CN1651499A - High performance polymer composite material capable of forming inorganic nano-particle network and its preparation method - Google Patents

High performance polymer composite material capable of forming inorganic nano-particle network and its preparation method Download PDF

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CN1651499A
CN1651499A CN 200510020118 CN200510020118A CN1651499A CN 1651499 A CN1651499 A CN 1651499A CN 200510020118 CN200510020118 CN 200510020118 CN 200510020118 A CN200510020118 A CN 200510020118A CN 1651499 A CN1651499 A CN 1651499A
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inorganic nano
particle
high performance
composite material
polymer composite
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CN100344688C (en
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傅强
张琴
杨红
杜荣昵
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Guangdong Silver Age Sci & Tech Co ltd
Sichuan University
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Sichuan University
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Abstract

A high-performance polymer composition able to form inorganic nano-particle web is composed of basic polymer material, elastomers and inorganic nano-particles, which are coated on the surface of elastomer and distributed in web mode, so increasing toughness and improving performance.

Description

Can form high performance polymer composite material of inorganic nano-particle network and preparation method thereof
One, technical field
The invention belongs to polymer composites and preparing technical field thereof, be specifically related to a kind ofly can form high performance polymer composite material of inorganic nano-particle network and preparation method thereof.
Two, background technology
Polymkeric substance is as structured material, and strength and toughness is two important mechanical performance indexs.The polymer toughening that is used as plastics is the research focus in modifying plastics and the application always.At present, widely used plastic toughening method be with elastomerics as toughner, realize the purpose of toughening modifying.Though can obtain the ideal toughening effect with the elastic body toughening plastics, damaged the intensity and the rigidity of material preciousness, also influenced the processing fluidity and the resistance to heat distorsion of material simultaneously, and owing to need the elastomerics of adding more, so cost is also higher.
From the eighties, the someone has sprouted the idea that replaces elastomerics or rubber toughened polymkeric substance with rigid particles fully, and has proposed to utilize the inorganic rigid particle filled toughening to strengthen the new way (Kurauchi of polymkeric substance, T., Ohta, J., J.Mater.Sci., 1984,19:1699).Use the rigid particles toughened plastics, though can be when improving the material shock resistance, do not reduce the tensile strength and the rigidity of material, its processing fluidity and resistance to heat distorsion also are improved, make the further high performance of material, and can reduce cost, the broadened application field, for the toughening modifying of plastics has been opened up new approach.But inorganic rigid particle is obvious not as good as elastic body toughening to the toughening effect of polymkeric substance.
In order to obtain low cost, high performance plastic material, people begin again inorganic rigid particle and elastomerics coordination plasticizing system are studied.The inventor finds under study for action, uses inorganic rigid particle and elastomerics that the effect that polymkeric substance carries out modification is depended primarily on the morphological structure of disperse phase in blend polymer.Analyze theoretically, the disperse phase in this class blend generally has three kinds of discrete form: 1, two disperse phase are scattered in the polymeric matrix independently; 2, inorganic rigid particle is coated by elastomerics, and hard outer soft nuclear-shell structure is scattered in the polymeric matrix in forming; 3, elastomerics is coated by inorganic rigid particle, and soft outer stone-shell structure is scattered in the polymeric matrix in forming.For these three kinds of structures, it is generally acknowledged, dispersed texture is beneficial to the raising of system inflexible separately, interior hard outer soft nuclear-shell structure then helps the raising of system shock strength, if elastomerics is coated by inorganic rigid particle, soft outer stone-shell structure in forming then can reach toughness reinforcing and the enhanced purpose simultaneously.First kind of dispersed texture form is with inorganic rigid particle, elastomerics and three kinds of components of polymer matrix material in the blend process, disposable in proportion adding blend makes, second kind of existing report of dispersed texture form ZL02128048.7, and the third dispersed texture form yet there are no report.
Three, summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of high performance polymer composite material that can form inorganic nano-particle network is provided.Another object of the present invention provides the method for this matrix material of preparation.
The high performance polymer composite material that can form inorganic nano-particle network provided by the invention, comprise polymer matrix material, elastomerics, it is characterized in that this matrix material also contains inorganic nano-particle, gross weight based on this matrix material, the weight percent content of each component is: polymer matrix material 70~94%, elastomerics 3~20%, inorganic nano-particle 3~10%, wherein inorganic nano-particle is coated on outside the dispersive elastomerics, and the formation that distributes in polymer matrix material is network-like.
Wherein polymer matrix material is any in polypropylene, polyethylene, nylon 6, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, the polyphenylene sulfide.
Inorganic nano-particle is any in lime carbonate, silicon-dioxide, polynite, kaolin, potter's clay, talcum powder, wollastonite powder, vermiculite, graphite, the carbon black, the preferred 50~200nm scope of its particle diameter.
Elastomerics is any in polyolefin elastomer, ethylene-propylene rubber(EPR), paracril, the urethane.
The method of the high performance polymer composite material that can form inorganic nano-particle network that preparation provided by the invention is above-mentioned is characterized in that:
(1) will 100~120 ℃ down dry 4~6 hours inorganic nano-particles by weight 1~90 part with elastomerics by weight 5~95 parts carry out thorough mixing earlier, make masterbatch with twin screw extruder or in room temperature with double roll mill at 100~210 ℃ then;
(2) be after 3~10% the ratio and polymer matrix material premix in the content of inorganic nano-particle in the matrix material of final acquisition with masterbatch, 130~350 ℃ of melt blendings promptly obtain to form the high performance polymer composite material of inorganic nano-particle network on twin screw extruder.
The present invention has following advantage:
1, because after the present invention adopts a spot of elastomerics of adding (≤20%) and inorganic nano-particle interworking to make masterbatch, again the masterbatch fusion is scattered in the matrix material that makes in the polymeric matrix, not only reach elastomerics is coated by inorganic rigid particle, soft outer stone-shell structure is scattered in the intended purposes in the polymeric matrix in forming, also having obtained unexpected structural form---inorganic nano-particle has formed special networks structure (see figure 1) in polymeric matrix, this structure not only realizes the enhancing toughening effect of polymer matrix material (is seen Fig. 3 simultaneously, 4 and table 1), can also become stress transfer center, make the matrix material that obtains have more excellent performance.
If 2 inorganic nano-particles that add are functional fillers,, can form the conductivity that inorganic nano-particle network can greatly improve material as electro-conductive materials such as graphite, carbon blacks.
3, the elastomerics consumption that adopts owing to the inventive method reduces, and does not also have the consumption of other additive, thereby the cost of material can descend significantly.
4, preparation method provided by the invention can not only give matrix material special morphological structure, makes performance of composites more excellent, and simple to operate, technical maturity.
Four, description of drawings
Fig. 1 is the sem photograph of the high-performance polypropylene composite sample section of the present invention's preparation; Fig. 2 is the sem photograph of comparative example 1 sample section; Fig. 3 is the notched Izod impact strength test curve figure of the high-performance polypropylene matrix material of the present invention's preparation; Fig. 4 is the tensile strength test curve figure of the high-performance polypropylene matrix material of the present invention's preparation.
Five, 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 detailed; 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.Following examples are raw materials used to be not specifically noted, and is weight part.
Embodiment 1
Will 100 ℃ down dry 6 hours, particle diameter is 1 part in the lime carbonate of 50nm, with 4 parts of polyolefin elastomers is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, carry out melt blending then and make masterbatch on 130~210 ℃ twin screw extruder, masterbatch contains lime carbonate 20%; Again with behind 1 part of masterbatch, 3 parts of first premixs of polyethylene, melt blending on 140~200 ℃ twin screw extruder promptly makes calcium carbonate content and is 5%, the polyolefin elastic body burden is 20% the high performance polymer composite material that can form inorganic nano-particle network.
Embodiment 2
Will 120 ℃ down dry 4 hours, particle diameter is 20 parts of the silicon-dioxide of 80nm, with 30 parts of ethylene-propylene rubber(EPR) is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, at room temperature make masterbatch with blend on the double roll mill then, masterbatch contains silicon-dioxide 40%; Again with behind 3 parts of masterbatch, 37 parts of first premixs of polypropylene, melt blending on 140~200 ℃ twin screw extruder promptly makes dioxide-containing silica and is 3%, ethylene-propylene rubber(EPR) content is 4.5% the high performance polymer composite material that can form inorganic nano-particle network.
Embodiment 3
Will be 40 parts of 110 ℃ of polynites following dry 5 hours, that usefulness cationite hexadecyl amine salt was handled, with 80 parts of paracrils is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, on 130~210 ℃ twin screw extruder, carry out melt blending then and make masterbatch, masterbatch montmorillonoid-containing 33%; Again with behind 10 parts of masterbatch, 6 37 parts of first premixs of nylon, melt blending on 140~250 ℃ twin screw extruder promptly makes polynite content and is 7%, paracril content is 14% the high performance polymer composite material that can form inorganic nano-particle network.
Embodiment 4
Will 100 ℃ down dry 6 hours, particle diameter is 70 parts of the kaolin of 200nm, with 70 parts of ethylene-propylene rubber(EPR) is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, carry out melt blending then and make masterbatch on 130~210 ℃ twin screw extruder, masterbatch contains kaolin 50%; Again with behind 30 parts of masterbatch, 120 parts of first premixs of polyethylene terephthalate, melt blending on 140~280 ℃ twin screw extruder promptly makes kaolin content and is 10%, polyethylene terephthalate content is 10% the high performance polymer composite material that can form inorganic nano-particle network.
Embodiment 5
Will 100 ℃ down dry 5 hours, particle diameter is 90 parts in the graphite of 100nm, with 95 parts of urethane is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, on 130~210 ℃ twin screw extruder, carry out melt blending then and make masterbatch, masterbatch graphitiferous 48%; Again with behind 20 parts of masterbatch, 100 parts of first premixs of polyphenylene sulfide, melt blending on 140~350 ℃ twin screw extruder promptly makes content of graphite and is 8%, polyphenylene sulfide content is 8% the high performance polymer composite material that can form inorganic nano-particle network.
Embodiment 6
Will 120 ℃ down dry 4 hours, particle diameter is 5 parts of the silica 1s of 80nm, with 90 parts of ethylene-propylene rubber(EPR) is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, at room temperature make masterbatch with blend on the double roll mill then, masterbatch contains silicon-dioxide 7.3%; Again with behind 22 parts of masterbatch, 78 parts of first premixs of polypropylene, melt blending on 140~200 ℃ twin screw extruder promptly makes dioxide-containing silica and is 3%, ethylene-propylene rubber(EPR) content is 19% the high performance polymer composite material that can form inorganic nano-particle network.
Comparative example 1
Will 120 ℃ down dry 4 hours, particle diameter is 3 parts of the silicon-dioxide of 80nm, with 97 parts of polypropylene is to stir on the homogenizer of 1000rpm to carry out thorough mixing at rotating speed, and promptly to make dioxide-containing silica be 3% polypropylene composite material to melt blending on 140~200 ℃ twin screw extruder.
Metamorphosis for the high performance polymer composite material that can form inorganic nano-particle network of observing the present invention preparation, with the dioxide-containing silica of the matrix material of the embodiment of the invention 6 gained and comparative example 1 gained is that 3% polypropylene composite material is respectively through the liquid nitrogen brittle failure, after the matrix material of embodiment 6 gained also etches away ethylene-propylene rubber(EPR) with dimethylbenzene, JEOLJSM-5900LV type scanning electronic microscope with Jeol Ltd.'s production, under acceleration voltage 20KV, the form that observation post gets is seen Fig. 1,2.As can be seen from Figure 1, the matrix material of gained of the present invention, silicon-dioxide are to coat outside the ethylene-propylene rubber(EPR) elastomerics, and are scattered in and have formed reticulated structure in the polypropylene matrix, and the shown silicon-dioxide of Fig. 2 just is dispersed in the matrix, and does not form network structure.
For the high performance polymer composite material that can form inorganic nano-particle network of investigating the present invention preparation and virgin pp with compare with the polypropylene of traditional method modification, its intensity and flexible change, with the matrix material of the embodiment of the invention 6 gained and virgin pp with the polypropylene sample preparation respectively of traditional method modification, carried out notched Izod impact strength, carried out tensile strength, carried out the test of flexural strength and modulus in flexure by the GB/T1843-1996 standard respectively, the results are shown in Table 1 by the GB9341 standard by the GB/T1040-92 standard.By table 1 as seen, its notched Izod impact strength of the matrix material of gained of the present invention is equivalent to add the elastomeric effect of 30wt% in polypropylene, and lose intensity and modulus simultaneously hardly, the adding of mineral filler is described and forms network structure to substitute the toughner of most of elastomerics, realize enhancement simultaneously polymkeric substance as polymkeric substance.
In order to verify mother material provided by the invention, the performance difference that the matrix material of preparation is brought with traditional single stage method (three kinds of disposable in proportion adding blend of component), the inventor also will be after under 120 ℃ dry 4 hours, particle diameter is that the silicon-dioxide of 80nm is by 0,1,3,5 parts, use single stage method and two step method and 80 parts of polypropylene respectively, 20 parts of ethylene-propylene rubber(EPR), melt blending makes corresponding matrix material on 140~200 ℃ twin screw extruder, sample preparation, carried out notched Izod impact strength by GB/T1843-1996 standard standard, carry out the test of tensile strength by the GB/T1040-92 standard, the results are shown in Figure 3,4.The result shows, the notched Izod impact strength and the tensile strength of the matrix material that makes with mother material all are higher than the matrix material that single stage method makes far away, the contribution that the network structure that this matrix material silicon-dioxide that may be mother material makes forms is done in polymeric matrix.
Table 1
Figure A20051002011800091

Claims (10)

1, a kind of high performance polymer composite material that can form inorganic nano-particle network, comprise polymer matrix material, elastomerics, it is characterized in that this matrix material also contains inorganic nano-particle, gross weight based on this matrix material, the weight percent content of each component is: polymer matrix material 70~94%, elastomerics 3~20%, inorganic nano-particle 3~10%, wherein inorganic nano-particle is coated on outside the dispersive elastomerics, and the formation that distributes in polymer matrix material is network-like.
2, the high performance polymer composite material that can form inorganic nano-particle network according to claim 1 is characterized in that polymer matrix material is any in polypropylene, polyethylene, nylon 6, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, the polyphenylene sulfide.
3, the high performance polymer composite material that can form inorganic nano-particle network according to claim 1 and 2 is characterized in that inorganic nano-particle is any in lime carbonate, silicon-dioxide, polynite, kaolin, potter's clay, talcum powder, wollastonite powder, vermiculite, graphite, the carbon black.
4, the high performance polymer composite material that can form inorganic nano-particle network according to claim 1 and 2, the particle diameter that it is characterized in that inorganic nano-particle is 50~200nm.
5, the high performance polymer composite material that can form inorganic nano-particle network according to claim 3, the particle diameter that it is characterized in that inorganic nano-particle is 50~200nm.
6, the high performance polymer composite material that can form inorganic nano-particle network according to claim 1 and 2 is characterized in that elastomerics is any in polyolefin elastomer, ethylene-propylene rubber(EPR), paracril, the urethane.
7, the high performance polymer composite material that can form inorganic nano-particle network according to claim 3 is characterized in that elastomerics is any in polyolefin elastomer, ethylene-propylene rubber(EPR), paracril, the urethane.
8, the high performance polymer composite material that can form inorganic nano-particle network according to claim 4 is characterized in that elastomerics is any in polyolefin elastomer, ethylene-propylene rubber(EPR), paracril, the urethane.
9, the high performance polymer composite material that can form inorganic nano-particle network according to claim 5 is characterized in that elastomerics is any in polyolefin elastomer, ethylene-propylene rubber(EPR), paracril, the urethane.
10, a kind ofly prepare each described method that can form the high performance polymer composite material of inorganic nano-particle network in the claim 1~9, it is characterized in that:
(1) will 100~120 ℃ down dry 4~6 hours inorganic nano-particles by weight 1~90 part with elastomerics by weight 5~95 parts carry out thorough mixing earlier, make masterbatch with twin screw extruder or in room temperature with double roll mill at 100~210 ℃ then;
(2) be after 3~10% the ratio and polymer matrix material premix in the content of inorganic nano-particle in the matrix material of final acquisition with masterbatch, 130~350 ℃ of melt blendings promptly obtain to form the high performance polymer composite material of inorganic nano-particle network on twin screw extruder.
CNB2005100201181A 2005-01-07 2005-01-07 High performance polymer composite material capable of forming inorganic nano-particle network and its preparation method Expired - Fee Related CN100344688C (en)

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CN102070914A (en) * 2010-11-19 2011-05-25 深圳市华力兴工程塑料有限公司 Inorganic particle-coated plastic granules and preparation method and application thereof
CN102702747A (en) * 2012-06-14 2012-10-03 南京同辉新型材料科技有限公司 Insulating and heat-conducting high polymer and preparation method thereof
CN102888112A (en) * 2011-07-18 2013-01-23 四川得阳特种新材料有限公司 Manufacturing method of polyphenylene sulfide composite granulates containing highly-filled materials
CN102952333A (en) * 2012-10-19 2013-03-06 芜湖太平洋塑胶有限公司 Improved polypropylene (PP) dinner plate material and processing method thereof
CN102952378A (en) * 2012-10-19 2013-03-06 芜湖太平洋塑胶有限公司 Modified nano-clay dinner plate material and processing method thereof
CN105255004A (en) * 2015-10-26 2016-01-20 四川大学 Graphite resin composite material of core-shell structure and preparation method thereof
CN110911617A (en) * 2019-12-10 2020-03-24 安徽新衡新材料科技有限公司 High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof
CN112143222A (en) * 2020-09-22 2020-12-29 横店集团得邦工程塑料有限公司 Low-temperature wear-resistant PA66/GF composite material and preparation method thereof
CN112876842A (en) * 2021-01-15 2021-06-01 宿迁联盛科技股份有限公司 Preparation method of anti-aging polymer composite material with enhanced core-shell structure
CN113045839A (en) * 2021-03-02 2021-06-29 中国地质大学(北京) Composite material for reinforcing thermoplastic polymer resin and preparation method thereof

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Cited By (14)

* Cited by examiner, † Cited by third party
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CN102070914A (en) * 2010-11-19 2011-05-25 深圳市华力兴工程塑料有限公司 Inorganic particle-coated plastic granules and preparation method and application thereof
CN102888112B (en) * 2011-07-18 2014-06-25 四川得阳特种新材料有限公司 Manufacturing method of polyphenylene sulfide composite granulates containing highly-filled materials
CN102888112A (en) * 2011-07-18 2013-01-23 四川得阳特种新材料有限公司 Manufacturing method of polyphenylene sulfide composite granulates containing highly-filled materials
CN102702747A (en) * 2012-06-14 2012-10-03 南京同辉新型材料科技有限公司 Insulating and heat-conducting high polymer and preparation method thereof
CN102952333B (en) * 2012-10-19 2015-03-25 芜湖太平洋塑胶有限公司 Improved polypropylene (PP) dinner plate material and processing method thereof
CN102952378A (en) * 2012-10-19 2013-03-06 芜湖太平洋塑胶有限公司 Modified nano-clay dinner plate material and processing method thereof
CN102952333A (en) * 2012-10-19 2013-03-06 芜湖太平洋塑胶有限公司 Improved polypropylene (PP) dinner plate material and processing method thereof
CN105255004A (en) * 2015-10-26 2016-01-20 四川大学 Graphite resin composite material of core-shell structure and preparation method thereof
CN105255004B (en) * 2015-10-26 2018-06-01 四川大学 A kind of graphite resin composite material with nucleocapsid and preparation method thereof
CN110911617A (en) * 2019-12-10 2020-03-24 安徽新衡新材料科技有限公司 High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof
CN112143222A (en) * 2020-09-22 2020-12-29 横店集团得邦工程塑料有限公司 Low-temperature wear-resistant PA66/GF composite material and preparation method thereof
CN112876842A (en) * 2021-01-15 2021-06-01 宿迁联盛科技股份有限公司 Preparation method of anti-aging polymer composite material with enhanced core-shell structure
CN113045839A (en) * 2021-03-02 2021-06-29 中国地质大学(北京) Composite material for reinforcing thermoplastic polymer resin and preparation method thereof
CN113045839B (en) * 2021-03-02 2022-06-28 中国地质大学(北京) Composite material for reinforcing thermoplastic polymer resin and preparation method thereof

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