay nano composite material.
10. the preparation method of matrix material according to claim 9, it is characterized in that: when polymeric amide is mixed with chain layered magnesium silicate minerals clay, further add the antioxidant of 0.05～2 parts by weight of relative 100 parts by weight polymeric amide, and/or add the lubricant of 0.1～2 parts by weight of relative 100 parts by weight polymeric amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510011817 CN1869123A (en) | 2005-05-27 | 2005-05-27 | Polyurethanel clay nanometer composite material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510011817 CN1869123A (en) | 2005-05-27 | 2005-05-27 | Polyurethanel clay nanometer composite material and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1869123A true CN1869123A (en) | 2006-11-29 |
Family
ID=37442910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510011817 Pending CN1869123A (en) | 2005-05-27 | 2005-05-27 | Polyurethanel clay nanometer composite material and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1869123A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382396A (en) * | 2011-09-29 | 2012-03-21 | 芜湖海杉型材有限公司 | Novel plastic pipe and preparation method thereof |
| CN103146186A (en) * | 2013-02-28 | 2013-06-12 | 金发科技股份有限公司 | Nylon modified material and preparation method thereof |
| 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 |
| CN106009639A (en) * | 2016-06-17 | 2016-10-12 | 无锡英普林纳米科技有限公司 | Nano nylon composite and preparation method thereof |
| CN110437610A (en) * | 2019-08-14 | 2019-11-12 | 天津长芦海晶集团有限公司 | Using polyamide 6 as clay polymer composite of matrix and preparation method thereof |
| CN111670220A (en) * | 2018-11-08 | 2020-09-15 | 株式会社Lg化学 | Conductive concentrated resin composition, conductive polyamide resin composition, process for producing the same, and molded article |
-
2005
- 2005-05-27 CN CN 200510011817 patent/CN1869123A/en active Pending
Cited By (9)
| 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 |
| CN102382396A (en) * | 2011-09-29 | 2012-03-21 | 芜湖海杉型材有限公司 | Novel plastic pipe and preparation method thereof |
| CN103146186A (en) * | 2013-02-28 | 2013-06-12 | 金发科技股份有限公司 | Nylon modified material and preparation method thereof |
| CN103146186B (en) * | 2013-02-28 | 2015-04-22 | 金发科技股份有限公司 | Nylon modified material and preparation method thereof |
| CN106009639A (en) * | 2016-06-17 | 2016-10-12 | 无锡英普林纳米科技有限公司 | Nano nylon composite and preparation method thereof |
| CN111670220A (en) * | 2018-11-08 | 2020-09-15 | 株式会社Lg化学 | Conductive concentrated resin composition, conductive polyamide resin composition, process for producing the same, and molded article |
| CN111670220B (en) * | 2018-11-08 | 2023-03-10 | 株式会社Lg化学 | Conductive concentrated resin composition, conductive polyamide resin composition, method for producing same, and molded article |
| US11912868B2 (en) | 2018-11-08 | 2024-02-27 | Lg Chem, Ltd. | Conductive concentrated resin composition, conductive polyamide resin composition comprising conductive concentrated resin composition, method of preparing same and molded article |
| CN110437610A (en) * | 2019-08-14 | 2019-11-12 | 天津长芦海晶集团有限公司 | Using polyamide 6 as clay polymer composite of matrix and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bhattacharya et al. | Synergy in carbon black-filled natural rubber nanocomposites. Part I: Mechanical, dynamic mechanical properties, and morphology | |
| CN102250395B (en) | Preparation method of oil-filled chemigum/attapulgite nanocomposite | |
| CN1869123A (en) | Polyurethanel clay nanometer composite material and its preparation method | |
| CN1760265A (en) | A kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite | |
| CN103146186B (en) | Nylon modified material and preparation method thereof | |
| Bhattacharya et al. | Influence of different nanofillers and their dispersion methods on the properties of natural rubber nanocomposites | |
| CN104497567B (en) | Long carbon chain nylon/calcium silicate whisker composite and its preparation method and application | |
| KR20120077647A (en) | Polymer/carbon nano tube composites and preparation method thereof | |
| CN1464008A (en) | Nano particle polyarylthio-ether composite and method for making same | |
| KR101042894B1 (en) | Rubber vibration isolator with excellent heat-resistant and oil-resistant properties and a nanocomposite composition for the same | |
| CN1202173C (en) | Polyamide 66 composite material and preparing method thereof | |
| CN1252169C (en) | Composite for preparing polyethylene tube and method for preparing the same | |
| Zhao et al. | Melt process and performance of multi‐walled carbon nanotubes reinforced LDPE composites | |
| CN102020805B (en) | Polypropylene resin composition and preparation method thereof | |
| CN1107092C (en) | Polyamide 66 composite material and prepn. method therefor | |
| Wang et al. | Properties of abs/organic-attapulgite nanocomposites parts fabricated by fused deposition modeling | |
| CN103173016A (en) | Conductive carbon nanometer highly heat resisting mPSU (Polysulfone) compound | |
| KR101070801B1 (en) | Cellulosic nanocomposite film | |
| Balakrishnan | Environmental sustainability through the utilization of seashell wastes in the development of MWCNT-reinforced nylon 66 composites | |
| CN1831216A (en) | Polymer compounding fiber composed by surface-modified, inorganic filler and polymer | |
| Gao et al. | Facile fabrication of high-performance PA66/MWNT nanocomposite fibers | |
| CN1765974A (en) | Nanometer polypropylene packaging material and its production method | |
| CN1284827C (en) | Master batch of polyamide/rectorite nano composite materials and method for preparing same | |
| Yuan et al. | Investigation of melt-intercalated PET-clay nanocomposites | |
| CN1504506A (en) | Desquamation type polyvinyl chloride nanometer composite material and preparing process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |