EP1931351A2 - Produits chimiques métallisés nanostructurés alliés dans des polymères - Google Patents

Produits chimiques métallisés nanostructurés alliés dans des polymères

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Publication number
EP1931351A2
EP1931351A2 EP06851608A EP06851608A EP1931351A2 EP 1931351 A2 EP1931351 A2 EP 1931351A2 EP 06851608 A EP06851608 A EP 06851608A EP 06851608 A EP06851608 A EP 06851608A EP 1931351 A2 EP1931351 A2 EP 1931351A2
Authority
EP
European Patent Office
Prior art keywords
polymer
poms
metallized
compounding
group
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.)
Withdrawn
Application number
EP06851608A
Other languages
German (de)
English (en)
Other versions
EP1931351A4 (fr
Inventor
Joseph D. Lichtenhan
Xuan Fu
Joseph J. Schwab
Paul Wheeler
H. C. L. Abbenhuis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hybrid Plastics Inc
Original Assignee
Hybrid Plastics Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hybrid Plastics Inc filed Critical Hybrid Plastics Inc
Publication of EP1931351A2 publication Critical patent/EP1931351A2/fr
Publication of EP1931351A4 publication Critical patent/EP1931351A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
    • A61K31/505—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim
    • A61K31/513—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim having oxo groups directly attached to the heterocyclic ring, e.g. cytosine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring

Definitions

  • This invention relates generally to methods for enhancing the physical properties of a polymer and, more particularly, to methods for alloying a metallized nanostructured chemical into a polymer to enhance the properties of the polymer.
  • polymer morphology is a major factor that limits the ability of conventional fillers from accessing the free volume regions in a polymer system. Additional processing/compounding effort is normally required to force compatibilization between a filler and a polymer system because conventional fillers are physically larger than most polymer dimensions, are chemically dissimilar, and usually are high melting solids.
  • plasticizers or plasticizing agents with small, low molecular weight molecules (liquids and solids) known as plasticizers or plasticizing agents and with macro, micro and nanoscale particulates of dissimilar composition (e.g. inorganic) to that of the polymer (organic).
  • the function of a plasticizing agent is to aid in the slippage of polymer chains by one another, thus improving the processability and manufacturability of a particular polymer system.
  • fillers which have traditionally been composed of fibrous or particulate solids, have been combined with polymers to enhance physical properties such as dimensional stability, impact resistance, tensile and compressive strengths, and thermal stability.
  • metallic particles that are monodisperse or which have controlled and narrow particle size distributions as these are expected to form the most stable dispersions within polymer systems.
  • these particles would be well below the length scale necessary to scatter light and hence should appear transparent when compounded into plastics.
  • Nanostructured chemicals can be based on low-cost Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS).
  • POS Polyhedral Oligomeric Silsesquioxanes
  • POMS Polyhedral Oligomeric Metallosesquioxanes
  • cages that contain one or more metals inside or outside or bonded to the cage. In certain instances cages may contain more than one metal atom, or types of metal atoms or metal alloys.
  • POMS are illustrated by the representative structure and formula shown in Figure 3. Note that POMS are structurally and compositionally diverse and may contain several polyhedra, polymorphs, and compositional variances that can be utilized to control the physical properties of the POMS and the materials into which they are incorporated ( Figure 4).
  • POMS systems contain hybrid (i.e. organic-inorganic) compositions in which the internal frameworks are primarily comprised of inorganic silicon-oxygen bonds.
  • the exterior of a nanostructure is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic polymers.
  • R reactive and nonreactive organic functionalities
  • these POMS nanostructured chemicals are of low density (range 1.17 g/ml to 2.04 g/ml); highly dispersible into polymers and solvents; exhibit excellent inherent fire retardancy; optical, electronic properties, and radiation tolerance; and can range in diameter from 0.5 nm to 50 nm.
  • the present invention describes methods of preparing new polymer compositions by compounding metallized nanostructured chemicals into polymers.
  • the resulting nano-alloyed polymers are wholly useful by themselves, in combination with other polymers, or in combination with macroscopic reinforcements such as fiber! clay, glass mineral, nonmetallized POSS cages, metal particulates, and other fillers including diamond dust.
  • the nano-alloyed polymers are particularly useful for producing polymeric compositions with desirable physical properties such as adhesion to polymeric, composite and metal surfaces; water repellency; reduced melt viscosity; low dielectric constant; resistance to abrasion and fire; biological compatibility; lubrication; gas diffusion control; chemical resistance; and optical quality plastics.
  • compositions contain two primary material combinations: (1 ) metallized nanostructured chemicals, metallized nanostructured oligomers, or metal containing nanostructured polymers from the chemical classes of polyhedral oligomeric silsesquioxanes, polyhedral oligometallasilsesquioxanes, polyhedral oligomeric silicates, polyhedral oligometallosilicates, polyoxometallates, metallized fullerenes, carboranes, boranes, and polymorphs of carbon; and (2) traditional amorphous polymer systems such as acrylics, carbonates, epoxies, esters, silicones, polyolefins, polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides, and polymers containing functional groups, or traditional semicrystalline and crystalline polymer systems such as styrenics, amides, nitriles, olefins, aromatic oxides, aromatic s,
  • the compounding of metallized nanostructured chemicals into polymers is preferably accomplished via blending into the polymer system of interest with the metallized nanostructure. All types and techniques of blending, including melt blending, dry blending, solution blending, and reactive and nonreactive blending are effective.
  • selective incorporation of nanostructured chemicals into a specific region of a polymer can be accomplished by compounding into the polymer a metallized nanostructured chemical with a chemical potential (miscibility) compatible with the chemical potential of the region within the polymer to be alloyed.
  • the metallized nanostructure may be encouraged to associate with a specific region of the polymer because of the presence of reactive groups on the polymer with the metal contained in the nanostructure.
  • Reactive groups typically incorporated into polymers include olefins, cyanates, acrylates, amines, amides, alcohols, carbohydrates, esters, acids, nitriles and boron. The Lewis basicity of these groups provide an association with the metallized nanostructures' inherent Lewis acidity.
  • metallized nanostructured chemicals can be tailored to show compatibility or incompatibility with nearly all polymer systems.
  • Their physical size in combination with their tailorable compatibility enables metallized nanostructured chemicals to be selectively incorporated into plastics and control the dynamics of coils, blocks, domains, and segments, and subsequently favorably impact a multitude of physical properties.
  • Properties favorably improved are time dependent mechanical and thermal properties such as heat distortion, creep, compression set, strength, toughness, visual appearance, feel and texture, CTE, electrical, radiation, and oxidation stability, shrinkage, modulus, hardness, and abrasion resistance.
  • other physical properties favorably improved include biological compatibility, antimicrobial activity, thermal and electrical conductivity, adhesion, surface lubrication, laser-marking, fire resistance, gas and moisture permeation control, and paint, print, film and coating properties.
  • FIG. 1 shows the relative positions of an internal free volume and an external free volume of a polymer.
  • FIG. 2 illustrates different regions of phase separated polymer microstructure.
  • FIG. 3 illustrates a sample POMS nanostructure [(RSiO 1 . 5 ) 4 (RSi0 2 )3M] ⁇ 8 ).
  • FIG. 4 illustrates representative structures for POMS nanostructured chemicals.
  • FIG. 5 shows transmission of ultraviolet and visible light through various ((RSiOi .5 ) 4 (RSiO 2 ) 3 M] ⁇ 8 POMS.
  • FIG. 6 contains thermogravimetric plots showing decomposition and char yields of [(RSiOi.5)4(RSiO 2 ) 3 M] ⁇ 8 POMS.
  • FIG. 7 shows components of an acrylic based Gd POMS thermoset coating.
  • FIG. 8 shows a comparison of 40 wt% Gd POMS/Coating relative to Pb and Al X-ray shielding.
  • FIG. 9 illustrates the measured and calculated thermal neutron attenuation resulting from [(JBuSiOLs) 4 (JBuSiO 2 ) S Gd]I 8 .
  • FIG. 10 is a thermogravimetric plot for paraffin wax -vs- 70 wt% [(iBuSiOi .5)4(iBuSiO 2 ) 3 Gd] ⁇ 8 / 30% paraffin alloy.
  • R is the same as defined above and X includes but is not limited to OLi, ONa 1 OK, OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR 2 ) isocyanate (NCO), and R.
  • the symbol M refers to metallic elements within the composition that include low and high atomic number metals, s and p block metals, d and f block metals including transition, lanthanide, actinide metals.
  • ML represents a metal as defined above and a (L) ligand coordinated to the metal.
  • a variety of ligands may coordinate to the metal in a covalent fashion to maintain proper oxidation state or in a dative fashion to maintain coordination sphere electronics of the metal atom.
  • transition metals containing s,p,d orbitals generally prefer electron counts of eighteen at the metal center whereas actinide and lanthanides can exceed this rule due to the presence of f orbitals.
  • Typical L groups include solvent molecules such as tetrahydrofuran, pyridine, water, or alkoxides, amides, oxides, and halides.
  • the symbols m, n and j refer to the stoichiometry of the composition.
  • the symbol ⁇ indicates that the composition forms a nanostructure and the symbol # refers to the number of silicon atoms contained within the nanostructure.
  • the value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12. It should be noted that ⁇ # is not to be confused as a multiplier for determining stoichiometry, as it merely describes the overall nanostructural characteristics of the system (aka cage size).
  • POMS metallized nanostructured chemicals
  • the keys that enable POMS to function as molecular level reinforcing and alloying agents are: (1 ) their unique size with respect to polymer chain dimensions, and (2) their ability to be compatibilized with polymer systems to overcome repulsive forces that promote incompatibility and expulsion of the nanoreinforcing agent by the polymer chains. That is, metallized nanostructured chemicals can be tailored to exhibit preferential affinity/compatibility with polymer microstructures through variation of the R groups on each nanostructure. The metallized nanostructure may be encouraged to associate with a specific region of the polymer because of the presence of reactive groups on the polymer with the metal contained in the nanostructure.
  • Reactive groups typically incorporated into polymers include acrylates, amines, amides, alcohols, esters, nitriles and boron.
  • the Lewis basicity of these groups provide an association site for the metal atom in the nanostructure as it is inherent a Lewis acid.
  • POMS can be tailored to be incompatible with microstructures within a polymer, thus allowing for selective reinforcement of specific polymer microstructure or migration to the surfaces of such polymers for modification of surface properties. Therefore, the factors to effect a selective nanoreinforcement include specific nanosizes of metallized nanostructured chemicals, distributions of nanosizes, and incompatibilities and disparities between the R groups on the POMS and the polymer the types of functionality present in the specific polymer system.
  • Metallized nanostructured chemicals such as the POMS structures illustrated in Figure 4, are available as both solids and oils.
  • the physical form is largely controlled by the type of R group on each cage and the topology of the structures.
  • POMS with rigid structure or rigid R groups will generally render crystalline solids.
  • Both crystalline and amorphous POMS dissolve in solvents, monomers, and molten polymers thus solving the long-standing dispersion problem associated with traditional particulate fillers.
  • POSS and POMS dissolve in plastics at the molecular level, the forces (Le ⁇ free energy) from solvation/mixing are sufficient to prevent the cages from coalescing and forming micron sized agglomerated domains as occurs with traditional and other organofunctionalized fillers. Agglomeration of particulate fillers has been a problem that has traditionally plagued compounders and molders.
  • Table 1 lists the size range of POSS relative to polymer dimensions and filler sizes.
  • the size of POSS is roughly equivalent to that of most polymer dimensions, thus at a molecular level POSS can effectively alter the motion of polymer chains which favorably impacts physical properties.
  • the present invention demonstrates that additional property enhancements can be realized by the incorporation of metallized nanostructured chemicals into plastics. This greatly simplifies the prior art processes and affords a greater degree of property control as a direct result of the incorporation of metal atoms into the resulting material.
  • metallized nanostructured chemicals possess spherical shapes (per single crystal X-ray diffraction studies) like molecular spheres, and because they dissolve, they are also effective at reducing the viscosity of polymer systems. This benefit is similar to what is produced through the incorporation of plasticizers into polymers, yet with the added benefits of reinforcement of the individual polymer chains due to the nanoscopic nature of the entity.
  • ease of processability and reinforcement effects are obtainable through the use of POMS where prior art would have required the use of both POSS and metal fillers.
  • cost and weight advantages are realized as metal fillers are more dense than POMS and in many cases the properties of the atom are desired rather than any inherent property of the metallic particle.
  • Example 1 Alloying POMS into Polycarbonate
  • a series of POMS were compounded into Bayer Makrolon ® polycarbonate 2405 using a twin screw extruder.
  • the POMS and polymer were dried prior to compounding to ensure a maximum state of alloying.
  • the POMS-reinforced samples were then molded into discs, dogbones and other test specimens and subjected to physical characterization.
  • the optical characteristics of POMS polycarbonate is especially important to the application of polycarbonate as an optical resin. Optical properties were retained (e.g. in polycarbonate containing 2 wt% loadings of (a) [(PhSiOi.
  • compositions, sizes, and loading levels of POMS are observed to have a pronounced effect on the degree of various physical property enhancement.
  • the mechanism for this enhancement is observed to be associated with the chain motion and free volume between the POMS and the polymer chain.
  • the incorporation of POMS provides for an enhanced hydrophobic surface which allows for improved hydrophobicity and weatherability of PC.
  • metals such as Cerium which provide for UV stabilization.
  • the incorporation of metal atoms into POMS can be highly effective.
  • the incorporation of cerium and titanium atoms into the corner of POMS can protect polymers against UV induced chain cleavage and discoloration (Figure 5).
  • Gadolinium POMS [(PhSiOi. 5 )4(PhSiO 2 ) 3 Gd] ⁇ 8 , [(iBuSiOi. 5 )4(iBuSiO 2 )3Gd] ⁇ 8 and Boron POMS [(PhSiOi. 5 )4(PhSiO 2 ) 3 B] ⁇ 8 , [(iBuSiOi. 5 ) 4 (iBuSiO 2 ) 3 B] ⁇ 8 were compounded into hot melt waxes using extrusion and single pot low shear blending techniques. The compatibility as evidenced by visual solubilization was found to range from 0.1 through 80 wt% into hot wax.
  • the combination of polyamide, polyurethane, polyolefin and POSS and POMS into formulations are highly desirable as the polyamide and polyurethane provides broad adhesive properties, while the polyolefin provides low cost and low melting point.
  • the POSS/POMS provides compatibility between the two resin systems and enhancement of physical properties. POSS/POMS is especially useful for improving chemical and oil resistance of the final formulation. POSS/POMS are also useful for improving the compatibility of the dissimilar polymer systems. Zhang et al. in 2002 reported that methacrylate POSS compatibilized polymethacrylate and polystyrene on the microscopic scale, 35 Macromolecules 8029-38 (2002). POMS has now been reduced to practice for the formulation of dissimilar polymer systems.
  • POSS and POMS can be utilized to obtain a synergy with conventional stabilizers and fragrances, pigments, dyes, and processing aids.
  • thermoplastics are highly desirable as coatings for shielding of electronic components against X-ray, thermal neutrons, protons and electrons.
  • Example 4 X-Ray Radiation Barrier in Crosslinked Coating A series of X-ray absorption measurements were conducted on Gd POMS coatings to determine their effectiveness at providing shielding from X-ray radiation.
  • the advantages of the Gd POMS coating is its ductility, rapid and low-cost coating method, light weight, and electrically insulative properties. The results confirmed
  • the Gd POMS is as good as solid Al metal.
  • the absolute flux was determined from the measured induced activity in the gold foils.
  • a preferred method of incorporating Gd POMS onto a semiconductor is to alloy the Gd POMS into a hot melt wax adhesive and then cast this alloy into a suitable shape for application.
  • the rods of the alloyed polymer can be incorporated into a hot melt glue gun and the Gd POMS/polymer can be applied directly over the bare chip or its dye and thereby fully protect it against ionizing thermal neutrons, X-ray, and moisture.
  • Example 6 Metallized POSS for improved oxidative stability.
  • the POSS alloyed and POMS catalyzed epoxy resin exhibit improved resistance to steam and ozone. After 100 ozone sterilization cycles, a total weight loss of 20% was observed for the POSS/POMS alloyed resin as compared to a 40% weight loss for the same system cured with imidazole curing agents. After 50 steam sterilization cycles, a total weight gain of 5% for the was observed for the POSS/POMS alloyed resin as compared to a 10% weight gain for the same system cured with commercial imidazole. Additionally the POSS/POMS alloyed resin retained its original optical clarity, texture, and bond strength relative to systems without the POSS/POMS. The incorporation of [(PhSiOi.
  • Example 7 POMS for improved fire retardancy.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Les produits chimiques métallisés nanostructurés selon l'invention sont incorporés au niveau moléculaire sous forme d'agents d'alliage pour le renfort de microstructures polymères, y compris des bobines, domaines, chaînes et segments polymères. Des processus de mélange direct sont efficaces en raison de la compatibilité adaptable des produits chimiques métallisés nanostructurés avec les polymères.
EP06851608A 2005-08-19 2006-08-21 Produits chimiques métallisés nanostructurés alliés dans des polymères Withdrawn EP1931351A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US70963805P 2005-08-19 2005-08-19
PCT/US2006/032651 WO2008051190A2 (fr) 2005-08-19 2006-08-21 Produits chimiques métallisés nanostructurés alliés dans des polymères

Publications (2)

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EP1931351A2 true EP1931351A2 (fr) 2008-06-18
EP1931351A4 EP1931351A4 (fr) 2010-06-23

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EP (1) EP1931351A4 (fr)
JP (1) JP2009509030A (fr)
KR (1) KR20080065588A (fr)
CN (1) CN101405132A (fr)
RU (1) RU2008110470A (fr)
TW (1) TW200728359A (fr)
WO (1) WO2008051190A2 (fr)

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JP2009185224A (ja) * 2008-02-08 2009-08-20 Kri Inc 樹脂材料光学物性改質用添加剤およびその製造方法ならびに光学樹脂組成物およびその製造方法
CN103159948B (zh) * 2013-04-06 2014-12-10 吉林大学 一种低介电常数poss/含氟聚芳醚酮纳米复合材料及其制备方法
JP6439684B2 (ja) * 2013-04-23 2018-12-19 三菱瓦斯化学株式会社 ポリアミド樹脂組成物、及び成形体
CN103755847B (zh) 2013-12-31 2015-09-16 京东方科技集团股份有限公司 聚丙烯酸酯分散剂、颜料分散液、彩色光刻胶、彩膜基板和显示装置
CN104319008A (zh) * 2014-10-29 2015-01-28 江苏俊知技术有限公司 一种耐高温低损耗复合绝缘同轴电缆
CN108475552B (zh) * 2015-12-29 2022-07-12 3M创新有限公司 用于高频电磁干扰(emi)应用的复合物
CN109553949B (zh) * 2018-11-21 2021-03-02 金发科技股份有限公司 一种抗菌聚碳酸酯复合材料及其制备方法
KR102415476B1 (ko) * 2019-02-25 2022-07-01 국보운수 (주) 내구성이 향상된 파레트.
CN111732775A (zh) * 2020-07-02 2020-10-02 北京科技大学 一种用于空间中子屏蔽的聚合物复合材料及其制备方法

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Publication number Publication date
TW200728359A (en) 2007-08-01
WO2008051190A9 (fr) 2009-01-08
CN101405132A (zh) 2009-04-08
JP2009509030A (ja) 2009-03-05
WO2008051190A3 (fr) 2008-11-13
EP1931351A4 (fr) 2010-06-23
WO2008051190A2 (fr) 2008-05-02
KR20080065588A (ko) 2008-07-14
RU2008110470A (ru) 2009-09-27

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