CN100348655C - Preparation of polymer composite material from halloysite nanometer tube - Google Patents
Preparation of polymer composite material from halloysite nanometer tube Download PDFInfo
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- CN100348655C CN100348655C CNB2005100353818A CN200510035381A CN100348655C CN 100348655 C CN100348655 C CN 100348655C CN B2005100353818 A CNB2005100353818 A CN B2005100353818A CN 200510035381 A CN200510035381 A CN 200510035381A CN 100348655 C CN100348655 C CN 100348655C
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Abstract
The present invention relates to a method for preparing polymer composite material from halloysite nanometer tubes, which comprises the steps: halloysite nanometer tubes are mixed with polymer according to the weight ratio of 40 to 99: 0.5 to 60, and are homogeneously dispersed in a polymeric matrix; then, polymer composite material is obtained through forming. The halloysite nanometer tubes are natural clay minerals which are in a micro tubular structure formed by twisting silicate sheet layers under the natural condition. The polymer is one or more than one of thermoplastic plastic, thermosetting plastic and rubber. The polymer nanometer composite material which has obviously enhanced mechanical performance and flame retardant performance is formed. The present invention overcomes the defect that the existing nanometer fillers are not easily dispersed, and fillers are cheap and are easily obtained without dust pollution.
Description
Technical field
The present invention relates to the polymer composites technical field, be meant that specifically halloysite nanotubes is used to prepare the method for polymer composites.
Background technology
The principal character of nano composite material (Nanocmposites) be the one or more components in the compound system have at least one dimension with nano-scale (≤100nm) be evenly dispersed in the matrix of another component, be called hybrid materials or hybrid material (Hybrid Materials) sometimes again.The Organic that polymkeric substance and some inorganics are formed, its polymkeric substance forms even and firm combining with the inorganics with nano-scale, the nanophase specific surface area is big, and phase spacing is little, there is special interaction, so its performance has been compared significant difference with corresponding macroscopic view or micron order matrix material (for example, traditional Inorganic Fillers Filled is polymer-modified), shows brand-new performance or function.
To have the properties-correcting agent of nano-scale and filler and polymkeric substance compound is the main method of preparation polymer nanocomposites.
The used filler of polymer nanocomposites can be divided into two classes, promptly natural Nano filling and synthetic Nano filling at present.
Natural nano level filler is meant the structural unit that contains nanoscale in the structure, the structural unit of nanoscale can be scattered in to form polymer nanocomposites in the polymkeric substance in the preparation of polymkeric substance.What this type of material application was maximum is various layered silicates, for example polynite and kaolin etc.The main difficulty that this class nano-sized filler is used is to overcome the interlayer ion key and could forms nano level dispersion, thereby preparation process is often relatively more difficult, and dispersion effect is undesirable.
The synthetic Nano filling comprises various synthetic mineral filler powders, for example nano-calcium carbonate, nano silicon, nano titanium oxide, nano-sized magnesium hydroxide etc.For various synthetic nano-powders, there are many shortcomings that are difficult to overcome.Preparation technology's relative complex of nano-powder at first, cost are high always; Secondly, the nano-powder tap density is extremely low, causes reuniting very easily taking place, and dust pollution is serious; Moreover the reunion of nano-powder makes its surface modification difficulty, further causes its difficulties in dispersion.
Summary of the invention
The objective of the invention is to defective at the prior art existence, the method that provides a kind of halloysite nanotubes to be used to prepare polymer composites, formation has the polymer nanocomposites of the mechanical property and the flame retardant properties of obvious raising; Overcome the shortcoming of existing Nano filling difficulties in dispersion, and filler is cheap and easy to get, does not have dust pollution.
The method that halloysite nanotubes of the present invention is used to prepare polymer composites comprises: halloysite nanotubes and polymkeric substance mix by the weight ratio of 1: 10,1: 100,40: 100 or 1: 5, halloysite nanotubes is dispersed in the polymeric matrix, and moulding obtains the polymer composites goods then.
Described halloysite nanotubes is a kind of natural clay mineral, and the micro-tube shaped structure by the silicate lamella curls and forms under natural condition has 1: 1 identical SiO
2/ Al
2O
3Ratio, laminated structure has been curled into SiO
2At outer, Al
2O
3Barrel-like structure at internal layer.General halloysite nanotubes is curled by a plurality of lamellas and forms, and external diameter of pipe is about 10-50nm, and internal diameter is about 5-20nm, and length is about 2-40 μ m, so be natural many walls microtubule.When the pH value is between 4～9, the surperficial Z current potential of halloysite nanotubes-20～-change between the 50mV.When pH less than 6 the time, have faint negative charge in the pipe.The spacing of adjacent tube wall (interlamellar spacing) has 7.3 dusts and two numerical value of 10.1 dusts according to whether moisture.It should be noted that halloysite owing to be curled into pipe fully, do not resemble and have ion exchangeable or swelling property other clay mineral.From chemical property, the halloysite nanotubes top layer has and SiO
2Closely similar surface properties, and internal layer character and Al
2O
3Similar.
Described polymkeric substance is one or more in thermoplastics, thermosetting resin, the rubber.
Described thermoplastics comprises one or more mixtures in polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene terpolymer (ABS), polymethylmethacrylate general-purpose plastics such as (PMMA) and polymeric amide (nylon), thermoplastic polyester (PET and PBT), polyoxymethylene (POM), the polycarbonate engineering plastics such as (PC) etc.;
Described thermosetting resin comprises one or more mixtures in Resins, epoxy (EP), unsaturated polyester resin (UP), allylic resin, aminoresin, thermoset polyimide resin, cyanate ester resin, bimaleimide resin (BMIs), resol, the heat-curable urethane (PU) etc.;
Described rubber comprises natural rubber (NR) and various synthetic rubber, as styrene-butadiene rubber(SBR) (SBR), polyisoprene (IR), isoprene-isobutylene rubber (IIR), polybutadiene rubber (PBR), acrylonitrile butadiene copolymer (NBR), and one or more the mixture in the various thermoplastic elastomers etc.
Halloysite nanotubes and mixed with polymers and moulding can be adopted general mixing equipment of prior art and molding device.For example adopt twin screw extruder, Banbury mixer or other mixing equipment to carry out melting mixing, with equipment moulding such as forcing machine or injector to the thermoplastics base polymer; The used mixing equipment of thermosetting resin base polymer is comprised shredder and stirrer etc.; The used mixing equipment of rubber polymer is comprised various compounding rubber equipment.
In order further to improve the consistency of halloysite nanotubes and thermoplastics, strengthen combining between halloysite nanotubes and the polymeric matrix, and halloysite nanotubes is fully disperseed in polymeric matrix, the present invention can also adopt surface-modifying agent that the halloysite nanotubes material is carried out surface treatment, described surface treatment is to adopt this area method in common, and the consumption of surface-modifying agent accounts for 0.5～5% weight of halloysite nanotubes.
Described surface-modifying agent can adopt the general surface-modifying agent in this area, and the contriver explores through creative, finds that the best surface properties-correcting agent that the present invention adopts comprises three classes, wherein
(1) various organosilanes such as γ-An Jibingjisanyiyangjiguiwan, γ-epoxypropyl triethoxyl silane, ethenylphenyl Edamine propyl trimethoxy silicane mono-hydrochloric salts, γ-methacryloxypropyl trimethoxy silane, titanate coupling agent.This class surface-modifying agent can directly add in the mixed system of halloysite nanotubes or halloysite nanotubes and polymkeric substance.
(2) be used for halloysite nanotubes grafted vinyl monomer, comprise maleic anhydride (MAH) and ester thereof, fumaric acid anhydride (FAH) and ester thereof, vinylformic acid (AA), methacrylic acid (MA), long-chain acrylate or methacrylic ester, propenoic acid beta-hydroxy propyl ester (HPA), Jia Jibingxisuanβ-Qiang Yizhi (HEMA), acrylamide, divinylbenzene, Ethylene glycol dimethacrylate etc.; This class surface-modifying agent can be under thermal initiation or light-initiated condition and the halloysite nanotubes grafting.
(3) be used to improve the macromolecular coupling agent at polymkeric substance and halloysite nanotubes interface, comprise polypropylene grafted maleic anhydride and polycthylene grafted maleic anhydride etc.This class surface-modifying agent can directly add in the mixed system of halloysite nanotubes and polymkeric substance.
The present invention compared with prior art has following advantage and beneficial effect:
1, the halloysite nanotubes that adopts of the present invention is with low cost, and aboundresources can reduce the production cost of polymer composites greatly.
2, the polymer composites of the present invention's preparation can be applicable to make various thermoplasticss, thermosetting resin and vulcanized rubber article, also can be used for other polymer arts such as tackiness agent, coating, has broad application prospects.
3, the thermoplasticity of the present invention's preparation and the mechanical properties such as shock strength, modulus in flexure and flexural strength of thermoset polymer composite significantly improve, and the flame retardant properties of heat decomposition temperature and raising polymkeric substance also obviously improves.
4, the polymer composites of the present invention's preparation is used for rubber materials, can improve modulus, tensile strength, tensile yield, tension set, tear strength and the hardness of rubber significantly, also can improve cross-linking density, aging resistance, dynamic properties and the processing characteristics of rubber.
Embodiment
Embodiment 1
The first step: 1 gram γ-An Jibingjisanyiyangjiguiwan is dissolved in the small amount of acetone, evenly is sprayed in the halloysite nanotubes material then, treat then the halloysite nanotubes of modification to be dried 4 hours under 80 ℃ of conditions after acetone volatilizees naturally.
Second step: the halloysite nanotubes of 100 gram surface modifications is mixed with 1000 gram polyvinyl resins, carry out the melt blending granulation with twin screw extruder then.
The 3rd step: with injector the mixture that obtains in second step is carried out injection molding, make polyethylene/halloysite nanotubes composite product.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing halloysite nanotubes is dispersed in the polyethylene matrix with nanoscale, illustrates to have made polymkeric substance/halloysite nanotubes matrix material.
Embodiment 2
The first step: 1 gram ethenylphenyl Edamine propyl trimethoxy silicane mono-hydrochloric salts is dissolved in the small amount of ethanol, hydrolysis evenly was sprayed in the halloysite nanotubes after 3 minutes, treated then the halloysite nanotubes of modification to be dried 5 hours under 90 ℃ of conditions after ethanol volatilizees naturally.
Second step: the halloysite nanotubes of 1 gram surface modification is mixed with 100 gram Resins, epoxy, stirred 2 hours under the room temperature.
The 3rd step: 15 gram m-xylene diamines are joined in the said mixture, stir, the degassing is poured in the test mould then.
The 4th step: after room temperature is parked 24 hours,, make Resins, epoxy/halloysite nanotubes matrix material with 70 ℃ of after fixing one hour.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing halloysite nanotubes is dispersed in the Resins, epoxy with nanoscale, illustrates to have made polymkeric substance/halloysite nanotubes matrix material.
Embodiment 3
The first step: the modification halloysite nanotubes that 10 examples two that restrain are obtained joins in the proper amount of acetone, adds 3 gram Isooctyl acrylate monomers and 0.1 gram photoinitiator then, stirs 10 minutes.Place pallet then, treat that acetone volatilizees naturally, the treatment with ultraviolet light certain hour is used in oven dry, makes the modification halloysite nanotubes.
Second step: adopt two roller mill mixing natural rubbers (NR), Synergist S-421 95, reach modification halloysite nanotubes material, after spending the night, rubber unvulcanizate uses the vulcanizing press sulfidization molding, cure conditions is: 143 ℃ * sulfurizing time, make natural rubber/halloysite nano composite material.
The rubber unvulcanizate basic recipe: natural gum 100, modification halloysite nanotubes 40, stearic acid 2, ZnO4 promotes CZ 1.5, promotes DM 0.5, sulphur 1.5.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing halloysite nanotubes is dispersed in the natural rubber matrix with the yardstick of tens nanometers, illustrates to have made natural rubber/halloysite nanotubes matrix material.
Table 1 has been listed the influence to the natural rubber vulcanized rubber cross-linking density of halloysite modification and content, from table, can see, the cross-linking density of natural gum has only 0.194, and after adding the unmodified halloysite nanotubes of 40wt%, the cross-linking density of system raises, the cross-linking density of the system of adding 40wt% modification halloysite nanotubes is then by significantly raising, risen to 0.310 from 0.194 of unmodified halloysite nanotubes filling, illustrated that Chemical bond takes place on properties-correcting agent and halloysite surface, and two key generation chemical actions with rubber, form good cross-linked network, make halloysite play the effect of physical crosslinking point, thereby improved the cross-linking density of system greatly.
Trachelospermum jasminoide modification of table 1 dust and content are to the influence of natural rubber vulcanized rubber cross-linking density
| Sample | Natural rubber | NR/ halloysite nanotubes (100/40) | NR/ modification halloysite nanotubes (100/40) |
| Cross-linking density | 0.194 | 0.220 | 0.310 |
Table 2 is physical and mechanical propertiess of natural gum/modification halloysite nanotubes matrix material.Can to natural gum good enhancement be arranged by the modification halloysite nanotubes from table 2, this is to fill the finer and close enhancing network structure of network because the tubular structure of halloysite nanotubes forms than tradition.Therefore the halloysite nanotubes infill system greatly reduces tension set, has improved tensile strength.This mainly is because the silanol groups generation Chemical bond on properties-correcting agent and halloysite surface, form and stablize bonding action, and when vulcanizing, system forms good cross-linked network, improve the interface interaction power of halloysite nanotubes and rubber, formed physical and mechanical properties natural rubber/modification halloysite nano composite material preferably.
The physical and mechanical properties of table 2 natural gum/modification halloysite nanotubes matrix material
| Mechanical property | NR | NR/ modification halloysite nanotubes (10wt %) | NR/ modification halloysite nanotubes (30wt %) | NR/ carbon black (50 part of half reinforcement) |
| 300% stress at definite elongation, the MPa tensile strength, the MPa tensile yield, the % tensile set, % hardness (Shao Er A), degree | 1.7 24.7 730 12 42 | 6.6 32.0 630 25 58 | 7.2 26.5 550 37 63 | 9.6 27.9 560 38 65 |
Embodiment 4
The first step: the two γ-methacryloxypropyl trimethoxy silane of 1 gram are dissolved in the small amount of acetone, evenly are sprayed on then in the halloysite nanotubes material, then the halloysite nanotubes of modification was dried 4 hours under 80 ℃ of conditions.
Second step: the halloysite nanotubes of 200 gram surface modifications is mixed with 1000 gram acrylic resins, carry out the melt blending granulation with twin screw extruder then.
The 3rd step: with injector the mixture that obtains in second step is carried out injection molding, make polypropylene/halloysite nanotubes matrix material.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing halloysite nanotubes is dispersed in the polypropylene matrix with nanoscale, illustrates to have made polymkeric substance/halloysite nanotubes matrix material.
Table 3 has been listed the part mechanical property of polypropylene/halloysite matrix material.Table can be seen thus, polypropylene/the mechanical properties such as shock strength, tensile strength, modulus in flexure and flexural strength of halloysite nano composite material all have the raising of different amplitudes than virgin pp, particularly with the nanometer composite polypropylene material of modification halloysite nanotubes filling, its shock strength, flexural strength and modulus in flexure are by significantly improving.
The influence of table 3 polypropylene/halloysite composite materials property
| Properties-correcting agent | Shock strength (KJ/m 2) | Tensile strength (MPa) | Modulus in flexure (MPa) | Flexural strength (MPa) |
| Pure PP halloysite nanotubes modification halloysite nanotubes | 4.06 6.36 8.36 | 32.4 32.0 34.5 | 1183.00 1254.67 1592.55 | 40.65 41.96 46.86 |
Embodiment 5
The first step: 1 gram propenoic acid beta-hydroxy propyl ester and 0.5 gram tolylene diisocyanate blending surface properties-correcting agent are dissolved in the small amount of acetone, evenly be sprayed on then in the 100 gram halloysite nanotubes materials, treat after acetone volatilizees naturally the halloysite nanotubes of modification to be dried 4 hours under 80 ℃ of conditions.
Second step: the halloysite nanotubes of surface modification is mixed with acrylic resin, carry out the melt blending granulation with twin screw extruder then.
The 3rd step: with injector the mixture that obtains in second step is carried out injection molding, make polypropylene/halloysite nanotubes matrix material.
Table 4 has been listed various polypropylene/halloysite nanotubes matrix material thermal degradation temperature.
The various polypropylene of table 4/halloysite nanotubes matrix material thermal degradation temperature
| Form | Weightless 5% temperature (℃) | Weightless 10% temperature (℃) | Maximum weight loss rate temperature (℃) |
| The unmodified halloysite nanotubes 10% unmodified halloysite nanotubes 30% modification halloysite nanotubes 10% modification HNT 20 modification HNT 30% of pure PP | 384 415 381 445 433 433 | 399 430 400 461 445 447 | 451 460 440 487 474 478 |
Can see that by table 4 the highest the raising above 60 ℃ of temperature in PP weightlessness 5% illustrates that thermostability improves greatly.
Claims (8)
1, a kind of halloysite nanotubes is used to prepare the method for polymer composites, it is characterized in that halloysite nanotubes and polymkeric substance mix by the weight ratio of 1: 10,1: 100,40: 100 or 1: 5, halloysite nanotubes is dispersed in the polymeric matrix, and moulding obtains the polymer composites goods then; Described halloysite nanotubes is a kind of natural clay mineral, by silicate lamella curling micro-tube shaped structure that forms under natural condition; Described polymkeric substance is one or more in thermoplastics, thermosetting resin, the rubber.
2, method according to claim 1 is characterized in that described thermoplastics comprises one or more the mixture in polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene terpolymer, polymethylmethacrylate, polymeric amide, thermoplastic polyester, polyoxymethylene, the polycarbonate.
3, method according to claim 1 is characterized in that described thermosetting resin comprises one or more the mixture in Resins, epoxy, unsaturated polyester resin, allylic resin, aminoresin, thermoset polyimide resin, cyanate ester resin, bimaleimide resin, resol, the heat-curable urethane.
4, method according to claim 1 is characterized in that described rubber comprises one or more the mixture in styrene-butadiene rubber(SBR), polyisoprene, isoprene-isobutylene rubber, polybutadiene rubber, the acrylonitrile butadiene copolymer.
5, according to the described method of one of claim 1-4, it is characterized in that halloysite nanotubes being carried out surface treatment with surface-modifying agent, the surface-modifying agent consumption accounts for 0.5～5% weight of halloysite nanotubes.
6, method according to claim 5 is characterized in that surface-modifying agent is γ-An Jibingjisanyiyangjiguiwan, γ-epoxypropyl triethoxyl silane, ethenylphenyl Edamine propyl trimethoxy silicane mono-hydrochloric salts, γ-methacryloxypropyl trimethoxy silane or titanate coupling agent.
7, method according to claim 5 is characterized in that described surface-modifying agent is one or more in maleic anhydride and ester, fumaric acid anhydride and ester thereof, vinylformic acid, methacrylic acid, long-chain acrylate, methacrylic ester, propenoic acid beta-hydroxy propyl ester, Jia Jibingxisuanβ-Qiang Yizhi, acrylamide, divinylbenzene, the Ethylene glycol dimethacrylate.
8, method according to claim 5 is characterized in that described surface-modifying agent is polypropylene grafted maleic anhydride or polycthylene grafted maleic anhydride.
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| CN116925516B (en) * | 2023-08-17 | 2024-02-09 | 韦尔通科技股份有限公司 | High-temperature-resistant and low-temperature-resistant bio-based hot melt adhesive pipe and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810734A (en) * | 1987-03-26 | 1989-03-07 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Process for producing composite material |
| JPH07324390A (en) * | 1994-05-31 | 1995-12-12 | Nippon Kayaku Co Ltd | Humidity conditioning material |
| CN1318657A (en) * | 2000-04-04 | 2001-10-24 | 石美秀 | Manufacture of fibre containing functional mineral powder and fibre prepared by the same |
| CN1346385A (en) * | 1999-02-10 | 2002-04-24 | Basf公司 | Thermoplastic nanocomposites |
| CN1362641A (en) * | 2000-12-28 | 2002-08-07 | 伊斯曼柯达公司 | Imaging element with supporter containing nano composition material |
| KR20030020190A (en) * | 2001-09-03 | 2003-03-08 | 한국화학연구원 | An Preparation Method of Polymer-kaolinite Nanocomposite |
| CN1473176A (en) * | 2001-07-23 | 2004-02-04 | ������������ʽ���� | Thermoplastic resin composition, molded article, and process for producing the same |
-
2005
- 2005-06-24 CN CNB2005100353818A patent/CN100348655C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810734A (en) * | 1987-03-26 | 1989-03-07 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Process for producing composite material |
| JPH07324390A (en) * | 1994-05-31 | 1995-12-12 | Nippon Kayaku Co Ltd | Humidity conditioning material |
| CN1346385A (en) * | 1999-02-10 | 2002-04-24 | Basf公司 | Thermoplastic nanocomposites |
| CN1318657A (en) * | 2000-04-04 | 2001-10-24 | 石美秀 | Manufacture of fibre containing functional mineral powder and fibre prepared by the same |
| CN1362641A (en) * | 2000-12-28 | 2002-08-07 | 伊斯曼柯达公司 | Imaging element with supporter containing nano composition material |
| CN1473176A (en) * | 2001-07-23 | 2004-02-04 | ������������ʽ���� | Thermoplastic resin composition, molded article, and process for producing the same |
| KR20030020190A (en) * | 2001-09-03 | 2003-03-08 | 한국화학연구원 | An Preparation Method of Polymer-kaolinite Nanocomposite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617974A (en) * | 2012-04-01 | 2012-08-01 | 宁波康氏塑料科技有限公司 | Acrylonitrile butadiene styrene (ABS)/ nerchinskite composite material and preparation method thereof |
| CN102634242A (en) * | 2012-04-18 | 2012-08-15 | 天津大学 | Method for preparing composite material by modifying halloysite nanotube and compounding waterborne polyurethane |
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