US3722181A - Chromatographic packing with chemically bonded organic stationary phases - Google Patents

Chromatographic packing with chemically bonded organic stationary phases Download PDF

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US3722181A
US3722181A US00039665A US3722181DA US3722181A US 3722181 A US3722181 A US 3722181A US 00039665 A US00039665 A US 00039665A US 3722181D A US3722181D A US 3722181DA US 3722181 A US3722181 A US 3722181A
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stationary phase
substrate
aromatic hydrocarbon
bonded
packing
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J Kirkland
P Yates
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/283—Porous sorbents based on silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
    • B01J20/3261—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3276—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica

Definitions

  • ABSTRACT A process for making a chromatographic packing having'a polymeric stationary phase in which molecules having the formula Mar. 27, 1973 wherein R is a hydroxyl, or an aliphatic or aromatic hydrocarbon monovalent radical, and
  • R is a monovalent aliphatic or aromatic hydrocarbon radical
  • the polymeric stationary phase has a repeating unit of the formula wherein A is --O or a monovalent aliphatic or aromatic hydrocarbon radical, Y and is chemically bonded to the-surface of the substrate by an where silicon is part of a repeating unit.
  • polymolecular silicones have been reacted to chromatographic supports by employing two series of steps.
  • dimethyldichlorosilane or methyltrichlorosilane is bonded to the silica substrate.
  • organochlorosilanes are attached to the above methylchlorosilanes. Due to the 'use of highly reactive chlorosilanes in both series of steps, the extent of reaction in each series is difficult to control, which usually results in films of variable thickness.
  • the first series of steps places methyl groups on the substrate surface which reduces the effective polarity of the packing. This clearly represents a detriment when polarity is desired.
  • the second series of steps does not permit the use :of volatile organochlorosiles, thus restricting the choice of resultant stationary phases.
  • the particular organochlorosilanes that would be required as starting reagents toplace certain functional (e.g., amino) groups on the. surface would be self-reactive and thus selfdestructive.
  • R is a monovalent aliphatic or aromatic hydrocarbon.
  • R or K may contain atoms other than carbon and hydrogen.
  • the bonded polymolecular stationary phase has arepeating unit with the formula wherein A is a monovalent aliphatic or aromatic hydrocarbon radical.
  • the stationary phase is bonded to the polyvalent metaLcontaining substrate surface through an linkage, where M is the metal and is part of a repeating unit.
  • the chemically bonded stationary phase may be produced with a variety of functional groups, resulting in chromatographic packing with widely diverse selectivity.
  • the resulting packings may vary from extremely polar to non-polar according to the needs of the particular separation to be performed.
  • bonded stationary phase is controlled by controlling the quantities of starting materials.
  • bonded stationary phase may be deposited that is controllably monomolecularly or polymolecularly thick.
  • a polymolecular layer of predetermined thickness which will allow for precise diffusions, may be bonded to the substrate.
  • compositions of these blends are determined by controlling the concentrations of initial reactants.
  • a particularly .useful type of blend is one by which the degree ,of cross-linking in the bonded and polymerized stationary phase can be controlled. Greater concentrations of starting reagents in which R 'is a hydroxyl result in higher degree of cross-linking, which is particularly useful for gas chromatography (hereinafterreferred to as G.C.). On the other hand, greater concentrations of compounds with R being non-hydroxyl result in less cross-linking which is desired for liquid chromatography (hereinafter referred to as L.C. The extreme degrees of cross-linking are obtained by using either one of these (hydroxyl or non-hydroxyl) alone.
  • FIG. 1 is a diagrammatical representation of a crosssection of a preferred chromatographic support material.
  • FIG. 2 is a schematic cross-section of a polymeric stationary phase chemically bonded to a substrate.
  • FIG. 3 shows the chemical structure of the polymeric stationary phase.
  • FIG. 4 is a part of the liquid chromatographic separation of sulfonamides using the present invention.
  • FIG. 5 compares liquid chromatographic HETP v. Carrier Velocity Plots of the present invention with the prior art.
  • FIG. 6 is a plot of the'liquid chromatographic separation of thiolhydroxamates using the present invention.
  • FIG. 9 compares chromatograms showing the selectivity in gas chromatography of the ether bondedphase of the present invention.
  • FIG. 10 is a plot showing the relative bleed rate of a nitrile stationarybonded-phase of the present invention as against a column of the prior art.
  • FIG. 1 l is a plot of a thermograviometric curve for a vention.
  • FIG. 12 is a plot of. gas chromatographic separation of aromatic hydrocarbons with a nitrile bondedphase.
  • Chromatographic packings may be prepared having chemically bonded organic stationary phases with'a variety of functional groups, resulting in widely diverse chromatographic selectivity. Bonded-phase packings may be prepared for gas and liquid chromatography on a variety of substrates.
  • the composition of the substrate is not critical, except that its surface must be capable of chemically reacting with silanols. Silicacontaining substrates are preferred, although any polyvalent metal-containing substrate may be used where the valence of the metal is from-three'through five.
  • useful substrates include diatomaceous earths, silica gel, glasses, sand, alu- V chemically bonded nitrile packing of the present inminosilicates', quartz, porous silica beads, and clays. Additionally, non-alkaline metal oxides, alumina,
  • thoria titania, zirconia, and non-alkaline metals with an oxide skin may be utilized.
  • the shape of the particles is not critical. Examples of shapes include rings, polyhedra, saddles, platelets, fibers, hollow tubes, rods, or cylinders. Spherical supports are preferred because of their regular and reproducible packing characteristics and ease and con- .veniencein handling.
  • the controlled surface porosity, support of FIG. 1 (described in U.S. Pat. No. 3,505,785 and sold under the trade name Zipax by E. I. du Pont de Nemours and Company, Wilmington, Del.) is a preferred embodiment of a support structure. It has an impervious core 11, preferably of glass or other ceramic material and a porous coating 15 made up of sequentially adsorbed monolayers 13 of microparticles. It consists of discrete spherical particles having a large number of superficial shallow pores l2 and no deep pores. It has regular and reproducible packing characteristics,' ease and convenience in handling, and desirable characteristics for high-speed, high-efficiency gas and liquid chromatography.
  • the support or. substrate surface prefferably has a high initial population of metal-hydroxy, or preferably -SiOI-I groups. This is best accomplished by treating the surface with acid or base. The preferred procedure is to heat the support with concentrated nitric or hydrochloric acid on a steam bath for several hours. Excess acid or base should be removed from the surface by thorough washing before the support is dried for reaction with the silane reagents.
  • the reagents employed to produce the chemically bonded organic stationary phase are silanols having the formula where R and R are given above. They are preferably prepared from silicate esters with the formula where R and R5 are alkoxy, R is alkoxy or R and R is given above. 1
  • Table I A list of commercially available reagents is shown in Table I. Table II gives other reagents which are not presentlyv known to be commercially available. Their structures encompass a variety of configurations. These may be synthesized according to the general techniques contained in Chemistry of the Silicones, by R. G. Rochow, John Wiley & Sons, New York, 2nd Ed. l.
  • Methyltriethoxysilane (a, c).. CH Si(O C1115);
  • Methyltrimethoxysilane (b). CHJSI(O CH3);
  • a silicate ester when used as the reagent, must first more than about a lOO-fold equivalent excess.
  • the hydrolysis is northis hydrolysis include: mally run at elevated temperatures (preferably the 50 boiling point of the non-aqueous solvent) for a period 1. high or low pH (b or id of about 30 minutes to several hours.
  • the hydrolysis is preferably carried Pamal P y f P h sllahee before eafihon out by refluxingthe reagent in a non-aqueous solvent to the substrate 15 essemlal h produclng a m ly containing several molar excesses of water with an acid bonded Stational'y Phase haymg the requll'ed thlckness catalyst.
  • the solvent in addition to having some soluand porosity.
  • initiation of polymerization may be deterbility for water should be non-reactive with the reagent mmed y p e g a Small amount of the -e f water or the (acid or base) catalyst. It should boil in the ing luti n In Water.
  • the appearance of cloudiness mrange of about 25 to 300C, preferably 50 to 200C. dicates that the prepolymerization, having progressed Ethers such as tetrahydrofuran and dioxane have to the point where at least part of the silane reagent is worked satisfactorily. insoluble in water, is sufficient.
  • the reaction of the prepolymerized silane to the substrate, followed by the final polymerization, is carried out at temperatures from about 50 to 350C, a range of lO-250C. being' preferred. Times required for this step vary from a few minutes to several hours, but usually l-3 hours is adequate for the preferred temperature range.
  • silane ester reagents may be prepolymerized and reacted to the chromatographic substrates.
  • silane ester reagent is deposited on the chromatographic substrate by evaporation from a suitable volatile solvent.
  • the reagent is then hydrolyzed and prepolymerized by passing moist air or steam through the coated support.
  • the reaction with the surface and polymerization is then carried out by heating.
  • silicate ester reagent contained in a volatile unreactive solvent such as tetrahydrofuran is hydrolyzed and prepolymerized by adding aqueous hydrochloric acid and refluxing the mixture.
  • the substrate is added to this solution.
  • the volatile organic solvent is then removed by low temperature vacuum distillation. A large excess of toluene, xylene or other suita ble solvent is added to the wet powder and the watersolvent azeotrope is continuously removed until the reaction and polymerization is complete.
  • a final extraction step may be used to remove any silane not bonded to the substrate.
  • the solvents used in this step should have some solubility for the unbonded polymer which insures that the polymer left on the substrate is indeed chemically bonded thereto.
  • silane molecules may also be used in the prepolymerization, reaction, and polymerization steps. In this manner, bonded stationary phases having blends of various properties suitable for particular separations may be developed.
  • a particularly useful type of blend is the one controlling the extent of cross-linking in the polymerization process.
  • Packings for gas chromatography generally require a highly cross-linked structure, in order for the polymer to have optimum stability at high temperatures.
  • packings for liquid chromatography should have a less cross-linked polymeric phase. This lower order of cross-linking permits better penetration of the carrier, with subsequent improved 1 accessibility of the solute into the solvated polymeric structure.
  • the chemically bonded stationary phases also possess unique chemical and physical properties because of theirability to swell in certain solvents and to form gelatinous, ordered structures which function as selective stationary gel phases.
  • R Si (OR') reagents to the usual trialkoxysilicate, R Si (OR') reagents.
  • the addition of dialkoxysilicates to the reaction significantly reduces the cross-linking, since the other group (R") attached to the silicon atom does not engage in the polymerization.
  • the addition of the modifying functional group R also may impart desirable physical and chemical properties to the bonded phase.
  • the reaction of the silicate reagents to the substrate surface proceeds very close to quantitatively.
  • a monolayer film may be produced, for example, where it is desired to effect selective adsorption.
  • a substrate with a polymolecular layer is utilized.
  • the polymeric stationary phase is basically a three-dimensional porous network of repetitive, functional groups of the silane structure, chemically bonded to the support surface by an A schematic cross-section representation of the porous polymer structure is shown in FIG. 2 where the substrate is indicated at 20, the chemically bonded stationary phase at 21, a portion of polymer at 22, and the pores at 23.
  • FIG. 3 gives an exploded schematic representation of the claimed structure of a piece of polymer 22.
  • This chemically-bonded organic phase should have an average thickness of 30 A to 10,000 A, with 502,000 A being preferred. This preferred range encompasses sufficient thickness to ensure the desired chromatographic interactions without being so large (thick) so as to greatly affect column efficiency as a result of resistance to mass transfer of the solute within the polymeric phase.
  • the bonded stationary phase should have about 20 to 95 percent of its volume consisting of pores, with a range of 35 to percent preferred.
  • the polymer should be sufiiciently porous to allow penetration by the carrier phase and the sample components, while having sufficient cross-linking to ensure that the desired mechanical and chemical stability will be obtained.
  • the substrate is a particulate support. These particles are coated with the stationary phase and packed into columns. In the present invention, this stationary phase is chemically bonded to the support particles, which are then packed into columns in the usual way. However, the present invention is also useful in other forms of chromatography.
  • the stationary phase may be bonded to a substrate of silica gel. Also, where a capillary tube without p a particulate support is used for the column, a stationa- 'ry phase may be bonded directly onto the column wall diatomaceous earth with one of the bonded polymers.
  • This chromatographically active material is coated in thin layers on plates in the usual manner. The plates are usually glass and flat, but other materials and shapes may be used.
  • EXAMPLE 1 Preparation of Ether/Zipax" Packing for Liquid Chromatography Twenty-five grams of 40 microns Zipax and 150 ml. of concentrated nitric acid are placed in a 250 ml. beaker and heated on a steam bath for 2hours with occasional stirring. The resulting support is. washed free of acid by repeatedly slurrying with distilled water. The
  • FIG. 5 shows I comparative HETP (height equivalent to a theoretical plate), versus linear carrier velocity plots for. two
  • I columns made from the same original 325-400 mes Zipax supports.
  • One column embodies mechanicallyheld I percent Bfi-oxydipropionitrile as the stationary phase, while the other consists of a' 0.94 percent ether bonded-phase.
  • HETP data .for the bonded I phase column is slightly higher than that for the conventional liquid-liquid column for two solutes of which acetophenone is essentially unretarded and benzyl alcohol is moderately retained.
  • the ether bonded-phase column was operated at input pressures up to5,000 psi and carrier linear velocities up to 40 cm./sec. Even under these very drastic conditions, the column showed little degradation, as evidenced by the especially'marked points 25 in the FIG. 5 plot. Operation of conventional liquid-liquid chromatographic columns at carriervelocities of 40 cm./sec. is very difficult, because of the loss of mechanically held stationary phase.
  • FIG. 6 The uniqueness of the etherfbonded-phase for liquid chromatographic separations is further illustrated in FIG. 6.
  • This synthetic mixture of the thiolhydroxamates shown was separated in a 1 meter X 2:1 mm. i.d., column of the 325-400 mesh Zipax containing 0.94 percent ether bonded-phase, the column being operated at 27C., with a carrier of 1.0 percent chloroform in hexane.
  • These compounds are difficult to separate with conventional liquid-liquid chromatographic systems because of their polyfunc tionality and their, high polarity. They are strongly retained on most conventional stationary phases, and
  • the resulting bonded-phase showed 0.23, 0.232 percent carbon, 0.032, 0.034 percent hydrogen, and 0.087, 0.089 percent nitrogen.
  • the packing material contained 0.83 percent silicone polymer (calculated on the structure proposed below), or 90 percent of theoretiabsolute methanol.
  • the a-cyanoacetanilide peak in FIG. 7 has a HETP of 1.89 mm. at a flowrate of 4.35 cc./min., which corresponds to 8.0 theoretical plates/sec. (4.8 effective plates/sec). When operated at a carrier linear velocity of 1 cm./sec. or less, this column demonstrates HETP of less than 1 mm. for similar solutes.
  • the efficiency of the bonded-phase liquid chromatographic columns depends on the type and polarity of the carrier used. Columns with nitrile bonded-phase packing show poor efficiency with hexane as carrier. However, as' the polarity of the carrieris increased, so does the efficiency of the column .(equal solute partition ratios). s
  • This hydrolysis mixture is then added to 20 grams of 400 mesh- Zipax contained in a shallow evaporating dish, and the solvent removed while gently stirring the mixture under warm air from a heat gun. The resulting mixture is then heatedfor 1 hour at 150C. in a circulating air oven. The treated support is then transferred to a 500 ml. round-bottom flask which contains 200 ml. of absolute methanol. The mixture is refluxed for l5 minutes, the
  • FIG. 8 Use of the -ether bonded-phase packing for a gas chromatographic separation is shown in FIG. 8. This separation was carried out on a 1 meter X A inch o.d., inch i.d. glass column, using helium carrier gas flowrate of 50 cc./min. andla flame ionization detector sensitivity of l X 10* amp. full-scale, with a Beckman GC-4 gas chromatograph. 0.2 Microliters of the test mixture was injected at an initial column temperature of C., and the temperature of the column was continuously increased at 133C. per minute. The versatility of this column permits the separation of both low boiling compounds (hexane) and very high boiling 1 compounds (di-normal butyl-phthalate). The bleed of 'thisfether bonded-phase column at high temperatures is minimal, as evidenced by the slight increase in baseline of the chromatogram approaching 300C. for
  • FIG. 9 The unique selectivity of the chemically bonded polymeric ether packing for gas chromatographic separations is illustrated in FIG. 9.
  • the upper curve shows the separation of a mixture of aliphatic hydrocarbons and 4-bromobiphenyl on a column of 1.1 percent bonded ether on Zipax" support operated at 275C.
  • the lower curve is the same mixture chromatographed under identical conditions on a 1.0 percent Carboxwax M (aliphatic polyether) column, except that the temperature was 200C.
  • the separation factors were very high for these compounds on the ether bonded-phase column operated at- 275C., compared to those on Carbowax 20M at 200C.
  • a similar pattern is apparent for the aromatic compound, 4-bromobiphenyl; its retention time on the ether" column at 275C. is 1.4 minutes, as compared to 0.25
  • FIG. 10 The very high temperature stability of the B- cyanoethyl bonded-phase packing is illustrated in FIG. 10.
  • This figure shows thebackground current of a flame ionization detector operated at l X 10 amp., full-scale, when a V4 inch o.d. Vs inch i.d. glass column of fl-cyanoethyl bonded-phase was programmed from 100 to'. 300C.
  • the background current obtained under the same conditions (slightly displaced upward on the scale to show differences) for a similar column of 1 percent General Electric XE-60 (25 percent cyanoethyl, methyl silicon polymer), mechanically dispersed on 100-120 mesh Zipax support.- vBoth of these columns were conditioned at 250C.
  • the bonded nitrile packing shows essentially no fbleed at 275C.'
  • the conventional XE-60 column starts to show significant background at about 225C.
  • the nitrile column is stable to at least 300C., while the Co., Inc., Wilmington, Del.) operated at a heating rate of 10C. per minute, using a flow of 85 cc'./min. of air.
  • the curve shows the weight loss on a 100 mg. sample of the nitrile material as a function of temperature; This study indicates that the organic polymeric phase is essentially stable to about 325C, then begins to degrade slowly at higher temperatures.
  • EXAMPLE 6 Ion Exchange Bonded-Phase for Liquid Chromatography by passing concentrated nitric acid through the tubing while heating over a steam bath. The capillary is then thoroughly washed with distilled water to-eliminate all acid, rinsed with reagent grade acetone and dried with dry nitrogen. About 50 ml. of a 5 percent (by weight) solution of Union Carbide Silane A-16 (amyltriethox ysilane) is passed through the capillary, dry nitrogen I connected to the tubing, and the excess solution removed by the pressure of the gas. The flow of dry nitrogen is continued through the capillary .until all of the excess solvent has been evaporated, leaving a thin I film of A-16 onthe interior surface of the glass.
  • A-16 amyltriethox ysilane
  • tract ed beads are filtered off on a sintered glass stream of moist air (relative humidity of about 85 percent) is then passed through the capillary until the silane ester is completely hydrolyzed, as evidenced by no more ethanol being evolved from the tubing.
  • the capillary is then placed in a 110C. oven and a stream of dry nitrogen slowly passed through the tubing for several hours.
  • capillary bondedephase column is particularly useful for separating complex mixtures of aliphatic and substituted aromatic hydrocarbons.
  • This weak anion exchange packing can be used to separate a wide variety of acidic compounds, or other materials which are retained on this basic chromatographic medium.
  • the amino functionality can'also be quaternized to a strongly basic tetraalkylammonium derivation by well-known organic reactions.
  • the quaternized form is a useful strong anion exchanger.
  • said metal of said substrate having a valence of 3 ,5, said stationary phase being chemically'bonded to the surface of said substrate by an linkage, wherein M is said polyvalent metal and wherein A is O- or a monovalent aliphatic or aromatic hydrocarbon radical and R is a monovalent or aliphaticor aromatic hydrocarbon radical,
  • said metal of said substrate having a valence of 35, said stationary phase being chemically bonded to the surface of said substrate by an linkage, wherein M is said polyvalent metal and is part of one of said repeating units of said stationary phase.
  • An apparatus for use in chromatographic separations comprising a resolving zone through which,
  • said resolving zone comprising a packing having a polyvalent metalcontaining substrate and a stationary phasehaving an average thickness of about 3.0 A to 10,000 A, said stationary phase comprising a'porous polymer having the repeating unit of the formula 4 7 wherein A is -O or a monovalent aliphatic or aromatic hydrocarbon radical and R is a monovalent aliphatic or aromatic hydrocarbon radical, I
  • said metal of said substrate having a valence. of 3-5, said stationary phase being chemically bonded to the surface of said substrate by an linkage, wherein M is said polyvalent metal and is part of one of said repeating units of said stationary phase, and said polymer comprising 5 to 80 percent of the volume of said stationary phase.
  • An improved process for performing chromato graphic separations comprising:
  • said material and said carrier fluid wit a packing having a polyvalent metal-containing substrate and a stationary phase having an average thickness of about from 30 A to 10,000 A, said stationary phase comprising a porous polymer having the repeating unit of the formula wherein A is --O- or a monovalent aliphatic or aromatic hydrocarbon radical and R is a monovalent or aliphatic or aromatic hydrocarbon radical,
  • said metal of said substrate having a valence of 3.5
  • M is said polyvalent metal and is part of one of said repeating units of said stationary phase, and said polymer Comprising about to 80 per cent of the volume of said stationary phase.
  • said packing comprises at least two copolyrneriied portions, A inthe first of said portions being O, and A in the second of said portions being a monovalent aliphatic or aro- 17.
  • said resolving zone is disposed within a column.
  • packing comprises a thin layer upon a surface.

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US3983299A (en) * 1974-03-04 1976-09-28 Purdue Research Foundation Bonded carbohydrate stationary phases for chromatography
US3984349A (en) * 1971-07-26 1976-10-05 Societe Rhone-Progil Modified porous bodies
US3987058A (en) * 1975-02-27 1976-10-19 The United States Of America As Represented By The Secretary Of Agriculture Preparation and uses of stable, bound stationary phases
US4005046A (en) * 1974-11-12 1977-01-25 Dow Corning Limited Catalysts and carriers therefor
US4029583A (en) * 1975-02-28 1977-06-14 Purdue Research Foundation Chromatographic supports and methods and apparatus for preparing the same
US4045353A (en) * 1974-10-15 1977-08-30 Toyo Soda Manufacturing Co., Ltd. High-energy radiation induced polymerization on a chromatographic solid support
US4118316A (en) * 1976-10-13 1978-10-03 Calgon Corporation Quaternized siliceous supports for gel permeation chromatography
US4140653A (en) * 1975-09-30 1979-02-20 Toyo Soda Manufacturing Co., Ltd. Solid support for liquid chromatography
US4169790A (en) * 1975-05-02 1979-10-02 South African Inventions Development Corporation Solid surface texture suitable for a stationary phase for chromatography
US4199330A (en) * 1978-02-13 1980-04-22 The Dow Chemical Company Bonded organo-pellicular packings for chromatographic columns
US4209554A (en) * 1979-02-22 1980-06-24 Scm Corporation Polydentate metal salts used in the process for the deactivation of glass surfaces and capillary columns therewith
US4242227A (en) * 1979-07-31 1980-12-30 The Dow Chemical Company Chromatographic column packing having a bonded organosiloxane coating
US4243753A (en) * 1978-02-27 1981-01-06 Purdue Research Foundation Apparatus for enzyme detection
US4324689A (en) * 1980-02-26 1982-04-13 Shah Ramesh M High carbon content chromatographic packing and method for making same
US4540486A (en) * 1983-11-25 1985-09-10 J. T. Baker Chemical Company Polyethylenimine bound chromatographic packing
US4551245A (en) * 1985-04-22 1985-11-05 J. T. Baker Chemical Co. Acylated polyethylenimine bound chromatographic packing
US4591455A (en) * 1982-11-24 1986-05-27 Pedro B. Macedo Purification of contaminated liquid
US4648975A (en) * 1983-08-17 1987-03-10 Pedro B. Macedo Process of using improved silica-based chromatographic supports containing additives
US4705725A (en) * 1986-11-28 1987-11-10 E. I. Du Pont De Nemours And Company Substrates with sterically-protected, stable, covalently-bonded organo-silane films
US4737316A (en) * 1982-11-24 1988-04-12 Pedro B. Macedo Purification of contaminated liquid
US4743377A (en) * 1985-07-02 1988-05-10 Shiseido Company Ltd. Packing material for liquid chromatography
US4746572A (en) * 1986-11-28 1988-05-24 E. I. Dupont De Nemours And Company Structures surface modified with bidentate silanes
US4756971A (en) * 1984-12-28 1988-07-12 Ksv-Chemicals Oy Surface treatment agents and polymers comprising substituted phenyl silanes and siloxanes
US4828704A (en) * 1985-03-15 1989-05-09 Cosmo Oil Company, Ltd. Thin-layer rod for chromatography
US4874518A (en) * 1985-11-01 1989-10-17 E. I. Du Pont De Nemours And Company Porous silica microspheres having a silanol enriched surface
US5032266A (en) * 1985-11-01 1991-07-16 E. I. Du Pont De Nemours And Company Porous silica microspheres having silanol-enriched and silanized surfaces
US5055194A (en) * 1989-07-28 1991-10-08 University Of Pennsylvania Support for high performance liquid chromatography in a magnetically stabilized fluidized bed
US5087597A (en) * 1990-07-19 1992-02-11 Armada De La Republica De Venezuela Carbon dioxide adsorbent and method for producing the adsorbent
US5108595A (en) * 1985-11-01 1992-04-28 E. I. Du Pont De Nemours And Company Porous silica microspheres having silanol-enriched and silanized surfaces
US5154822A (en) * 1986-07-28 1992-10-13 3I Research Exploitation Limited Bonded chromatographic stationary phase
US5248426A (en) * 1992-02-10 1993-09-28 Dionex Corporation Ion chromatography system using electrochemical suppression and detector effluent recycle
US5518622A (en) * 1992-02-10 1996-05-21 Dionex Corporation Electrochemical pretreatment system for liquid sample analysis
US5637135A (en) * 1995-06-26 1997-06-10 Capillary Technology Corporation Chromatographic stationary phases and adsorbents from hybrid organic-inorganic sol-gels
US5667674A (en) * 1996-01-11 1997-09-16 Minnesota Mining And Manufacturing Company Adsorption medium and method of preparing same
US5759405A (en) * 1995-03-03 1998-06-02 Alltech Associates, Inc. Apparatuses and methods for electrochemically modifying the retention of species on chromatography material
US5762803A (en) * 1994-07-20 1998-06-09 Cu Chemie Uetikon Ag Silicon dioxide based microspheres for rapid chromatographic separation of biomolecules
US5869724A (en) * 1997-06-20 1999-02-09 Hewlett-Packard Company Asymmetric bidentate silanes
US5915269A (en) * 1997-04-15 1999-06-22 The Perkin-Elmer Corporation Method and apparatus to compensate for gas chromatograph column permeability
US5935443A (en) * 1995-03-03 1999-08-10 Alltech Associates, Inc. Electrochemically regenerated ion neutralization and concentration devices and systems
US5948531A (en) * 1997-06-20 1999-09-07 Hewlett-Packard Company Propylene-bridged bidentate silanes
WO2002072225A1 (en) * 2001-03-09 2002-09-19 University Of South Florida High efficiency sol-gel gas chromatography column
US20040129141A1 (en) * 2002-03-08 2004-07-08 Abdul Malik High efficiency sol-gel gas chromatography column
US20060005877A1 (en) * 2004-07-06 2006-01-12 General Electric Company Passivated, dye-sensitized oxide semiconductor electrode, solar cell using same, and method
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US20070187313A1 (en) * 2005-12-16 2007-08-16 Akzo Nobel N.V. Silica based material
US20090311533A1 (en) * 2008-06-13 2009-12-17 Wu Chen Porous silica microspheres having organosilane modified surfaces
US9340443B2 (en) 2012-12-13 2016-05-17 Corning Incorporated Bulk annealing of glass sheets
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US10510576B2 (en) 2013-10-14 2019-12-17 Corning Incorporated Carrier-bonding methods and articles for semiconductor and interposer processing
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US11097509B2 (en) 2016-08-30 2021-08-24 Corning Incorporated Siloxane plasma polymers for sheet bonding
US11167532B2 (en) 2015-05-19 2021-11-09 Corning Incorporated Articles and methods for bonding sheets with carriers
US11192340B2 (en) 2014-04-09 2021-12-07 Corning Incorporated Device modified substrate article and methods for making
US11331692B2 (en) 2017-12-15 2022-05-17 Corning Incorporated Methods for treating a substrate and method for making articles comprising bonded sheets
US11535553B2 (en) 2016-08-31 2022-12-27 Corning Incorporated Articles of controllably bonded sheets and methods for making same
US11905201B2 (en) 2015-06-26 2024-02-20 Corning Incorporated Methods and articles including a sheet and a carrier
US11999135B2 (en) 2017-08-18 2024-06-04 Corning Incorporated Temporary bonding using polycationic polymers

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CN113000028A (zh) * 2021-04-27 2021-06-22 临沂海普新材料科技有限公司 一种用于废酸中磷酸回收的吸附剂制备方法

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US3984349A (en) * 1971-07-26 1976-10-05 Societe Rhone-Progil Modified porous bodies
US3922392A (en) * 1972-05-27 1975-11-25 Merck Patent Gmbh Process for coating nonporous material with a porous silicon dioxide layer
US3878092A (en) * 1973-03-12 1975-04-15 Phillips Petroleum Co Chromatographic colums
US3983299A (en) * 1974-03-04 1976-09-28 Purdue Research Foundation Bonded carbohydrate stationary phases for chromatography
US4045353A (en) * 1974-10-15 1977-08-30 Toyo Soda Manufacturing Co., Ltd. High-energy radiation induced polymerization on a chromatographic solid support
US4005046A (en) * 1974-11-12 1977-01-25 Dow Corning Limited Catalysts and carriers therefor
US3987058A (en) * 1975-02-27 1976-10-19 The United States Of America As Represented By The Secretary Of Agriculture Preparation and uses of stable, bound stationary phases
US4029583A (en) * 1975-02-28 1977-06-14 Purdue Research Foundation Chromatographic supports and methods and apparatus for preparing the same
US4169790A (en) * 1975-05-02 1979-10-02 South African Inventions Development Corporation Solid surface texture suitable for a stationary phase for chromatography
US4140653A (en) * 1975-09-30 1979-02-20 Toyo Soda Manufacturing Co., Ltd. Solid support for liquid chromatography
US4118316A (en) * 1976-10-13 1978-10-03 Calgon Corporation Quaternized siliceous supports for gel permeation chromatography
US4199330A (en) * 1978-02-13 1980-04-22 The Dow Chemical Company Bonded organo-pellicular packings for chromatographic columns
US4243753A (en) * 1978-02-27 1981-01-06 Purdue Research Foundation Apparatus for enzyme detection
US4209554A (en) * 1979-02-22 1980-06-24 Scm Corporation Polydentate metal salts used in the process for the deactivation of glass surfaces and capillary columns therewith
US4242227A (en) * 1979-07-31 1980-12-30 The Dow Chemical Company Chromatographic column packing having a bonded organosiloxane coating
US4324689A (en) * 1980-02-26 1982-04-13 Shah Ramesh M High carbon content chromatographic packing and method for making same
US4591455A (en) * 1982-11-24 1986-05-27 Pedro B. Macedo Purification of contaminated liquid
US4737316A (en) * 1982-11-24 1988-04-12 Pedro B. Macedo Purification of contaminated liquid
US4648975A (en) * 1983-08-17 1987-03-10 Pedro B. Macedo Process of using improved silica-based chromatographic supports containing additives
US4540486A (en) * 1983-11-25 1985-09-10 J. T. Baker Chemical Company Polyethylenimine bound chromatographic packing
US4756971A (en) * 1984-12-28 1988-07-12 Ksv-Chemicals Oy Surface treatment agents and polymers comprising substituted phenyl silanes and siloxanes
US4828704A (en) * 1985-03-15 1989-05-09 Cosmo Oil Company, Ltd. Thin-layer rod for chromatography
US4551245A (en) * 1985-04-22 1985-11-05 J. T. Baker Chemical Co. Acylated polyethylenimine bound chromatographic packing
US4743377A (en) * 1985-07-02 1988-05-10 Shiseido Company Ltd. Packing material for liquid chromatography
US4874518A (en) * 1985-11-01 1989-10-17 E. I. Du Pont De Nemours And Company Porous silica microspheres having a silanol enriched surface
US5108595A (en) * 1985-11-01 1992-04-28 E. I. Du Pont De Nemours And Company Porous silica microspheres having silanol-enriched and silanized surfaces
US5032266A (en) * 1985-11-01 1991-07-16 E. I. Du Pont De Nemours And Company Porous silica microspheres having silanol-enriched and silanized surfaces
US5154822A (en) * 1986-07-28 1992-10-13 3I Research Exploitation Limited Bonded chromatographic stationary phase
US4705725A (en) * 1986-11-28 1987-11-10 E. I. Du Pont De Nemours And Company Substrates with sterically-protected, stable, covalently-bonded organo-silane films
US4847159A (en) * 1986-11-28 1989-07-11 E. I. Du Pont De Nemours And Company Substrates coated with organo-silanes that are sterically-protected
US4746572A (en) * 1986-11-28 1988-05-24 E. I. Dupont De Nemours And Company Structures surface modified with bidentate silanes
US5055194A (en) * 1989-07-28 1991-10-08 University Of Pennsylvania Support for high performance liquid chromatography in a magnetically stabilized fluidized bed
US5087597A (en) * 1990-07-19 1992-02-11 Armada De La Republica De Venezuela Carbon dioxide adsorbent and method for producing the adsorbent
US5248426A (en) * 1992-02-10 1993-09-28 Dionex Corporation Ion chromatography system using electrochemical suppression and detector effluent recycle
US5352360A (en) * 1992-02-10 1994-10-04 Dionex Corporation Ion chromatography system using electrochemical suppression and detector effluent recycle
US5518622A (en) * 1992-02-10 1996-05-21 Dionex Corporation Electrochemical pretreatment system for liquid sample analysis
US5597481A (en) * 1992-02-10 1997-01-28 Dionex Corporation Electrochemical pretreatment system for liquid sample analysis
US5762803A (en) * 1994-07-20 1998-06-09 Cu Chemie Uetikon Ag Silicon dioxide based microspheres for rapid chromatographic separation of biomolecules
US5759405A (en) * 1995-03-03 1998-06-02 Alltech Associates, Inc. Apparatuses and methods for electrochemically modifying the retention of species on chromatography material
US6235197B1 (en) 1995-03-03 2001-05-22 Alltech Associates, Inc. Electrochemically regenerated ion neutralization and concentration devices and systems
US7364646B2 (en) 1995-03-03 2008-04-29 Dionex Corporation High-purity eluant generator
US7780834B2 (en) 1995-03-03 2010-08-24 Dionex Corporation Apparatuses and methods for electrochemically modifying the retention of species on chromatography material
US20030209439A1 (en) * 1995-03-03 2003-11-13 Alltech Associates, Inc. High-purity eluant generator
US20050252774A1 (en) * 1995-03-03 2005-11-17 Anderson James M Jr Method and apparatus for generating a high purity eluant
US5935443A (en) * 1995-03-03 1999-08-10 Alltech Associates, Inc. Electrochemically regenerated ion neutralization and concentration devices and systems
US7531075B2 (en) 1995-03-03 2009-05-12 Dionex Corporation Method and apparatus for generating a high purity eluant
US6558551B1 (en) 1995-03-03 2003-05-06 Alltech Associates, Inc. Method and system for generating a high purity eluant
US6093327A (en) * 1995-03-03 2000-07-25 Anderson, Jr.; James M. Apparatuses and methods for electrochemically modifying the retention of species on chromatography material
US20080190850A1 (en) * 1995-03-03 2008-08-14 Dionex Corporation Apparatuses and methods for electrochemically modifying the retention of species on chromatography material
US5637135A (en) * 1995-06-26 1997-06-10 Capillary Technology Corporation Chromatographic stationary phases and adsorbents from hybrid organic-inorganic sol-gels
US5667674A (en) * 1996-01-11 1997-09-16 Minnesota Mining And Manufacturing Company Adsorption medium and method of preparing same
US5968652A (en) * 1996-01-11 1999-10-19 3M Innovative Properties Company Silane coated particle
US5876595A (en) * 1996-01-11 1999-03-02 Minnesota Mining And Manufacturing Company Adsorption medium and method of preparing same
US5915269A (en) * 1997-04-15 1999-06-22 The Perkin-Elmer Corporation Method and apparatus to compensate for gas chromatograph column permeability
US5948531A (en) * 1997-06-20 1999-09-07 Hewlett-Packard Company Propylene-bridged bidentate silanes
US5869724A (en) * 1997-06-20 1999-02-09 Hewlett-Packard Company Asymmetric bidentate silanes
US8685240B2 (en) 2001-03-09 2014-04-01 University Of South Florida High efficiency sol-gel gas chromatography column
WO2002072225A1 (en) * 2001-03-09 2002-09-19 University Of South Florida High efficiency sol-gel gas chromatography column
US20070062874A1 (en) * 2001-03-09 2007-03-22 Abdul Malik High efficiency sol-gel gas chromatography column
US20040129141A1 (en) * 2002-03-08 2004-07-08 Abdul Malik High efficiency sol-gel gas chromatography column
US20060005877A1 (en) * 2004-07-06 2006-01-12 General Electric Company Passivated, dye-sensitized oxide semiconductor electrode, solar cell using same, and method
WO2006039507A2 (en) 2004-10-01 2006-04-13 Phenomenex, Inc. Ph stable chromatographic media using templated multilayer organic/inorganic grafting
EP1804950B1 (en) * 2004-10-01 2016-06-01 Phenomenex, Inc. Ph stable chromatographic media using templated multilayer organic/inorganic grafting
US9308520B2 (en) 2005-12-16 2016-04-12 Akzo Nobel N.V. Silica based material
US20070187313A1 (en) * 2005-12-16 2007-08-16 Akzo Nobel N.V. Silica based material
US20090311533A1 (en) * 2008-06-13 2009-12-17 Wu Chen Porous silica microspheres having organosilane modified surfaces
US8277883B2 (en) * 2008-06-13 2012-10-02 Agilent Technologies, Inc. Porous silica microspheres having organosilane modified surfaces
US10543662B2 (en) 2012-02-08 2020-01-28 Corning Incorporated Device modified substrate article and methods for making
US9340443B2 (en) 2012-12-13 2016-05-17 Corning Incorporated Bulk annealing of glass sheets
US9889635B2 (en) 2012-12-13 2018-02-13 Corning Incorporated Facilitated processing for controlling bonding between sheet and carrier
US10014177B2 (en) 2012-12-13 2018-07-03 Corning Incorporated Methods for processing electronic devices
US10086584B2 (en) 2012-12-13 2018-10-02 Corning Incorporated Glass articles and methods for controlled bonding of glass sheets with carriers
US10538452B2 (en) 2012-12-13 2020-01-21 Corning Incorporated Bulk annealing of glass sheets
US10510576B2 (en) 2013-10-14 2019-12-17 Corning Incorporated Carrier-bonding methods and articles for semiconductor and interposer processing
US10046542B2 (en) 2014-01-27 2018-08-14 Corning Incorporated Articles and methods for controlled bonding of thin sheets with carriers
US11123954B2 (en) 2014-01-27 2021-09-21 Corning Incorporated Articles and methods for controlled bonding of thin sheets with carriers
US11192340B2 (en) 2014-04-09 2021-12-07 Corning Incorporated Device modified substrate article and methods for making
US11167532B2 (en) 2015-05-19 2021-11-09 Corning Incorporated Articles and methods for bonding sheets with carriers
US11660841B2 (en) 2015-05-19 2023-05-30 Corning Incorporated Articles and methods for bonding sheets with carriers
US11905201B2 (en) 2015-06-26 2024-02-20 Corning Incorporated Methods and articles including a sheet and a carrier
US11097509B2 (en) 2016-08-30 2021-08-24 Corning Incorporated Siloxane plasma polymers for sheet bonding
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US11535553B2 (en) 2016-08-31 2022-12-27 Corning Incorporated Articles of controllably bonded sheets and methods for making same
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DE2125428A1 (de) 1971-12-02
JPS5217078B1 (enrdf_load_stackoverflow) 1977-05-13
FR2093601A5 (enrdf_load_stackoverflow) 1972-01-28
JPS49125098A (enrdf_load_stackoverflow) 1974-11-29
SE399647B (sv) 1978-02-27
DE2125428C2 (de) 1984-05-30
NL7107016A (enrdf_load_stackoverflow) 1971-11-24
GB1354357A (en) 1974-06-05
CH578732A5 (enrdf_load_stackoverflow) 1976-08-13

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