CN100371384C - Reacting nano inorganic particle/polymer composite material - Google Patents
Reacting nano inorganic particle/polymer composite material Download PDFInfo
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- CN100371384C CN100371384C CNB2006100340117A CN200610034011A CN100371384C CN 100371384 C CN100371384 C CN 100371384C CN B2006100340117 A CNB2006100340117 A CN B2006100340117A CN 200610034011 A CN200610034011 A CN 200610034011A CN 100371384 C CN100371384 C CN 100371384C
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Abstract
The present invention discloses a reacting nanometer inorganic particle/polymer composite material which comprises the following components of the weight percentage: 1 to 5% of modified nanometer inorganic particle, 2.5 to 10% of functional reacting polymer compatibilizer and 85 to 96.5% of polymer matrix. The present invention uses a reacting compatibilization technique, and thus, inorganic nanometer particles chemically react with the polymer on the original positions in the mixing process by a conventional mixing method so as to generate grafting substances. As a result, the interface action between the inorganic nanometer particles and the polymer matrix is greatly enhanced, and the interface binding strength of the inorganic nanometer particles and the polymer matrix is greatly increased. Meanwhile, the dispersion of the inorganic nanometer particles in the matrix is effectively improved. Thus, the mechanical performance of the prepared composite material is effectively enhanced. The present invention has the advantages of no need of special equipment and technology, adoption of conventional processing equipment, simple technology and favorable comprehensive performance of prepared composite material.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of reacting nano inorganic particle/polymer composites.
Background technology
The size range of nano inoganic particle is 1～100nm normally, and it is little to have size, and specific surface area is big, surface energy height, characteristics such as the surface atom ratio is big.Can under low levels, significantly improve the mechanical property of polymkeric substance and produce effects such as some special light, electricity, magnetic.Therefore the research of nano composite material has in recent years caused people's great interest, becomes the most dynamic research object in the current novel material research field.
But the surface energy of inorganic nano-particle is very big, causes it very easily to take place to reunite and assemble, and therefore is difficult to obtain the homodisperse of real nanoscale with general direct blend method.For nanoparticle is disperseed uniformly and and macromolecular material between good interface bonding is arranged, generally at present adopt more special preparation method, mainly contain graft process and in-situ compositing.
Graft process is meant organic monomer or polymkeric substance is inserted between the lamella of laminated inorganic matter, utilizes thermodynamics or power chemical action that sheet interlayer spacing is increased to peel off into the primary particle of nanoscale and is dispersed in the polymeric matrix.According to preparation method's difference, can obtain insert type and exfoliated nano composite material, but this method is confined to the mineral filler that minorities such as clay, illiteracy holder soil, graphite have laminate structure, limited the range of application of this method.
In-situ compositing is that the monomer polymerization original position forms nano composite material under the situation that nanoparticle exists, or prepares nano composite material by sol-gel method.It is less that this method can obtain particle diameter, finely dispersed nano composite material, but this method is more loaded down with trivial details, and workload is big, and solvent is selected difficulty, generally is confined to laboratory study, is difficult to application.
From the angle analysis of polymer processing, nanoparticle and polymer melt blend are the most convenient feasible a kind of methods of preparation nano composite material.From the development of present domestic nano material, the research of nano-powder and preparation development are rapid, but its applied research relatively lags behind.
Because the polarity difference of inorganic nano-particle and polymeric matrix is very big, the two consistency is poor, and interface bonding between the two is very weak, adds the easy reunion of nanoparticle self again, so use conventional blend method, be difficult to obtain scattered, reunite less, the nano composite material of superior performance.For this reason, generally need carry out surface modification, make its reversing, improve consistency with matrix to particle.Usually the method for usefulness is that coupling agent or grafting are handled, but these methods all are by introducing long-chain at particle surface, change the surface property of particle, thereby increase the avidity of particle and matrix, the entanglement of the molecular chain by long-chain on the particle surface and matrix improves the interface bonding between particle and matrix, improves particle dispersive purpose in matrix thereby reach.But this interchain entanglement effect is more weak, is difficult to effectively change the effect between particle and matrix.
Summary of the invention
The objective of the invention is to overcome the problem that above-mentioned existing nano composite material exists, provide between a kind of nano inoganic particle and the polymeric matrix functionality strong, the interface binding intensity height, particle is uniformly dispersed in matrix, reacting nano inorganic particle/polymer composites that over-all properties is good.
Purpose of the present invention can realize by following measure: with coupling agent nano inoganic particle is carried out pre-treatment, make its surface have energy polymeric organic group, then nanoparticle graft polymerization in solution is introduced and had reactive functional group, in this process, can effectively stop the reunion of nanoparticle.Simultaneously by fusion-grafting, import on the polymkeric substance can with the reactive group of radical reaction on the particle, make the functionalized polymer reactive compatibilizer.Utilize existing processing technology, in the blend process, react between nano inoganic particle and the functionalized polymer reactive compatibilizer, thereby reach the purpose of reactive compatibilization.This will help the dispersion of particle in matrix, and inorganic nano-particle can better be disperseed in matrix.Simultaneously, the interface interaction between polymkeric substance and nano inoganic particle is strengthened greatly, improves interface bonding between the two effectively.
Reacting nano inorganic particle/polymer composites of the present invention is made up of following component and weight percentage: modified Nano inorganic particulate 1～5%, functionalized polymer reactive compatibilizer 2.5～10%, polymeric matrix 85～96.5%.
Above-mentioned modified Nano inorganic particulate is to be prepared from by following method:
1. the pre-treatment of nano inoganic particle: with toluene is solvent, under protection of inert gas, and coupling agent and nano inoganic particle back flow reaction, the consumption of coupling agent is 10～100 weight % of nano inoganic particle; Described nano inoganic particle can be nano silicon or nano-calcium carbonate etc., and nano silicon can be vapor phase process or precipitated silica, and median size is 7～50nm, and specific surface area is 150～640m
2/ g;
2. the functionalization of nano inoganic particle: with toluene is solvent, under protection of inert gas, and the graft polymerization in the presence of radical initiator with pretreated nano inoganic particle and monomer, 60～80 ℃ of temperature of reaction, 4～6 hours reaction times; The monomer consumption is 50～200 weight % of pre-treatment nano inoganic particle, and the radical initiator consumption is 0.1～0.5% of a monomer consumption; Described monomer is the mixture of a kind of in methyl propenoic acid glycidyl fat, vinylformic acid, methacrylic acid, maleic anhydride, maleimide, the Yi Xi oxazolin or itself and esters of acrylic acid.
Above-mentioned functions fluidized polymer reactive compatibilizer is prepared from by following method: in the presence of radical initiator, polymkeric substance and maleic anhydride are adopted fusion-grafting, 180～200 ℃ of temperature of reaction, 2～10 minutes reaction times; The maleic anhydride consumption is 5～10 weight % of polymer loading, and the consumption of radical initiator is 0.1～0.5 weight % of polymer loading; Behind maleic anhydride graft, maleic anhydride grafts diamine compounds fusion amination, 180～200 ℃ of temperature of reaction, in 4～8 minutes reaction times, the diamine compounds consumption is 1.8 weight % of maleic anhydride grafts consumption; Described polymkeric substance is polypropylene, ethylene-propylene terpolymer, polyethylene, (ethylene-octene) multipolymer or styrene-butadiene-styrene block copolymer.
Above-mentioned polymeric matrix is polypropylene (PP), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC).
Above-mentioned radical initiator is Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide (BPO); Described coupling agent is γ-methacryloxypropyl trimethoxy silane.
The preparation method of reacting nano inorganic particle/polymer composites of the present invention is: with modified Nano particle, functionalized polymer reactive compatibilizer, polymeric matrix melt blending, the time is 6～10 minutes, 160～200 ℃ of temperature.
Compared with prior art, the present invention has following beneficial effect: the present invention adopts the reactive compatibilization technology, utilize conventional blend method, make inorganic nano-particle original position and polymkeric substance generation chemical reaction in the blend process, generate grafts, strengthen the interface interaction between nano inoganic particle and polymeric matrix greatly, interface binding intensity is between the two greatly improved, effectively improved the dispersion of inorganic nano-particle in matrix simultaneously.The mechanical property of made matrix material is effectively improved.The present invention need not special equipment and technology, can adopt conventional processing units, and technology is simple, and the over-all properties of obtained matrix material is good, utilizes the inventive method can make macromolecular material effectively be strengthened toughness reinforcing and the raising rigidity.The present invention also can be applicable to prepare the nano composite material of polyethylene, polystyrene, polyvinyl chloride etc.
Description of drawings
Fig. 1 is silicon-dioxide after the PGMA graft modification, PP-g-NH
2, embodiment 2 gained matrix material blends resistates after the toluene extracting infrared spectrogram;
Fig. 2 is the thermogravimetric analysis figure of silicon-dioxide after the PGMA graft modification, amino functional polypropylene, virgin pp, embodiment 2 gained matrix material blends resistates after the toluene extracting.
Embodiment
With toluene is solvent, and under nitrogen protection, coupling agent is γ-methacryloxypropyl trimethoxy silane and nano-silicon dioxide particle back flow reaction 8 hours, obtains pretreated nano inoganic particle; Then with glycidyl methacrylate (GMA) graft polymerization in the presence of radical initiator Diisopropyl azodicarboxylate (AIBN), 80 ℃ of temperature of reaction, 5 hours reaction times; Make modified manometer silicon dioxide (SiO
2-g-PGMA).The GMA consumption is 100 weight % of pre-treatment nano inoganic particle, and the radical initiator consumption is 0.4 weight % of GMA consumption; The consumption of coupling agent γ-methacryloxypropyl trimethoxy silane is 50 weight % of nano-silicon dioxide particle.
With toluene is solvent, and under nitrogen protection, coupling agent is γ-methacryloxypropyl trimethoxy silane and nano-silicon dioxide particle back flow reaction 8 hours, obtains pretreated nano inoganic particle; The graft polymerization in the presence of radical initiator Diisopropyl azodicarboxylate (AIBN) with glycidyl methacrylate (GMA) and butyl acrylate (BA) then, 80 ℃ of temperature of reaction, 5 hours reaction times; Make modified manometer silicon dioxide (SiO
2-g-P (BA-co-GMA)).The GMA consumption is 100 weight % of pre-treatment nano inoganic particle, and the BA consumption is 50 weight % of pre-treatment nano inoganic particle, and the radical initiator consumption is 0.4 weight % of GMA and the total consumption of BA; The consumption of coupling agent γ-methacryloxypropyl trimethoxy silane is 50 weight % of nano-silicon dioxide particle.
In the presence of radical initiator Diisopropyl azodicarboxylate (AIBN), polypropylene (PP) and maleic anhydride (MA) are adopted fusion-grafting, 180 ℃ of temperature of reaction in 8 minutes reaction times, make Functionalization of Polypropylene by Maleic Anhydride (PP-g-MA); The MA consumption is 6 weight % of PP consumption, and the consumption of radical initiator Diisopropyl azodicarboxylate (AIBN) is 0.2 weight % of PP consumption.With PP-g-MA and hexanediamine (HMDA) fusion amination, 180 ℃ of temperature of reaction in 6 minutes reaction times, make amino functional polypropylene (PP-g-NH again
2), the HMDA consumption is the 1.8 weight % of PP-g-MA.
Concrete preparation method: with modified manometer silicon dioxide, functional poly propylene and polypropylene matrix melt blending in the Haake Rheocord 300P torque rheometer of German Haake company, complete processing is: temperature, 180 ℃; Time, 10min; Rotating speed, 60r/min.Plasticizing back material is injected into the standard batten with injector.According to above-mentioned preparation method's preparation feedback nanometer composite inorganic particle/polymer material, each embodiment and concrete consumption thereof are as shown in table 1.Each comparative example is as shown in table 2, and the performance of each embodiment and comparative example is more as shown in table 3.
Each composition proportion of each embodiment of table 1
| Modified manometer silicon dioxide weight (g) | Functional poly propylene (PP-g-NH 2) weight (g) | Polypropylene (g) | |
| |
2 (SiO 2-g-PGMA) 3 (SiO 2-g-PGMA) | 10 10 | 88 87 |
| Embodiment 3 embodiment 4 | 2 (SiO 2-g-P(BA-co-GMA)) 3 (SiO 2-g-P(BA-co-GMA)) | 10 10 | 88 87 |
Each composition proportion of table 2 part comparative example
| Nano silicon weight (g) | Functional poly propylene (PP-g-NH 2) weight (g) | Polypropylene (g) | |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 | 0 2 (SiO 2) 3 (SiO 2) 3 (SiO 2-g-PGMA) 2 (SiO 2-g-P(BA-co-GMA)) | 0 0 0 0 0 | 100 98 97 97 98 |
The performance of table 3 embodiment and Comparative Examples institute prepared material relatively
| Performance | Embodiment | Comparative example | |||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | 5 | |
| Simply supported beam notched Izod impact strength (kJ/m 2) tensile strength (MPa) tensile modulus (GPa) fusing point Tm (℃) the fastest temperature T c of crystallization (℃) Δ T=Tm-Tc (℃) crystallinity Xc (%) | 3.29 42.2 1.28 165.6 125.7 39.9 59.7 | 3.22 42.3 1.33 165.8 125.5 40.3 58.1 | 3.44 42.3 1.34 165.4 125.7 39.7 54.7 | 3.35 42.2 1.40 165.5 125.9 39.6 55.7 | 1.85 37.8 1.06 164.8 115.9 48.9 54.3 | 2.09 38.0 1.27 164.5 116.5 48.0 54.6 | 1.93 38.5 1.33 164.2 116.9 47.3 54.8 | 1.95 40.9 1.22 165.3 118.6 46.7 52.2 | 1.98 41.5 1.18 164.0 118.9 45.1 54.3 |
As seen from Table 3:
1. the normal temperature notched Izod impact strength of each embodiment sample is the highest, improves 80～90% than virgin pp (comparative example 1) approximately, and toughness reinforcing effect is obvious.By contrast, to nano inoganic particle modified, to polyacrylic normal temperature notched Izod impact strength increase rate seldom (comparative example 4,5), this illustrates that also reactive compatibilization is very effective to the raising of material impact performance as only.Simultaneously the tensile strength of each embodiment sample has improved approximately 12% than virgin pp (comparative example 1), also increases with respect to only nano-inorganic particle filled (comparative example 2,3,4,5).Illustrate that utilizing this inventive method that nano-silica filled polypropylene is reached strengthens toughness reinforcing purpose simultaneously.
2. the tensile modulus of each embodiment sample is all than virgin pp (comparative example 1) height, even than the same dioxide-containing silica direct modulus height of the sample of filling down, is higher than the tensile modulus of comparative example 2,5 as the tensile modulus of embodiment 1.The rigidity that the obtained nano composite material of the present invention is described is better.Illustrating also that the inventive method can not only strengthen simultaneously gives toughly, can also improve the rigidity of material simultaneously.
3. the data from crystal property compare, and the fusing point of each embodiment sample is compared with virgin pp (comparative example 1) and changed not quite, slightly raise, but the condensate depression variation are obvious, and supercooling temperature Δ T scope is obviously dwindled; Compare nano inoganic particle and directly fill, supercooling temperature Δ T scope is also obviously dwindled, and illustrates among the present invention that nanoparticle plays the heterogeneous nucleation effect behind reactive compatibilization, and the crystallization rate of polymkeric substance is accelerated, and degree of crystallinity increases simultaneously.
Fig. 1 has showed the infrared spectrogram of silicon-dioxide after the PGMA graft modification, amino functional polypropylene, embodiment 2 blends resistates after the toluene extracting respectively, three curve ratio, epoxy group(ing) (910cm on the extracting resistates
-1) obviously die down, polyacrylic characteristic peak (1385cm has appearred
-1), illustrate reaction in has taken place in the course of processing really, proved the feasibility of reactive compatibilization.
Fig. 2 has showed the thermogravimetric analysis figure of silicon-dioxide after the PGMA graft modification, amino functional polypropylene, polypropylene, embodiment 2 blends resistates after the toluene extracting respectively, this figure has illustrated too reaction has taken place that it is truly feasible that reactive compatibilization prepares nano composite material in the course of processing.
Claims (3)
1. a reacting nano inorganic particle/polymer composites is characterized in that being made up of following component and weight percentage: modified Nano inorganic particulate 1～5%, functionalized polymer reactive compatibilizer 2.5～10%, polymeric matrix 85～96.5%;
Described modified Nano inorganic particulate is to be prepared from by following method:
1. the pre-treatment of nano inoganic particle: with toluene is solvent, under protection of inert gas, and coupling agent and nano inoganic particle back flow reaction, the consumption of coupling agent is 10～100 weight % of nano inoganic particle; Described nano inoganic particle is nano silicon or Nano particles of calcium carbonate, and nano silicon can be by gas phase or precipitator method preparation, median size 7～60nm;
2. the functionalization of nano inoganic particle: with toluene is solvent, under protection of inert gas, and the graft polymerization in the presence of radical initiator with pretreated nano inoganic particle and monomer, 60～80 ℃ of temperature of reaction, 4～6 hours reaction times; The monomer consumption is 50～200 weight % of pre-treatment nano inoganic particle, and the radical initiator consumption is 0.1～0.5% of a monomer consumption; Described monomer is the mixture of a kind of in methyl propenoic acid glycidyl fat, vinylformic acid, methacrylic acid, maleic anhydride, maleimide, the Yi Xi oxazolin or itself and esters of acrylic acid;
Described functionalized polymer reactive compatibilizer is prepared from by following method: in the presence of radical initiator, polymkeric substance and maleic anhydride are adopted fusion-grafting, 180～200 ℃ of temperature of reaction, 2～10 minutes reaction times; The maleic anhydride consumption is 5～10 weight % of polymer loading, and the consumption of radical initiator is 0.1～0.5 weight % of polymer loading; Behind maleic anhydride graft, maleic anhydride grafts diamine compounds fusion amination, 180～200 ℃ of temperature of reaction, in 4～8 minutes reaction times, the diamine compounds consumption is 1.8 weight % of maleic anhydride grafts consumption; Described polymkeric substance is polypropylene, ethylene-propylene terpolymer, polyethylene, (ethylene-octene) multipolymer or styrene-butadiene-styrene block copolymer;
Described polymeric matrix is polypropylene, polyethylene, polystyrene, polyvinyl chloride.
2. reacting nano inorganic particle/polymer composites according to claim 1 is characterized in that described radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; Described coupling agent is γ-methacryloxypropyl trimethoxy silane.
3. the preparation method of the described reacting nano inorganic particle/polymer composites of claim 1, it is characterized in that for: with modified Nano particle, functionalized polymer reactive compatibilizer, polymeric matrix melt blending, time is 6～10 minutes, 180～200 ℃ of temperature.
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| EP2110388A1 (en) * | 2008-04-18 | 2009-10-21 | Nanoresins AG | Polymerisable substance with connected nanoparticles |
| BR112012007064A2 (en) * | 2009-09-29 | 2016-04-19 | Interfacial Soluitons Ip Llc | compatibilizer mixture for polymeric compositions |
| CN102504611A (en) * | 2011-10-17 | 2012-06-20 | 中科院广州化学有限公司 | Improved silicon dioxide, high-performance lithium ion battery separator membrane and application thereof |
| CN102604204B (en) * | 2012-01-18 | 2013-10-23 | 大连工业大学 | Polypropylene composite material and preparation method thereof |
| CN103275372A (en) * | 2013-05-21 | 2013-09-04 | 苏州旭光聚合物有限公司 | Wear-resistant PP (Propene Polymer)/PE (Poly Ethylene) composite |
| CZ307301B6 (en) | 2013-12-17 | 2018-05-23 | Univerzita Tomáše Bati ve Zlíně | A compact formation of a composite character and a method of its preparation |
| CN104962026B (en) * | 2015-07-09 | 2017-05-03 | 河北工业大学 | Preparing method of composite compatilizer |
| CN105482228A (en) * | 2016-01-05 | 2016-04-13 | 广州枫叶管业有限公司 | Polyethylene nano-modified composite and preparing method and application thereof |
| ZA201705821B (en) * | 2016-08-26 | 2021-07-28 | Csir | Isotatic polypropylene based composite |
| CN108623749A (en) * | 2018-04-23 | 2018-10-09 | 郑州大学 | Polypropylene compatibilization and toughening agent and preparation method thereof |
| CN108676344A (en) * | 2018-05-16 | 2018-10-19 | 江苏兆鋆新材料股份有限公司 | A kind of modified polycarbonate, its manufactured polycarbonate thermoplastic prepreg and preparation method |
| CN109135551B (en) * | 2018-08-09 | 2020-11-20 | 深圳市前海奇迹新材料有限公司 | High-flexibility water-based UV coating |
| CN112514685A (en) * | 2020-12-04 | 2021-03-19 | 安徽强茗塑业科技有限公司 | Reinforced grass planting grid and preparation method thereof |
| CN113667220A (en) * | 2021-09-30 | 2021-11-19 | 遵义职业技术学院 | Preparation method of synergistic interface layer applied to polypropylene/nano silicon dioxide composite material |
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| CN1493607A (en) * | 2002-10-29 | 2004-05-05 | 中国科学院化学研究所 | Polypropylene/clay nano complex substance and its preparation method and application |
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