GB1592463A - Process for the preparation of carbamic acid esters of high-boiling alcohols - Google Patents
Process for the preparation of carbamic acid esters of high-boiling alcohols Download PDFInfo
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- GB1592463A GB1592463A GB51149/77A GB5114977A GB1592463A GB 1592463 A GB1592463 A GB 1592463A GB 51149/77 A GB51149/77 A GB 51149/77A GB 5114977 A GB5114977 A GB 5114977A GB 1592463 A GB1592463 A GB 1592463A
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- Prior art keywords
- alcohol
- carbamic acid
- mole
- boiling
- acid ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The carbamates are prepared by reacting lower aliphatic carbamates with higher-boiling alcohols. Reaction is carried out in the presence of alkyl titanates as catalyst, with heating. The low molecular weight alcohols formed are distilled continuously from the reaction mixture. By using the alkyl titanates as catalyst, reaction times are greatly reduced.
Description
(54) PROCESS FOR THE PREPARATION OF CARBAMIC ACID ESTERS
OF HIGH-BOILING ALCOHOLS
(71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal
Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The present invention relates to the preparation of carbamic acid esters.
Carbamic acid esters of relatively high molecular weight may be synthesised from the corresponding relatively high molecular weight alcohol by phosgenation to produce a chlorocarbonic acid ester, followed by aminolysis of this ester.
This method of manufacture is generally rather expensive; an alternative process is the reaction of a lower aliphatic carbamic acid ester with a relatively high molecular weight alcohol. In U.S. Patent Specification 2 934 549, S. Beinfest et al. describe a process of this type, and propose the use of an aluminium alcoholate as catalyst.
The present invention provides a process for the conversion of the carbamic acid ester of a low-boiling alcohol (as hereinafter defined) into the carbamic acid ester of a high-boiling alcohol (as hereinafter defined), which comprises reacting the carbamic acid ester of a low-boiling alcohol with a high-boiling alcohol, the reaction being carried out using an alkyl titanate as catalyst, and the resulting low-boiling alcohol being distilled off from the reaction mixture. Preferably the alkyl titanate is of low molecular weight; preferably the lowboiling alcohol is distilled off from the reaction mixture continuously.
The process of the invention may also be used for the transesterification of
N-substituted carbamic acid esters.
The terms "low-boiling" and "lower" whenever used herein in connection with an alcohol refers to an alcohol having from 1 to 5 carbon atoms. The term "high-boiling" whenever used herein in connection with an alcohol refers to an alcohol having a boiling point of substantially 190"C or more.
When using an alkyl titanate as catalyst, it generally proves possible, under otherwise identical conditions, to shorten the reaction times to half, and in many cases to onetenth, of the time required when using an aluminium alcoholate. In addition, when using the process of the invention, it is generally not necessary to employ an excess of the lower aliphatic carbamic acid ester, as is described in Examples 1 and 5 to 7 of U.S.
Patent Specification 2,934,559. Thus, in the transesterification of ethyl carbamate with 1,5-pentanediol, described in Example 6 of
U.S. Patent Specification 2,934,559, it has proved possible, when using the process of the present invention, to increase the yield from 68.5% to 91% in spite of reducing the amount of carbamic acid ester from 1.3 moles to one mole equivalent. The reaction time was reduced from 4 hours to 12 hours.
In the case of the transesterification with a relatively high molecular weight polyglycol ether, the method according to U.S.
Patent Specification 2,934,559, using aluminium alcoholate as the catalyst, is generally disadvantageous; for example, when using a polyglycol of molecular weight 1,000, the reaction time must be increased by more than 20 hours in order to achieve 70% conversion.
Suitable high-boiling alcohols are especially alkanols or alkanediols, their oxyalkylation products, and oxyalkylation products of trihydric or tetrahydric aliphatic alcohols, which at normal conditions have a boiling point above 1900C and also above that of the low molecular weight carbamic acid ester employed.
The reaction temperature in the process of the invention is preferably in the range of from 80 to 210 C at a pressure in the range of from 25 to 760 mm Hg. The reaction temperature depends on the boiling point of the alcohol liberated and on the structure of the high boiling alcohol. Whilst, for example, polyethylene glycols of molecular weight up to about 300 generally undergo transesterification even at atmospheric pres sure and temperatures of from 160 to 1800C, it is usually necessary when using relatively high-molecular weight polyethylene glycols, to use reduced pressure of, for example, 100 to 300 mm Hg.
Lower pressures may be useful if the reaction can be carried out at a low reaction temperature. In the process of the invention, the reaction temperature and pressure are generally limited by the boiling point of the low molecular weight carbamic acid ester used. When using carbamic acid ethyl ester, for example, these limits are 1 800C at a pressure of 760 mm Hg or. for example, 140"C at a pressure of 24() mm Hg. Preferably the reaction is carried out a tempera ture in the range of from 140 to 1600 and a pressure in the range of from l00 to 240 mm Hg, provided the rcactants permit this.
High-boiling alcohols which may be used include aliphatic. saturated. monohydric or polyhydric (including dihydric) alcohols or ether-aleohols which have a boiling point.
under the reaction conditions. above that of the low molecular weight carbamic acid ester used. The boiling point of the highboiling alcohol should preferably be above l 90 C, preferably above 210 C. Highboiling alcohols which are especially useful are so-called fatty alcohols with about 8 to 20 carbon atoms, for example octyl alcohol, dodecyl alcohol, stcaryl alcohol or cetyl alcohol, and their reaction products with about l to 50 moles of ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, for example pentacthoxy-dedccanol and tetrapropoxy heptacthoxyoctadecanol. and alkanediols with 2 to 5 carbon atoms in the reaction products of these alkanediols or of trihydric and tetrahydric alcohols, such as pentacrythritol or glycerol, with about 1 to 200 moles of ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide.
Preferred high-boiling alcohols include ethylene glycol, diethylene glycol, polyethylene glycols having molecular weights of 150 to about 10,000, propylene glycol, butylene glycol and pcntane-1,5- glycol.
The reaction products of the present invention may be used as plasticisers for cellulose articles; for this use, polyethylene glycols with molecular weights of from about 200 to 5,0()0 are preferably used in the transcsterification reaction.
Low molecular weight carbamic acid esters which can be used include alkyl carbamates having from 2 to 5 carbon atoms.
for example methyl carbamate, ethyl carbamate, propyl carbamate, isopropyl carbamate and butyl carbamate or a mixture of two or more of these carbamates.
Suitable alkyl titanates are especially those having from 1 to 4 carbon atoms. for example methyl titanate, ethyl titanate or isopropyl titanate. The concentration of the alkyl titanate in the reaction mixture may vary within wide limits; and is suitably optimised in each particular case. Preferably, 0.001 to 0.1 mole of the alkyl titanate is used per mole of the high-boiling alcohol.
To carrv out the transesterification of the invention, the carbamic acid ester and the high-boiling alcohol are advantageously used in about equivalent amounts. The reaction time for the transesterification depends above all on the nature of the high-boiling alcohol and on the reaction conditions: in most cases, a reaction time of about 1 to 2 hours suffices; however, in order to complete the transesterification as far as possible. this may be followed by a post-rcaction period of about 2 to 4 hours.
The carbamic acid esters of high-boiling alcohols obtained by the process of the invention may be used as plasticisers for fibres and films of natural and regenerated cellulose and as agents for rendering synthetic fibres hydrophilic. Reaction of the carbamic acid esters with formaldehyde gives products which possess groups which are reactive towards cellulose and can be used as reactive plasticisers for cellulose fibres and films.
The following Examples illustrate the invention.
Exarnple 1:
200 g (1 mole) of a polyethylene glycol of molecular weight 200, 178 g (2 moles) of ethyl carbamate and 2 g of ethyl titanate were heated to 160 to 1800C in a fournecked flask equipped with a distillation attachment, thermometer, stirrer and heater. 82 g of ethanol (1.78 moles) distilled off over 2 hours. Polyethylene glycol (200) bis-carbamic acid ester was obtained in a yield of 258 g (890/o of theory).
ExatipTh 2 500 g (0.5 moles) of polyethylene glycol of molecular weight 1,000, 89 g (1 mole) of ethyl carbamate and 2 g of isopropyl titanate were heated under a pressure of 200 mm Hg to 140 to 1500C whilst stirring, and the ethanol formed was collected in a cold trap. After 90 minutes' reaction time, 41.5 g (90% of theory) of the alcohol distilled over.
In the course of a further 40 minutes' period of heating. a further 4.5 g of ethanol were obtained. 530 g of polyethylene glycol (1,000) bis-carbamic acid ester were obtained, corresponding to a conversion of 97.7%.
Example 3
135 g (0.5 mole) of octadecyl alcohol, 51.5 g (0.5 mole) of isopropyl carbamate and 1 g of isopropyl titanate are heated under a pressure of 300 mm Hg to 150 to 155"C, whilst stirring. 29 g of isopropanol distilled off over 75 minutes. Octadecyl car bamate was obtained in a yield of 136 g (99% of theory) and with a melting point of 93 to 94"C (after recrystallisation from ethanol).
Example 4
31 g (0.5 mole) of ethylene glycol and 89 g (mole) of ethyl carbamate were heated together with 2 g of isopropyl titanate.
Using an external temperature of 180 to 195"C, 41 g of ethanol distilled off over 6 hours through a descending condenser.
After recrystallisation from ethanol, 55 g of ethylene glycol bis-carbamic acid ester are obtained, corresponding to a yield of 74%.
Example 5
1,000 g (0.2 mole) of a polyether-alcohol of molecular weight 5,000, obtained by reacting 1 mole of pentaerythritol with 20 moles of propylene oxide and 80 moles of ethylene oxide, were heated with 35.6 g (0.4 mole) of ethyl carbamate and 2 g of isopropyl titanate to 1500C under a pressure of 300 mm Hg. 18.2 g of ethanol distilled off over 6 hours and were collected in a cold trap; this corresponds to a conversion of 98% based on the ethyl carbamate.
Example 6
500 g (0.5 mole) of a polyethylene glycol of molecular weight 1,000, 117 g (1.0 mole) of butyl carbamate and 1.3 g (0.05 mole) of ethyl titanate were heated under a pressure of 140 mm Hg to 150 to 1600C, whilst stirring. 65 g of butanol distilled off over 3 hours, and were collected, via a descending condenser, in an ice-cooled receiver. This corresponded to a conversion of 88%.
Polyethylene glycol (1,000) bis-carbamic acid ester was obtained in a yield of 548 g.
Example 7
338 g (0.4 mole) of a reaction product of 1 mole of dodecyl alcohol with 15 moles of ethylene oxide were heated with 47 g (0.4 mole) of butylurethane and 2 g of isopropyl titanate under a pressure of 140 mm Hg to 150 to 1600C, whilst stirring. After 2 hours, the pressure was reduced to 60 mm Hg. 31.7 g of alcohol distilled over, containing 26 g (82% of theory) of butanol were detected by gas chromatography. This corresponded to a conversion of 88%.
The yield of carbamic acid ester of ethoxylated dodecyl alcohol was 320 g (90% of theory).
WHAT WE CLAIM IS:
1. A process for the conversion of the carbamic acid ester of a low-boiling alcohol (as hereinbefore defined) into the carbamic acid ester of a high-boiling alcohol (as hereinbefore defined), which comprises reacting the carbamic acid ester of a lowboiling alcohol with a high-boiling alcohol, the reaction being carried out using an alkyl titanate as catalyst, and the resulting lowboiling alcohol being distilled off from the reaction mixture.
2. A process as claimed in claim 1, wherein the low-boiling alcohol produced is distilled off from the reaction mixture continuously.
3. A process as claimed in either claim 1 or claim 2, wherein the high-boiling alcohol is an aliphatic saturated alcohol or etheralcohol.
4. A process as claimed in claim 3, wherein the high-boiling alcohol is an alkanol or an alkanediol or an alkoxylated product of a mono-, di-, tri- or tetra-hydric alcohol.
5. A process as claimed in claim 4, wherein the high-boiling alcohol is a fatty alcohol having from 8 to 20 carbon atoms or a reaction product thereof with from 1 to 50 moles of ethylene oxide and/or propylene oxide; or an alkanediol having from 2 to 5 carbon atoms or a reaction product thereof with from 1 to 200 moles of ethylene oxide and/or propylene oxide; or a reaction product of a tri- or tetra-hydric alcohol with from 1 to 200 moles of ethylene oxide and/or propylene oxide.
6. A process as claimed in any one of claims 1 to 5, wherein the high-boiling alcohol has a boiling point greater than 210 C under normal atmospheric pressure.
7. A process as claimed in any one of claims 1 to 6, wherein the carbamic acid ester of a low-boiling alcohol has from 2 to 5 carbon atoms.
8. A process as claimed in any one of claims 1 to 7, wherein the alkyl titanate has from 1 to 4 carbon atoms.
9. A process as claimed in any one of claims 1 to 8, wherein there is used from 0.001 to 0.1 mole of alkyl titanate per mole of the high-boiling alcohol.
10. A process as claimed in any one of claims 1 to 9, wherein the reaction is carried out at a temperature in the range of from 80 to 210 C under a pressure in the range of from 25 to 760 mm Hg.
11. A process as claimed in claim 1, carried out substantially as described in any one of Examples herein.
12. An ester of carbamic acid whenever prepared by a process as claimed in any one of claims 1 to 11.
13. A process for the manufacture of carbamic acid esters of high-boiling alcohols (as hereinbefore defined) by transesterification of carbamic acid ester of a lower aliphatic alcohol (as hereinbefore defined) with a high-boiling alcohol which comprises heating the high-boiling alcohol and the carbamic acid ester of a lower aliphatic alcohol in the presence of an alkyl titanate as a catalyst and continuously distilling off from the reaction mixture the resulting lower alcohol.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
- **WARNING** start of CLMS field may overlap end of DESC **.bamate was obtained in a yield of 136 g (99% of theory) and with a melting point of 93 to 94"C (after recrystallisation from ethanol).Example 431 g (0.5 mole) of ethylene glycol and 89 g (mole) of ethyl carbamate were heated together with 2 g of isopropyl titanate.Using an external temperature of 180 to 195"C, 41 g of ethanol distilled off over 6 hours through a descending condenser.After recrystallisation from ethanol, 55 g of ethylene glycol bis-carbamic acid ester are obtained, corresponding to a yield of 74%.Example 5 1,000 g (0.2 mole) of a polyether-alcohol of molecular weight 5,000, obtained by reacting 1 mole of pentaerythritol with 20 moles of propylene oxide and 80 moles of ethylene oxide, were heated with 35.6 g (0.4 mole) of ethyl carbamate and 2 g of isopropyl titanate to 1500C under a pressure of 300 mm Hg. 18.2 g of ethanol distilled off over 6 hours and were collected in a cold trap; this corresponds to a conversion of 98% based on the ethyl carbamate.Example 6500 g (0.5 mole) of a polyethylene glycol of molecular weight 1,000, 117 g (1.0 mole) of butyl carbamate and 1.3 g (0.05 mole) of ethyl titanate were heated under a pressure of 140 mm Hg to 150 to 1600C, whilst stirring. 65 g of butanol distilled off over 3 hours, and were collected, via a descending condenser, in an ice-cooled receiver. This corresponded to a conversion of 88%.Polyethylene glycol (1,000) bis-carbamic acid ester was obtained in a yield of 548 g.Example 7338 g (0.4 mole) of a reaction product of 1 mole of dodecyl alcohol with 15 moles of ethylene oxide were heated with 47 g (0.4 mole) of butylurethane and 2 g of isopropyl titanate under a pressure of 140 mm Hg to 150 to 1600C, whilst stirring. After 2 hours, the pressure was reduced to 60 mm Hg. 31.7 g of alcohol distilled over, containing 26 g (82% of theory) of butanol were detected by gas chromatography. This corresponded to a conversion of 88%.The yield of carbamic acid ester of ethoxylated dodecyl alcohol was 320 g (90% of theory).WHAT WE CLAIM IS: 1. A process for the conversion of the carbamic acid ester of a low-boiling alcohol (as hereinbefore defined) into the carbamic acid ester of a high-boiling alcohol (as hereinbefore defined), which comprises reacting the carbamic acid ester of a lowboiling alcohol with a high-boiling alcohol, the reaction being carried out using an alkyl titanate as catalyst, and the resulting lowboiling alcohol being distilled off from the reaction mixture.
- 2. A process as claimed in claim 1, wherein the low-boiling alcohol produced is distilled off from the reaction mixture continuously.
- 3. A process as claimed in either claim 1 or claim 2, wherein the high-boiling alcohol is an aliphatic saturated alcohol or etheralcohol.
- 4. A process as claimed in claim 3, wherein the high-boiling alcohol is an alkanol or an alkanediol or an alkoxylated product of a mono-, di-, tri- or tetra-hydric alcohol.
- 5. A process as claimed in claim 4, wherein the high-boiling alcohol is a fatty alcohol having from 8 to 20 carbon atoms or a reaction product thereof with from 1 to 50 moles of ethylene oxide and/or propylene oxide; or an alkanediol having from 2 to 5 carbon atoms or a reaction product thereof with from 1 to 200 moles of ethylene oxide and/or propylene oxide; or a reaction product of a tri- or tetra-hydric alcohol with from 1 to 200 moles of ethylene oxide and/or propylene oxide.
- 6. A process as claimed in any one of claims 1 to 5, wherein the high-boiling alcohol has a boiling point greater than 210 C under normal atmospheric pressure.
- 7. A process as claimed in any one of claims 1 to 6, wherein the carbamic acid ester of a low-boiling alcohol has from 2 to 5 carbon atoms.
- 8. A process as claimed in any one of claims 1 to 7, wherein the alkyl titanate has from 1 to 4 carbon atoms.
- 9. A process as claimed in any one of claims 1 to 8, wherein there is used from 0.001 to 0.1 mole of alkyl titanate per mole of the high-boiling alcohol.
- 10. A process as claimed in any one of claims 1 to 9, wherein the reaction is carried out at a temperature in the range of from 80 to 210 C under a pressure in the range of from 25 to 760 mm Hg.
- 11. A process as claimed in claim 1, carried out substantially as described in any one of Examples herein.
- 12. An ester of carbamic acid whenever prepared by a process as claimed in any one of claims 1 to 11.
- 13. A process for the manufacture of carbamic acid esters of high-boiling alcohols (as hereinbefore defined) by transesterification of carbamic acid ester of a lower aliphatic alcohol (as hereinbefore defined) with a high-boiling alcohol which comprises heating the high-boiling alcohol and the carbamic acid ester of a lower aliphatic alcohol in the presence of an alkyl titanate as a catalyst and continuously distilling off from the reaction mixture the resulting lower alcohol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762655741 DE2655741A1 (en) | 1976-12-09 | 1976-12-09 | METHOD FOR PRODUCING CARBAMID ACID ESTERS OF HIGH-BOILING ALCOHOLS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1592463A true GB1592463A (en) | 1981-07-08 |
Family
ID=5995046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB51149/77A Expired GB1592463A (en) | 1976-12-09 | 1977-12-08 | Process for the preparation of carbamic acid esters of high-boiling alcohols |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5373520A (en) |
| AR (1) | AR220690A1 (en) |
| AT (1) | AT359516B (en) |
| AU (1) | AU514123B2 (en) |
| BE (1) | BE861700A (en) |
| BR (1) | BR7708161A (en) |
| CA (1) | CA1111063A (en) |
| CH (1) | CH630343A5 (en) |
| DE (1) | DE2655741A1 (en) |
| ES (1) | ES464677A1 (en) |
| FR (1) | FR2373520A1 (en) |
| GB (1) | GB1592463A (en) |
| IT (1) | IT1089317B (en) |
| NL (1) | NL7713388A (en) |
| ZA (1) | ZA777334B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001014431A2 (en) * | 1999-08-20 | 2001-03-01 | Ppg Industries Ohio, Inc. | Process for the preparation of carbamate functional polymers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3529531A1 (en) * | 1985-08-17 | 1987-02-26 | Basf Ag | METHOD FOR PRODUCING CARBAMID ACID ESTERS |
| US9334234B2 (en) * | 2014-05-08 | 2016-05-10 | Basf Coatings Gmbh | Method using titanium catalyst for producing carbamate-functional materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2184545B1 (en) * | 1972-05-17 | 1980-03-14 | Rhone Poulenc Ind |
-
1976
- 1976-12-09 DE DE19762655741 patent/DE2655741A1/en not_active Withdrawn
-
1977
- 1977-12-02 ES ES464677A patent/ES464677A1/en not_active Expired
- 1977-12-02 NL NL7713388A patent/NL7713388A/en not_active Application Discontinuation
- 1977-12-06 AT AT872277A patent/AT359516B/en not_active IP Right Cessation
- 1977-12-06 CH CH1490277A patent/CH630343A5/en not_active IP Right Cessation
- 1977-12-07 AR AR270276A patent/AR220690A1/en active
- 1977-12-07 IT IT30515/77A patent/IT1089317B/en active
- 1977-12-08 JP JP14666577A patent/JPS5373520A/en active Pending
- 1977-12-08 GB GB51149/77A patent/GB1592463A/en not_active Expired
- 1977-12-08 BR BR7708161A patent/BR7708161A/en unknown
- 1977-12-08 AU AU31361/77A patent/AU514123B2/en not_active Expired
- 1977-12-08 FR FR7736985A patent/FR2373520A1/en not_active Withdrawn
- 1977-12-08 CA CA292,686A patent/CA1111063A/en not_active Expired
- 1977-12-08 ZA ZA00777334A patent/ZA777334B/en unknown
- 1977-12-09 BE BE183330A patent/BE861700A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001014431A2 (en) * | 1999-08-20 | 2001-03-01 | Ppg Industries Ohio, Inc. | Process for the preparation of carbamate functional polymers |
| WO2001014431A3 (en) * | 1999-08-20 | 2001-08-30 | Ppg Ind Ohio Inc | Process for the preparation of carbamate functional polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| AT359516B (en) | 1980-11-10 |
| JPS5373520A (en) | 1978-06-30 |
| CA1111063A (en) | 1981-10-20 |
| ATA872277A (en) | 1980-04-15 |
| DE2655741A1 (en) | 1978-06-15 |
| ZA777334B (en) | 1978-10-25 |
| AU3136177A (en) | 1979-06-14 |
| IT1089317B (en) | 1985-06-18 |
| CH630343A5 (en) | 1982-06-15 |
| BE861700A (en) | 1978-06-09 |
| ES464677A1 (en) | 1978-09-01 |
| AR220690A1 (en) | 1980-11-28 |
| AU514123B2 (en) | 1981-01-29 |
| BR7708161A (en) | 1978-08-15 |
| NL7713388A (en) | 1978-06-13 |
| FR2373520A1 (en) | 1978-07-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |