Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2000-08-24
2002-06-18
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S198000
Reexamination Certificate
active
06407198
ABSTRACT:
TECHNICAL FIELD
The present invention is related to cyclocarbonate oligomers and polymer compounds based on them and, more specifically, to coatings, adhesives, composite materials, sealants, and synthetic leather and to methods of producing such materials.
BACKGROUND OF THE INVENTION
Nonisocyanate polyurethane oligomers and polymers are the product of the reaction of cyclocarbonate oligomers and primary amine oligomers. Typically the cyclocarbonate oligomer react with the primary aliphatic amine oligomer. By this reaction a cross-linked network polymer structure results in which an intermolecular hydrogen bond is formed through the hydroxyl group at the &bgr;-carbon atom of the polyurethane chain.
The blockage of carbonyl oxygen considerably lowers the susceptibility of the whole urethane group to hydrolysis. Moreover, materials containing intermolecular hydrogen bonds display chemical resistance 1.5-2 times greater in comparison with materials of similar structure without such bonds.
There is known method of production of linear nonisocyanate polyurethane based on reaction between oligomeric bifunctional cyclocarbonates and primary aliphatic amines (U.S. Pat. No. 5,340,889, published 23.08.94)
There is known method of preparing of nonisocianate compounds by mixing polyfunctional cyclocarbonate and primary amine oligomer (O. Figovsky, L. Shapovalov, N. Blank. Monolithic Chemical Resistant Floor Covering Based on Non-Isocyanate Polyurethanes./Corrosion and its control./Proceedings of CORCON-97, Mumbai, India. 1997. v.2 p.757-763.
But it is impossible to prepare nonisocyanate polyurethane materials using aromatic amines and cyclocarbonates because of forming CO
2
and low molecular weight of compounds. One of the possible processes for making cyclocarbonates is a reaction between carbon dioxide and an epoxy compound in the presence of a catalyst.
SUMMARY OF THE INVENTION
It is an object of the invention to provide for a new polyfunctional polycarbonate oligomers and for a new an improved method of preparing of polycarbonates.
According the invention the chemically resistant materials with high mechanical properties are provided by using polycyclocarbonates of special structure. The polycyclocarbonates are prepared by the reaction of oligocyclocarbonates containing ended epoxy groups with primary aromatic diamine.
One embodiment of the present invention relates to oligomers containing epoxy and cyclocarbonate groups, adduct of aromatic diamines with these oligomers. Such oligomers may be used by two ways—by curing the oligomers with primary aliphatic amines and by preparing adducts which are used for curing epoxy resins or cyclocarbonate oligomers for preparing constructive glues, sealants, coatings, construction, etc.
The new polyfunctional polycyclocarbonate oligomers of the present invention can be defined by the formula:
wherein: R
1
—aliphatic, cycloaliphatic, aromatic, alkylaromatic, oligoester or oligoether radicals
R
2
—aromatic radicals
R
3
—H, alkyl, aryl, alkylaryl
m=1-2; n=1-5
The method of preparing of new polyfunctional polycyclocarbonates comprises reacting a compound of the formula:
with primary aromatic diamines by stoichiometric ratio to epoxy groups.
The method also includes carrying out the reaction at a temperature from 100° C. to 150° C. both in “situ” and in an organic solvent.
The method also includes using oligomers, chosen from the group which includes oligomer's having the following structures:
where R
1
=
1. —O&Brketopenst;(CH
2
)
k
—O&Brketclosest;
y
k=2-6, y=1-20, n=1
2.
where: R
4
=CH
3
, C
2
H
5
y=1-20, n=1
3.
where: R
4
=H, CH
3
m+z+f=0-50
n=2
4.
where: R
4
=H, CH
3
p+e=0-50
q=1-2
n=2
where: X=—C
2
—, (CH
3
)
2
C═, —SO
2
—, (CF
3
)
2
C═;
R
5
, R
6
=—H, —CH
3
, —Cl, —Br; e=0-5, n=1
where: X=—CH
2
—, (CH
3
)
2
C═, —SO
2
—,
R
5
, R
6
=—H, —CH
3
, —Cl; n=3
where:
—(CH
2
)
m
—; e=0-2, n=1
10.
where: R
8
=—H, —CH
3
, —Br, —Cl;
n=1
where: R
9
=—H, —CH
3
; m=1-5, n=2-6
14.
where: R
11
=—H, —CH
3
;
y=1-2, n=2
15.
n=1
where: R
12
, R
13
=H, CH
3
; m+k=0-6, n=1
n=1
The method also includes preferably using oligomers, chosen from the following group:
The method also includes using aromatic diamines, chosen from the groups, which contain:
H
2
N—R—NH
2
where R:=
where: R
1
=—CH
3
, —Cl;
where: X=—CH
2
, (CH
3
)
2
═,
—O—
R
2
=—H, CH
3
—, Cl—;
The method also includes preferably using aromatic diamines, chosen from the group, which contain:
The present invention also includes using of polyfunctional Cyclocarbonate Oligomers for preparing amine hardeners having ended aminoalkyl groups:
DETAILED DESCRIPTION OF THE INVENTION
Polycyclocarbonate oligomers of the present invention are based upon oligomers with epoxy and cyclocarbonate groups which ware prepared by the reaction of carbon dioxide and an epoxy oligomer with catalyst according our pat. (Patent Israel 122763)
Such oligomers containing epoxy and cyclocarbonate groups react with aromatic diamines only by epoxy groups. It is possible to cure such cyclocarbonate oligomers by primary aliphatic amines and to prepare adducts of synthesised cyclocarbonates with primary aliphatic amines that are used as hardeners for epoxy oligomers.
For preparing polycyclocarbonate oligomers are used epoxy-cyclocarbonate olygomers preferably of such formula:
Suitable commercially available epoxy resins
DER-324, DER-332, DEN-431, DER-732 Dow Chemical Co (USA),
EPON 813, EPON 8021, EPON 8091,
EPON 825, EPON 828 Shell Chemical Co (USA),
NPEF-165 Nan Ya Plastic Corporation (R. China),
PEP 6180, PEP 6769, PEP 6760 Pacific Epoxy Polymers, Inc (USA),
Araldite 0510, MY-0501, MY-720 Ciba-Geigy A.G. (USA),
Laprolat 803, 703 “Macromer” Ltd. (Russia),
Ricopoxy 30 Ricon Resins Inc. (USA)
Preferably commercially available aromatic diamines: m-phenylendiamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyloxide, 2,4 and 2,6 diethyltoluelenediamine (Albermnarle Corporation).
Preferably commercially available primary amines: N,N-bis(3-aminopropyl) methylamine (BASF, Germany), m-xylylenediamine (Mitsubishi, Japan), triethyleneglycoldiamine (Jeffamine), EDR-148 (Huntsman Corporation, USA), 1,3-diaminopentane (Du Pont, USA), Isoforondiamine (BASF, Germany), Jeffamine T-403 (Huntsman Corporation, USA), etc.
REFERENCES:
patent: 4585566 (1986-04-01), Wollenberg
patent: 5175231 (1992-12-01), Rapport et al.
patent: 5340889 (1994-08-01), Crawford et al.
patent: 3624314 (1988-01-01), None
patent: 0303158 (1989-02-01), None
patent: 0535794 (1993-07-01), None
patent: 9858004 (1998-12-01), None
“Chemical Toughening of Epoxies. I. Structural Modification of Epoxy Resins by Reaction with Hydroxy-Terminated Poly(Butadiene-co-Acrylonitrile)”—J. Appl. Polym. Science, vol. 39, No. 7, 1990, pp. 1459-1466, S. Sankaran, M. Chanda.
Database WPI Week 9627 Derwent Publications Ltdl, London, GB; XP002133490—abstract—Nov. 20, 1995.
Database WPI Week 9637 Derwent Publications Ltd., London, GB; XP002133491—abstract—Dec. 20, 1995.
Database WPI Week 8251 Derwent Publications Ltd., London, GB; XP002133492—abstract—Feb. 28, 1982.
Blank Nelly
Buslov Florida
Figovsky Oleg
Shapovalov Leonid
Bierman, Muserlian and Lucas
Boykin Terressa M.
Chemonol Ltd.
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