A carboxylic acid ester is prepared by a process comprising:reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen as indicated by the following reaction:RCHOROHO2RCOORH2Oin the presence of a catalyst comprising at least palladium and an element X, wherein X is bismuth, lead or a combination thereof, supported on a carrier, wherein the catalyst has an acid strength, pKa, of more than 4.8 and shows an ammonia chemical adsorption amount at 0 C. of 0-150 mol/g-catalyst.

Description

24 parts

›TECHNICAL FIELD

The present invention relates to a process for producing a carboxylic acid ester by reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen by using a catalyst and to a catalyst used for the process.

›BACKGROUND ART

Catalysts which have been proposed to be used in a process for producing a carboxylic acid ester from an aldehyde and an alcohol in the presence of molecular oxygen by using a catalyst include, for example, a palladium-lead type catalyst disclosed in JP-B-57-35856, JP-B-4-72578, JP-A-57-50545 and others, a palladium-tellurium type catalyst disclosed in JP-A-61-243044, a palladium-thallium-mercury type catalyst disclosed in JP-B-57-35860, a palladium-alkaline earth metal-zinc-cadmium type catalyst disclosed in JP-B-57-19090, and a palladium-bismuth type catalyst disclosed in JP-B-61-60820, JP-B-62-7902, JP-A-5-148184 and others. As to the carrier of the catalyst used for such processes, there have been proposed, for example, calcium carbonate in JP-B-57-35856 and JP-B-57-35860, zinc oxide-alumina, titania-lanthanum oxide and zinc oxide-titania in JP-B-4-46618, zinc oxide in JP-B-4-72578, a carrier having a specific surface area of not more than 70 m 2 /g in JP-A-57-50942 and a hydrophobic carrier in JP-A-5-148184.

However, these catalysts are apt to differ in the yield of carboxylic acid esters even when the components and/or the carrier of the catalyst are of the same composition. Therefore, the development of a process, improved in the above-mentioned point, which can produce carboxylic acid esters with a high yield has been eagerly awaited.

›DISCLOSURE OF THE INVENTION · 1 of 2

The object of the present invention is to provide a process for producing a carboxylic acid ester from an aldehyde and an alcohol with a high yield and a catalyst used for the process.

Thus, the present invention provides a process for producing a carboxylic acid ester, comprising reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen by the use of a catalyst comprising at least palladium and X (X represents bismuth and/or lead) supported on a carrier, wherein the catalyst used has an acid strength, pKa, of more than 4.8 and shows an ammonia chemical adsorption amount at 0° C. of 0-150 μmol/g-catalyst.

The present invention further provides a catalyst used for producing a carboxylic acid ester by reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen, which comprises at least palladium and X (X represents bismuth and/or lead) supported on a carrier, has an acid strength, pKa, of more than 4.8 and shows an ammonia chemical adsorption amount at 0° C. of 0-150 μmol/g-catalyst.

In the catalyst and the process according to the present invention, the aldehyde used as a starting material may be, for example, aromatic aldehydes, such as benzaldehyde, methylbenzaldehyde, and nitrobenzaldehyde, saturated aliphatic aldehydes, such as acetaldehyde, propionaldehyde and isobutyl aldehyde, and unsaturated aliphatic aldehydes, such as acrolein, methacrolein and crotonaldehyde. The alcohol of a starting material may be, for example, methanol, ethanol, isopropanol, allyl alcohol and methallyl alcohol.

The catalyst of the present invention and the catalyst used in the process of the present invention comprise palladium, as a catalyst component, supported on a carrier and additionally bismuth and/or lead, as a catalyst component(s), supported on the carrier. The term “catalyst” herein refers not only to the catalyst components supported on a carrier but also to the whole catalyst system including the carrier. A starting material for palladium used in preparing the catalyst may be, for example, palladium acetate, palladium chloride, palladium nitrate, palladium ammonium chloride, and palladium-ammine complex salt, a starting material for bismuth may be, for example, bismuth acetate, bismuth carbonate, bismuth chloride, bismuth nitrate and bismuth sulfate, and a starting material for lead may be, for example, metal compounds, such as lead acetate, lead carbonate, lead chloride, lead nitrate, lead sulfate, lead tartrate and lead citrate. Besides palladium, bismuth and lead, third components, such as chromium, iron, cobalt, zinc, barium and silver, may be supported as catalyst components on the carrier. The catalyst components are present on the carrier in the form of a metal and/or a metal compound.

In the catalyst of the present invention and the catalyst used in the process of the present invention, the amounts of the respective catalyst components to be supported on the carrier are, based on 100 parts by weight of the carrier, preferably 1-15 parts by weight, more preferably 3-13 parts by weight for palladium, and 0.1-15 parts by weight, more preferably 0.5-12 parts by weight for X. When the catalyst component is a metal compound , the above-mentioned amount to be supported is calculated in terms of the weight of the metal atom in the metal compound. The carriers may be for example, calcium carbonate, zinc oxide, silica and silica-magnesia. Average particle diameter and specific surface area of the carrier are, for example, 5-150 μm and 50-200 m 2 /g, respectively.

The catalyst of the present invention and the catalyst used in the process of the present invention have an acid strength, pKa, of more than 4.8. The acid strength, pKa, herein is an index which indicates the degree of acidity of the surface of a material. It is signified that the larger the value of pKa, the weaker the acidity. The acid strength pKa is determined according to the method described in Shokubai (catalyst), vol. 11 pp. 210-216 (1969) (written by Isao Matsuzaki et al., published by Shokubai Gakkai (Catalyst Society)) by using an indicator which changes its color in a predetermined range of pKa. When a catalyst which has a pKa of not more than 4.8 is used, by-products such as acetals tend to be formed markedly to lower the yield of the carboxylic acid ester of the objective product.

The catalyst of the present invention and the catalyst used in the process of the present invention show an ammonia chemical adsorption amount at 0° C. (hereinafter referred to simply as “ammonia chemical adsorption amount”) of 0-150 μmol/g-catalyst, preferably 30-140 μmol/g-catalyst. The term “ammonia chemical adsorption amount”herein refers to the amount of ammonia chemically adsorbed to 1 g of catalyst at 0° C. It is signified that the larger the value of the above-mentioned amount, the larger the amount of acid sites per 1 g of the catalyst (hereinafter referred to as “acid amount”). To determine the ammonia chemical adsorption amount, the total adsorption amount, which is the sum of the chemical adsorption amount and the physical adsorption amount of ammonia, and the physical adsorption amount of ammonia are determined at 0° C. by using a common adsorption-desorption apparatus available on the market, and the “ammonia chemical adsorption amount” can be obtained from the difference of the two amounts determined above. When a catalyst which shows an ammonia chemical adsorption amount of more than 150 μmol/g-catalyst is used, by-products, such as acetals, tend to be formed markedly, to lower the yield of the objective product.

The catalyst of the present invention and the catalyst used in the process of the present invention can be prepared by conventional methods. As an example of the method of preparation, the preparation of a catalyst comprising palladium, bismuth and iron supported on a silica-magnesia carrier is described below. First, palladium chloride, bismuth nitrate and nitric acid are added to water, and the resulting mixture is heated to form a solution. Then, silica-magnesia powder, and thereafter a reducing agent such as formalin are added to the solution, and the resulting mixture is stirred with heating for a predetermined time. Thereafter, the mixture is filtered and the solid obtained is immersed in an aqueous solution of ferric nitrate. In this time, if desired, the solid may be reduced again with a reducing agent to deposit a metal. The solid is again collected by filtration, and then dried to obtain a catalyst. The catalyst obtained may also be activated by conventional methods.

›DISCLOSURE OF THE INVENTION · 2 of 2

In the present invention, a carboxylic acid ester is produced by reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen by using a catalyst which has an acid strength, pKa, of more than 4.8 and shows an ammonia chemical adsorption amount of 0-150 μmol/g-catalyst. The molar ratio of the aldehyde to the alcohol of the starting materials is preferably 1:100 to 1:1, more preferably 1:80 to 1:3.

In carrying out the reaction according to the process of the present invention, the catalyst is dispersed as a suspension in the liquid phase. The reaction may be conducted either batch-wise or semibatch-wise or continuously. The source of the molecular oxygen used as the oxidizing agent may be air, oxygen-enriched air, oxygen or the like. The reaction temperature is preferably 0-100° C., more preferably 30-80° C. The reaction may be conducted at ordinary pressure or under applied pressure.

The molecular oxygen is used in an amount sufficient to form the intended carboxylic acid ester. The amount is preferably 10-500 ml/min relative to 100 ml of the reaction liquid. As to a solvent used for forming the liquid phase, for example, the aldehyde and/or the alcohol used in the process of the present invention may be used as such to form the liquid phase, but the solvent is not limited thereto. For example, hexane, acetone, benzene and the like may be used as the solvent. The amount of the catalyst to be used is not particularly limited, and may be, for example, 0.01 g-1 g per 1 g of aldehyde.

›BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in detail below with reference to Examples and Comparative Examples, but the invention is in no way limited thereto. The “supported amount” of the metal and/or metal compound of the catalyst component refers to the weight of metal atom in the catalyst component, which is a value obtained by calculation from the amount of the starting material used for catalyst preparation. The catalyst composition was expressed by describing, behind the atomic symbol of the catalyst component, a supported amount per 100 parts by weight of the carrier and then, behind the slant line (/), the carrier. The acid strength, pKa, was determined according to the method described in Shokubai, Vol. 11, pp. 210-216 (1969) as mentioned above. The ammonia chemical adsorption amount at 0° C. was determined by using a BET type adsorption measuring apparatus. Analysis of a reaction product was made by means of gas chromatography. Conversion of the aldehyde of the starting material (hereinafter referred to as “conversion”), selectivity to the carboxylic acid ester of the objective product (hereinafter referred to as “ester selectivity”), selectivity to the acetal of by-product (hereinafter referred to as “acetal selectivity”) and yield of the carboxylic acid ester of the objective product (hereinafter eferred to as “yield”) were calculated according to the following definitions,

wherein A, B, C and D respectively represent:

A: the number of moles of fed starting material aldehyde,

B: the number of moles of reacted starting material aldehyde,

C: the number of moles of formed carboxylic acid ester,

D: the number of moles of formed acetal.

›Examples18

›EXAMPLE 1

In 50 ml of pure water was dissolved with heating 0.85 g of palladium chloride, 0.46 g of bismuth nitrate and 5 g of a 60 wt % aqueous nitric acid solution, then 10 g of a silica-magnesia powder with an average particle diameter of 100 μm was added to the solution, and the resulting mixture was stirred. To the mixture was added 50 ml of an aqueous solution containing 5 wt % of sodium hydroxide and 5 wt % of formalin, the resulting mixture was stirred at 70° C. for 30 minutes, then filtered, and the resulting cake was washed with water and dried to obtain a catalyst shown in Table 1. In a 300 ml flask fitted with a reflux condenser were placed 2 g of the catalyst obtained above, 4.3 g of benzaldehyde and 80 g of methanol, and the mixture was allowed to react at 50° C. for 2 hours while air was being blown thereinto at a flow rate of 100 ml/min, to obtain methyl benzoate as a carboxylic acid ester. The results thus obtained are shown in Table 2.

›EXAMPLE 2

In 50 ml of pure water were dissolved with heating 0.85 g of palladium chloride, 0.46 g of bismuth nitrate and 5 g of a 60 wt % aqueous nitric acid solution, then 10 g of a silica-magnesia powder with an average particle diameter of 100 μm was added to the solution, and the resulting mixture was stirred. To the mixture was added 50 ml of an aqueous solution containing 5 wt % of sodium hydroxide and 5 wt % of formalin, the resulting mixture was stirred at 70° C. for 30 minutes, then filtered, and the resulting cake was washed with water (solid A). The solid A was added to a solution of 0.72 g of ferric nitrate dissolved in 40 ml of pure water, and the mixture was stirred. Then 20 ml of a 5 wt % aqueous formalin solution was added to the mixture, the resulting mixture was filtered, and the cake obtained was washed with water and dried to obtain the catalyst shown in Table 1. A reaction was conducted using the catalyst under the same conditions as in Example 1, to obtain the results shown in Table 2.

›EXAMPLE 3

A catalyst was prepared in the same manner as in Example 2 except for using 0.34 g of zinc acetate in place of ferric nitrate, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1, to obtain the results shown in Table 2.

›EXAMPLE 4

›EXAMPLE 5

In 50 ml of pure water were dissolved with heating 0.85 g of palladium chloride, 0.16 g of lead nitrate and 2 g of a 60 wt % aqueous nitric acid solution, then 10 g of a silica-magnesia powder with an average particle diameter of 100 μm was added to the solution, and the resulting mixture was stirred. To the mixture was added 50 ml of an aqueous solution containing 5 wt % of sodium hydroxide and 5 wt % of formalin, the resulting mixture was stirred at 80° C. for 30 minutes, then filtered, and the cake was washed with water and dried (solid A). The solid A was added to an aqueous solution of 0.72 g of ferric nitrate dissolved in 40 ml of pure water and the mixture was stirred. Then 20 ml of a 5 wt % aqueous formalin solution was added to the mixture, the resulting mixture was filtered, and the cake was washed with water and then dried to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1, to obtain the results shown in Table 2.

›EXAMPLE 6

A catalyst was prepared in the same manner as in Example 5 except for using 0.34 g of zinc acetate in place of ferric nitrate, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1, to obtain the results shown in Table 2.

›EXAMPLE 7

A catalyst was prepared in the same manner as in Example 5 except for using 0.72 g of ferric nitrate and 0.17 g of zinc acetate in place of ferric nitrate, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1 to obtain the results shown in Table 2.

›EXAMPLE 8

In 50 ml of pure water were dissolved with heating 0.85 g of palladium chloride, 0.16 g of lead nitrate, 0.46 g of bismuth nitrate and 5 g of 60 wt % aqueous nitric acid solution, then 10 g of a silica-magnesia powder with an average particle diameter of 100 μm was added to the solution, and the resulting mixture was stirred. To the mixture was added 80 ml of an aqueous solution containing 5 wt % of sodium hydroxide and 5 wt % of formalin, the resulting mixture was stirred at 70° C. for 30 minutes, then filtered, and the resulting cake was washed with water and dried to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1, to obtain the results shown in Table 2.

›EXAMPLE 9

In 50 ml of pure water were dissolved with heating 0.85 g of palladium chloride, 0.16 g of lead nitrate, 0.46 g of bismuth nitrate and 5 g of a 60 wt % aqueous nitric acid solution, then 10 g of a silica-magnesia powder with an average particle diameter of 100 μm was added to the solution and the resulting mixture was stirred. To the mixture was added 80 ml of an aqueous solution containing 5 wt % of sodium hydroxide and 5 wt % of formalin, the resulting mixture was stirred at 70° C. for 30 minutes, then filtered, and the resulting cake was washed with water (solid A). The solid A was added to a solution of 0.72 g of ferric nitrate dissolved in 40 ml of pure water and the mixture was stirred. Then 20 ml of a 5 wt % aqueous formalin solution was added to the mixture, the resulting mixture was filtered, and the cake was washed with water and dried to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1 to obtain the results shown in Table 2.

›EXAMPLE 10

A catalyst was prepared in the same manner as in Example 9 except for using 0.34 g of zinc acetate in place of ferric nitrate, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1, to obtain the results shown in Table 2.

›EXAMPLE 11

A catalyst was prepared in the same manner as in Example 9 except for using 0.19 g of barium acetate in place of ferric nitrate and using a silica powder with an average particle diameter of 100 μm in place of silica-magnesia, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1 to obtain the results shown in Table 2.

›EXAMPLE 12

A catalyst was prepared in the same manner as in Example 9 except for using 0.42 g of cobalt acetate in place of ferric nitrate and using a silica powder with an average particle diameter of 100 μm in place of silica-magnesia, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1 to obtain the results shown in Table 2.

›EXAMPLE 13

A catalyst was prepared in the same manner as in Example 9 except for using a calcium carbonate powder with an average particle diameter of 6 μm in place of silica-magnesia, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1 to obtain the results shown in Table 2.

›EXAMPLE 14

A reaction was conducted under the same conditions as in Example 1 except for using the catalyst prepared in Example 2 and using 5.02 g of p-methyl-benzaldehyde as an aldehyde. Methyl p-toluate was obtained as a carboxylic acid ester. The results obtained are shown in Table 2.

›EXAMPLE 15

A reaction was conducted under the same conditions as in Example 1 except for using the catalyst prepared in Example 2 and using 6.41 g of p-nitro-benzaldehyde in place of benzaldehyde, to obtain methyl p-nitrobenzoate as a carboxylic acid ester. The results thus obtained are shown in Table 2.

›EXAMPLE 16

A reaction was conducted under the same conditions as in Example 1 using the catalyst prepared in Example 1 except for using 2.87 g of methacrolein in place of benzaldehyde and changing a reaction time to 4 hours, to obtain methyl methacrylate as a carboxylic acid ester. The results thus obtained are shown in Table 2.

›EXAMPLE 17

A reaction was conducted under the same conditions as in Example 1 except for using the catalyst prepared in Example 2, using 2.87 g of methacrolein in place of benzaldehyde and changing a reaction time to 4 hours, to obtain methyl methacrylate as a carboxylic acid ester. The results thus obtained are shown in Table 2.

›EXAMPLE 18

A reaction was conducted under the same conditions as in Example 1 except for using the catalyst prepared in Example 2, using 2.3 g of acrolein in place of benzaldehyde and changing a reaction time to 4 hours, to obtain methyl acrylate as a carboxylic acid ester. The results thus obtained are shown in Table 2.

COMPARATIVE EXAMPLE 1

A catalyst was prepared in the same manner as in Example 1 except for using a titania with an average particle diameter of 100 μm in place of silica-magnesia, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1. The results thus obtained are shown in Table 2.

COMPARATIVE EXAMPLE 2

A catalyst was prepared in the same manner as in Example 2 except for using a zirconia with an average particle diameter of 50 μm in place of silica-magnesia, to obtain a catalyst shown in Table 1. The catalyst was used to conduct a reaction under the same conditions as in Example 1, to obtain the results shown in Table 2.

›INDUSTRIAL APPLICABILITY

According to the process of the present invention, carboxylic acid esters can be produced with a high yield from aldehydes and alcohols.

›Tables in the description — 3

Conversion (%)	=	B/A × 100
Ester selectivity (%)	=	C/B × 100
Acetal selectivity (%)	=	D/B × 100
Yield (%)	=	C/A × 100

TABLE 1

		Acid	Ammonia chemical
	Catalyst	strength	adsorption amount
	composition	pKa	(μmol/g-cat)
Example 1	Pd5—Bi2/SiO2—MgO	pKa > 4.8	115.3
Example 2	Pd5—Bi2—Fe1/SiO2—MgO	pKa > 4.8	128.2
Example 3	Pd5—Bi2—Zn1/SiO2—MgO	pKa > 4.8	111.7
Example 4	Pd5—Pb1/SiO2—MgO	pKa > 4.8	130.5
Example 5	Pd5—Pb1—Fe1/SiO2—MgO	pKa > 4.8	120.3
Example 6	Pd5—Pb1—Zn1/SiO2—MgO	pKa > 4.8	106.5
Example 7	Pd5—Pb1—Fe1—Zn0.5/SiO2—MgO	pKa > 4.8	120.6
Example 8	Pd5—Bi2—Pb1/SiO2—MgO	pKa > 4.8	121.0
Example 9	Pd5—Bi2—Pb1—Fe1/SiO2—MgO	pKa > 4.8	107.6
Example 10	Pd5—Bi2—Pb1—Zn1/SiO2—MgO	pKa > 4.8	105.5
Example 11	Pd5—Bi2—Pb1—Ba1/SiO2	pKa > 4.8	54.1
Example 12	Pd5—Bi2—Pb1—Co1/SiO2	pKa > 4.8	68.1
Example 13	Pd5—Bi2—Pb1—Fe1/CaCO2	pKa > 4.8	59.6
Example 14	Pd5—Bi2—Fe1/SiO2—MgO	pKa > 4.8	128.2
Example 15	Pd5—Bi2—Fe1/SiO2—MgO	pKa > 4.8	128.2
Example 16	Pd5—Bi2/SiO2—MgO	pKa > 4.8	115.3
Example 17	Pd5—Bi2—Fe1/SiO2—MgO	pKa > 4.8	128.2
Example 18	Pd5—Bi2—Fe1/SiO2—MgO	pKa > 4.8	128.2
Comparative	Pd5—Bi2—Fe1/TiO2	4.0 < pKa ≦ 4.8	292.8
Example 1
Comparative	Pd5—Bi2—Fe1/ZrO2	4.0 < pKa ≦ 4.8	177.4
Example 2

TABLE 2

				Ester	Acetal
			Conversion	selectivity	selectivity	Yield
	Aldehyde	Alcohol	(%)	(%)	(%)	(%)
Example 1	Benzaldehyde	Methanol	91.1	92.5	2.2	84.3
Example 2	Benzaldehyde	Methanol	93.3	95.2	1.2	88.8
Example 3	Benzaldehyde	Methanol	91.0	93.3	2.5	84.9
Example 4	Benzaldehyde	Methanol	90.2	92.7	3.2	83.6
Example 5	Benzaldehyde	Methanol	90.2	90.8	2.9	81.9
Example 6	Benzaldehyde	Methanol	87.8	90.3	3.1	79.3
Example 7	Benzaldehyde	Methanol	90.1	93.5	2.9	84.2
Example 8	Benzaldehyde	Methanol	93.1	92.6	2.6	86.2
Example 9	Benzaldehyde	Methanol	94.3	95.8	1.1	90.3
Example 10	Benzaldehyde	Methanol	93.3	94.5	1.5	88.2
Example 11	Benzaldehyde	Methanol	91.5	93.6	1.3	85.6
Example 12	Benzaldehyde	Methanol	94.1	94.2	1.0	88.6
Example 13	Benzaldehyde	Methanol	89.1	92.8	2.0	82.7
Example 14	p-Methylbenzaldehyde	Methanol	97.8	93.7	2.1	91.6
Example 15	p-Nitrobenzaldehyde	Methanol	69.0	90.8	3.5	62.7
Example 16	Methacrolein	Methanol	88.0	96.8	0.31	85.2
Example 17	Methacrolein	Methanol	85.0	95.7	0.53	81.3
Example 18	Acrolein	Methanol	95.0	96.3	0.42	91.5
Comparative	Benzaldehyde	Methanol	97.2	0	98.0	0
Example 1
Comparative	Benzaldehyde	Methanol	92.9	0	90.8	0
Example 2

Claims as granted

12 claims

Classifications

12 codes

IPC · International Patent Classification

Section B — Performing operations; transporting

B01J23/89
B01J23/644
B01J23/62

Section C — Chemistry; metallurgy

C07C67/42
C07C201/12
C07C67/39
C07B61/00
C07C69/78
C07C205/57
C07C69/54

USPC · US Patent Classification

560/210560/20

Claim changes

Soon

Coming soonHow the claims changed between publication and grant

See which claims were amended, added or cancelled during examination, with every added and removed word marked.

AmendedAddedCancelledUnchanged

The published claims of this application are not paired with the granted ones in what we hold.

File wrapper

⤢ drag to zoom

USPTOApplicanthover for detail · click to open

Pendency

3.9 y

1,433 days filing → grant

Office actions

non-final + final

Responses

no RCE

Examiner

Gary Geist

art unit 1621 · TC 1600

Law firm

Law firm · Log in to unlock

Citations: 6 back · 3 forward

See the full prosecution history — every USPTO and applicant action on this file, in order.

Documents

Log in to open the documents of this file: the application as filed, every office action and response, the notice of allowance.

Chain of title

⤢ drag to zoom

Titlehover for detail · click to open

See the full assignment history — every owner this patent has passed through, with recordation dates and reel/frame numbers.