US4005056A
Expired / Lapsed
US
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Process for the preparation of polyhydantoins and polyparanic acids
Assignee: Bayer AG
•
Filing: 1975-01-30
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Granted: 1977-01-25
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Expires: 1995-01-30
Abstract
Abstract Process for the preparation of polyhydantoins or polyparabanic acids, characterized in that bis- or polyglycine derivatives or bis- or poly-monoamidooxalic acid derivatives are heated to temperatures of 20° to 250° C with di- or polyiso(thio)cyanate derivatives without solvents and the highly fluid melt which has a melt viscosity of at the most 40,000 m.Pa.s. is optionally subjected to a shaping process and is polycondensed by adjustment to the reaction of 80° to 700° C.
Inventors
- 👤 Willi Dunwald
- 👤 Jurgen Lewalter
- 👤 Rudolf Merten
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 17:46
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/30; C08G18/38; C08G18/3819; C08G18/3823; C08G18/3825; C08G18/3821; C08G73/00; C08G73/06; C08G73/0605; C08G73/0616
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
173 words
A process for the production of a foil, coating or other shaped product of a polyhydantoin or polyparabanic acid, wherein, in order to prepare the polyhydantoin, a bis- or polyglycine derivative of the formula ##STR7##wherein Ar is an n-valent aromatic group; the groups R 1 , which may be the same or different, are hydrogen, aryl or alkyl; R 2 is hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy and n is 2, 3 or 4, or, in order to prepare the polyparabanic acid, a bis- or polymonoamidooxalic acid of the formula ##STR8##wherein Ar, R 2 and n are as aforesaid, is heated in the absence of a solvent with at least one blocked reaction product of a di- or poly(thio) isocyanate and a compound containing Zerewitinoff-active hydrogen atoms, to a temperature which obtains a highly fluid melt having a melt viscosity of at most 40,000 m.Pa.s without unblocking said blocked reaction product and the resulting melt is subjected to a shaping process and polycondensed at a temperature of from 150° to 400° C.
Claim 2
Dependent Claim
173 words
A process for the production of a foil, coating or other shaped product of a polyhydantoin or polyparabanic acid, wherein, in order to prepare the polyhydantoin, a bis- or polyglycine derivative of the formula ##STR7##wherein Ar is an n-valent aromatic group; the groups R 1 , which may be the same or different, are hydrogen, aryl or alkyl; R 2 is hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy and n is 2, 3 or 4, or, in order to prepare the polyparabanic acid, a bis- or polymonoamidooxalic acid of the formula ##STR8##wherein Ar, R 2 and n are as aforesaid, is heated in the absence of a solvent with at least one blocked reaction product of a di- or poly(thio) isocyanate and a compound containing Zerewitinoff-active hydrogen atoms, to a temperature which obtains a highly fluid melt having a melt viscosity of at most 40,000 m.Pa.s without unblocking said blocked reaction product and the resulting melt is subjected to a shaping process and polycondensed at a temperature of from 150° to 400° C.
Claim 3
Dependent Claim
91 words
A process as claimed in claim 1 wherein the di- or polyiso(thio)cyanate derivative is based on an iso(thio)cyanate of the formula R.sup.3 (--NCO).sub. z or R.sup.3 (--NCS).sub.z, in which R 3 is alkyl having 1 to 20 carbon atoms; an aromatic group having 5 to 12 carbon atoms; cycloalkyl having 4 to 12 carbon atoms; an aliphatic-aromatic group having 6 to 36 carbon atoms or an aromatic or cycloaliphatic group having 3 to 12 carbon atoms which contains a hetero atom and z is an integer of from 1 to 4.
Claim 4
Dependent Claim
38 words
A process as claimed in claim 1 in which the bis- or polyglycine derivative or bis- or poly-monoamidooxalic acid derivative is heated with the di- or poly iso(thio)cyanate derivative to a temperature of from 70° to 180° C.
Claim 5
Dependent Claim
19 words
A process as claimed in claim 1 wherein Ar is an aromatic group having 6 to 12 carbon atoms.
Claim 6
Dependent Claim
17 words
A process as claimed in claim 1 wherein Ar represents an aromatic group which contains hetero atoms.
Claim 7
Dependent Claim
26 words
A process as claimed in claim 1 wherein at least one of the groups R 1 is an alkyl group having 1 to 4 carbon atoms.
Claim 8
Dependent Claim
24 words
A process as claimed in claim 1 wherein the alkyl moieties contained in the substituent R 2 having 1 to 4 carbon atoms. glycerol;
Claim 9
Dependent Claim
23 words
A process as claimed in claim 1 wherein the aryl moieties contained in the substituent R 2 have 6 to 10 carbon atoms.
Claim 10
Dependent Claim
22 words
A process as claimed in claim 1 wherein the di- or polyglycine derivative is N,N' -bis-[ethoxycarbonylmethyl]-4,4'-diamino-diphenylmethane; N,N'-bis-[2-methoxycarbonylpropyl-(2)]-4,4'-diamino-diphenylmethane; N,N'-bis-[2-methoxycarbonylpropyl-(2)]-4,4'-diaminodiphenyl ether or N,N' -bis-[2methoxycarbonylpropyl-(2)]-1,3-diaminobenzene.
Claim 11
Dependent Claim
18 words
A process as claimed in claim 1 wherein the bis- or poly-monoamidooxalic acid is N,N'-bis-[ethoxyoxalyl]-4,4'-diaminodiphenylmethane or N,N'-bis-[ethoxyoxalyl]-4,4'-diaminodiphenyl ether.
Claim 12
Dependent Claim
17 words
A process as claimed in claim 1 wherein the di- or polyiso(thio)cyanate is blocked with an alcohol.
Claim 13
Dependent Claim
50 words
A process as claimed in claim 11 wherein the alcohol is an aliphatic monohydric alcohol having 1 to 16 carbon atoms, a cycloaliphatic alcohol having 5 to 12 carbon atoms, an aliphatic diol or polyol with 1 to 12 carbon atoms or a phenol having 6 to 12 carbon atoms.
Claim 14
Dependent Claim
24 words
A process as claimed in claim 11 wherein the di- or polyiso(thio)cyanate is blocked with an oxime, secondary amine, cyclic amine or cyclic amide
Claim 15
Dependent Claim
50 words
A process as claimed in claim 1 wherein the di- or polyiso(thio)cyanate derivative comprises a mixture of blocked poly(iso)thiocyanates, in which 1 to 99 equivalent percent of the polyiso(thio)cyanates are blocked with an alkanol or cycloalkanol and 99 to 1 equivalent percent are blocked with a phenol, oxime or lactam.
Claim 16
Dependent Claim
37 words
A process as claimed in claim 14 wherein 50 to 99 equivalent percent of the polyiso(thio)cyanates are blocked with an alkanol or cycloalkanol and 50 to 1 equivalent percent are blocked with a phenol, oxime or lactam.
Claim 17
Dependent Claim
29 words
A process as claimed in claim 1 wherein equivalent quantities of di- or poly-glycine derivatives or bis- or poly-monoamido oxalic acid derivatives are heated with di- or polyiso(thio)cyanate derivatives.
Claim 18
Dependent Claim
42 words
A process as claimed in claim 1, characterised in that a quantity of 2/p to 4/p mol of the polyiso(thio)cyanate derivative with p blocked NCO-groups per molecule is used for 1 mol of bis-glycine or bis-monoamidooxalic acid derivative, where p is >1.
Claim 19
Dependent Claim
51 words
A process as claimed in claim 1, characterised in that the di- or poly iso(thio)cyanate derivatives are prepared directly in the reaction mixture by reaction of the corresponding iso(thio)cyanates with the blocking agents and then mixed and reacted with the di- or poly glycine derivatives or bis- or poly-monoamidooxalic acid derivatives.
Claim 20
Dependent Claim
38 words
A process as claimed in claim 1, wherein the polycondensation is carried out in the presence of low-molecular weight polyols, hydroxyl-containing epoxides, urethanes, imide esters, hydantoins, polyesters or polyethers and polyamines, aminoalcohols, polyamides, polyester imides or polyamido imines.
Claim 21
Dependent Claim
25 words
A process as claimed in claim 1 wherein up to 20 mols % of the blocked polyiso(thio)cyanate is replaced by a blocked monoisocyanate or monoisothiocyanate.
Claim 22
Dependent Claim
18 words
A process as claimed in claim 1 wherein the condensation reaction is accelerated by an isocyanate polyaddition catalyst.
Claim 23
Dependent Claim
38 words
A process as claimed in claim 21 wherein the isocyanate polyaddition catalyst is a tertiary amine; a silaamine with carbon-silicon bonds; a blocked nitrogen-containing base; an organic metal compound; a blocked aromatic hydroxy compound or a phenol-Mannich base.
Claim 24
Dependent Claim
28 words
A process as claimed in claim 21 wherein the catalyst is used in a quantity of from 0.01 to 5 % by weight, based on the blocked isocyanate.
Claim 25
Dependent Claim
28 words
A process as claimed in claim 23 wherein the catalyst is used in a quantity of from 0.1 to 1.0 % by weight, based on the blocked isocyanate.
Claim 26
Dependent Claim
15 words
A polyhydantoin or polyparabanic acid when prepared by a process as claimed in claim 1.
References Cited (Backward Citations)
US3397253A
Cited
US3448170A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-01-25 | 1980-07-26 | 1981-01-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-01-25 | 1984-07-26 | 1985-01-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-01-25 | 1988-07-26 | 1989-01-25 | $7700.00 | Window Closed / Lapsed |