Europaisches Patentamt

J European Patent Office

© Publication number: 0 485 063 A2
Office europeen des brevets

© EUROPEAN PATENT APPLICATION

© Application number: 91308916.5 © Int. CI.5: C08J 3/09, C08L 6 7 / 0 6 ,

//C08J1 1 / 0 8 , ( C 0 8 L 6 7 / 0 6 , 7 5 : 0 4 )
@ Date of filing: 30.09.91

® Priority: 19.11.90 US 615188 © Applicant: TEXACO CHEMICAL COMPANY

08.1 1.90 US 61 0635 3040 Post Oak Boulevard
13.1 2.90 US 62681 8 Houston, Texas 77056(US)
18.12.90 US 629513
@ Inventor: Marquis, Edward Thomas
© Date of publication of application: 9004 Collinfield Drive
13.05.92 Bulletin 92/20 Austin, Texas 78758(US)
Inventor: Cuscurida, Michael
© Designated Contracting States: 3543 Greystone Drive, Suite 1056
DEFRGBIT Austin, Texas 78731 (US)

© Representative: Brock, Peter William et al

URQUHART-DYKES & LORD 91 Wimpole
Street
London W1M 8AH(GB)

© A method of dissolving cured polyester.

© Cured polyester resin can be dissolved by solvent mixtures containing alkylene carbonates, preferably
ethylene carbonate or propylene carbonate, as co-solvents. For instance cured fibreglass resin can be removed
from tools or substrates in this manner.
A preferred solvent mixture comprises the alkylene carbonate and tetramethylene urea.

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 EP 0 485 063 A2

The invention relates to a method of dissolving cured polyester, and especially to a method for
loosening or removing cured fibreglass resin from tools, processing equipment and other substrates.
A variety of solvents has been used to clean processing equipment, metal parts and tools, after a
polyester resin (e.g. as fibreglass) has cured on them. Acetone, methyl ethyl ketone, and diacetone alcohol
5 are the solvents most commonly used to remove cured polyester resin from the substrates to which it is
attached. Acetone and methyl ethyl ketone are not favoured, however, because of safety hazards resulting
from their high volatilities and low flash points. Additionally, acetone and methyl ethyl ketone are suspected
to be neurotoxins. Diacetone alcohol is very polar, and therefore presents processing problems when used
alone. Thus, it would be a substantial improvement in the art if a relatively inexpensive yet effective solvent
io formulation were available to remove cured polyester resins from substrates, and that reduced or avoided
the environmental, health and safety problems of the prior art solvent formulations.
US-A-4514530 discloses that epoxy resins can be cured by means of an amine curing agent which is
extended by a solution of an elastomeric polyurethane in an alkylene carbonate . We have surprisingly
discovered, that a cured polyester resin may be dissolved and may therefore be removed from a substrate,
75 by contacting the polyester resin with an alkylene carbonate, as a co-solvent in a mixture containing one or
more other solvents. The present process, by substituting, in whole or in part, alkylene carbonate for the
more hazardous prior art solvents, reduces or avoids many of the health, safety and environmental hazards
associated with the prior art solvents, and is economically attractive as well.
The present invention relates to method of dissolving a cured polyester comprising contacting said
20 polyester with a solvent system, including an alkylene carbonate, preferably ethylene carbonate or
propylene carbonate, as co-solvent.
In a preferred embodiment, the cured polyester, e.g. in the form of fibreglass resin, can be removed
from a substrate by being dissolved.
Preferably, the polyester is dissolved at a temperature of 50 to 100° C.
25 According to one preferred embodiment, the alkylene carbonate co-solvent can be mixed with at least
one solvent selected from aromatic hydrocarbons, ketones, esters, ethers, glycol ethers, imidazoles,
tetramethyl urea, N,N'-dimethylethylene urea, and N-methylpyrrolidone.
A preferred solvent mixture comprises the alkylene carbonate and tetramethyl urea, most preferably in
a weight ratio of alkylene carbonate to tetramethyl urea of 1:4 to 4:1 .
30 If desired, the solvent mixture may additionally comprise toluene, methyl isobutyl ketone, or isobutyl
isobutyrate.
The preferred alkylene carbonates have the formula

35

40
R

where R is H or alkyl having 1 to 20 carbon atoms. Preferably R is H or methyl, i.e. the alkylene carbonate
45 is preferably ethylene carbonate or propylene carbonate. Ethylene carbonate and propylene carbonate are
commercially available from Texaco Chemical Co. as TexacarR EC Ethylene Carbonate and TexacarR PC
Propylene Carbonate, respectively. Alternatively, a mixture of alkylene carbonates may be used, preferably
a mixture of ethylene carbonate and propylene carbonate, such as, for example, TexacarR EC-50.
Solvents that may be diluted or replaced by alkylene carbonates in the present invention include
50 aromatic hydrocarbons, ketones, esters, ethers, glycol ethers, imidazoles, tetramethyl urea, N,N'-dimethyl
ethylene urea, and N-methyl pyrrolidone. For example, good results have been obtained using formulations
containing an alkylene carbonate and one or more of the following solvents: tetramethyl urea, toluene,
methyl isobutyl ketone, 1,2-dimethylimidazole, N,N'-dimethyl ethylene urea, propylene glycol methyl ether,
cyclohexanone, acetophenone, and isobutyl isobutyrate. Optionally, other solvents may be added to the
55 formulations of the present invention as well.
Preferably, the proportion of conventional solvent replaced with alkylene carbonate in a formulation
containing one or more conventional (non-alkylene carbonate) solvents will be such that the alkylene
carbonate and the conventional solvents in the formulation are present in a weight ratio of alkylene

2
 EP 0 485 063 A2

carbonate to total conventional solvent of about 2:1. Surprisingly, there was no improvement in dissolution
power when the weight ratio of alkylene carbonate to conventional solvent was decreased from 2:1 to 1:1.
The greatest percentage of cured polyester resin removed was observed when the weight ratio of akylene
carbonate to conventional solvents was about 1:3. Those skilled in the art will appreciate that the proportion
5 of conventional solvents in a formulation which should be replaced with alkylene carbonate for a given
polyester resin involves a balance of possible reduction in dissolution power versus the reduction or
avoidance of additional expense and/or environmental, health and safety risks associated with the conven-
tional solvents. Applicant has demonstrated the use of several different formulations in the example that
follow. Alkylene carbonate also may be used alone to dissolve cured polyester resins.
io A preferred solvent mixture contains the alkylene carbonate and tetramethyl urea, in any desired
relative weight percentage. Preferably, the alkylene carbonate and tetramethyl urea are present in a weight
ratio of alkylene carbonate to tetramethyl urea of 1:4 to 4:1, most preferably in a weight ratio of 1:1 or most
preferably of 1:2. One skilled in the art may find other weight ratios to be optimum and not depart from the
scope of the present invention.
is Optionally, other solvents may be added to the formulations of the present invention. For example,
excellent results have been obtained using formulations containing, in addition to an alkylene carbonate and
tetramethyl urea, one or more of the following solvents: toluene, methyl isobutyl ketone, and isobutyl
isobutyrate. When it is desirable to add an additional solvent to the alkylene carbonate/tetramethyl urea
mixture, toluene is preferred. Other aromatic hydrocarbons, ketones and esters may be added to the
20 alkylene carbonate/tetramethyl urea formulation, in addition to or in lieu of those mentioned above. Those
skilled in the art will appreciate that the use of such additional solvents involves the consideration of
obtaining an increase in percent of material loosened or dissolved versus the possible additional expense
and increase in environmental, health and safety risks associated with the extra solvents. Applicants have
demonstrated several different formulations in the examples that follow.
25 Optionally, other additives may be employed in the formulations of the present invention. For example,
suitable thickeners may be included, such as ethylcellulose, hydroxypropyl cellulose, organic modified clay,
hydrogenated castor oil, and the like. Surfactants, to enhance the water washability of the substrate, may be
included as well. Suitable surfactants include potassium oleate, the dioctyl ester of sodium sulphosuccinic
acid, sodium alkylnaphthalene sulphonate, and sodium alkylbenzene sulphonate.
30 The method according to the invention is effective at temperatures of from room temperature to 100°C
and at pressures from 0.1 to 10 MPa. Optionally, the process of the present invention may be performed at
an elevated temperature. While the process works well at room temperature, more effective dissolution may
be obtained by heating the alkylene carbonate-containing solvent to a temperature of 50 to 100°C (e.g. 50
to 75 °C). The alkylene carbonate-containing solvent may be applied to the polyester resin in any
35 conventional manner. Typically, the polyester resin-coated substrate will be placed in a vat or sonic bath
containing the alkylene carbonate (and, optionally, conventional co-solvent). The period for which the
alkylene carbonate-containing solvent should be permitted to work undisturbed on the polyester resin to be
removed will vary. After that period, agitation of the surfaces to be cleaned of the resin via wiping, brushing
or scraping is preferred.
40 In addition to their use for dissolving cured polyesters, the solvent mixtures described above may also
be used to dissolve cured flexible or rigid polyurethane foam, as described in Examples.
The invention will be further illustrated by the following Examples:

Examples
45
In the Examples recorded in the Tables below, the following procedure was used. Previously coated
stainless steel 19 mm (3/4") screw stock rods were wire brushed and cleaned with a solvent. Rods that had
been coated with cured fibreglass were treated with acetone to remove any fibreglass residue; those that
had been coated with cured flexible or rigid polyurethane foam were treated with methylene chloride. The
50 rods were then sand blasted with micro beads. The rods were then coated with the materials to be tested.
As a typical polyester, there was employed a glycol maleate polyester in styrene (BradcoatR by Bradson
Supply Inc.) that was cured with methyl ethyl ketone peroxide. The coatings were then allowed to cure for
two days or more before dissolution studies were begun. Each coated stock rod was then suspended in a
beaker from a ring stand. Each beaker contained one of the alkylene carbonate-containing formulations to
55 be tested. At the bottom of each beaker was a stirring bar. After from 16 to 22 hours at room temperature
the rods were observed and the approximate percentage of polyester resin removed by each formulation
was estimated and recorded.

3
 EP 0 485 063 A2

Table 1

Ex No. Co-Solvent System Components Wt. Ratio of Approximate % Polyester

Components Resin Removed
^
1 PC/1,2-DMI/Acetone 80/80/20 30 %
2 EC/TMU/IBIB 73/65.1/64 25 %
3 EC/TMU/MIBK 67.8/69/59.8 25 %
10
4 PC/Acetophenone/Cyclohexanone 45/45/90 25 %
5 PC/Acetophenone/Cyclohexanone 45/90/45 20 %
6 PC/Acetophenone/Cyclohexanone 60/60/60 5%
75 7 PC/Acetophenone/Cyclohexanone 90/45/45 2%
8 Acetophenone/Cyclohexanone 90/90 2%
9 Acetophenone/Cyclohexanone 120/60 1%
10 Acetophenone/Cyclohexanone 60/120 1%
2o
11 PC/1,2-DMI 60/120 25 %
12 PC/1,2-DMI 90/90 20 %
13 PC/1,2-DMI 120/60 20 %
14 PC/1,2-DMI/MIBK 80/80/20 20 %
15 PC/1,2-DMI/IBIB 60/60/60 5%
16 PC/TMU 110/110 10-25%
30 17 PC/NNDMEU/Acetone 60/60/60 15 %
18 PC/NNDMEU/1,2-DMI 60/60/60 10 %
19 PC/NNDMEU/MIBK 60/60/60 10 %
20 PC/Cyclohexanone 60/120 15 %
35
21 PC/Cyclohexanone 100/100 5%
22 PC/Cyclohexanone 120/60 5%
23 PC/Cyclohexanone/PM 60/60/60 10 %
40
24 PC/Acetophenone 100/100 5%
25 PC/Acetophenone 60/120 2%
26 PC/Acetophenone 120/60 2%
45 27 PC/Acetone 100/100 5%
28 PC/N-methyl pyrrolidone 100/100 5%
EC = Ethylene carbonate; PC = Propylene carbonate; TMU = Tetramethyl urea; MIBK = Methyl
isobutyl ketone; IBIB = Isobutyl isobutyrate; 1,2-DMI = 1,2-dimethylimidazole; NNDMEU =
50 N,N'-dimethyl ethylene urea; PM = Propylene glycol methyl ether.

4
 fcP U 485 063 A2

Table 2

5 Ex- Type of Co-Solvent Wt. R a t i o Approximate %

No. Material Cured System of Material
on Rod Components Components Removed
29 Cured F l e x i b l e EC/TMU/MIBK 26.3/41.8/ 100 %
U r e t h a n e Foam /Toluene 41.6/41.9
w ~ — —
" EC/TMU/ 66.4/59.2/ 95 %
30
Toluene 59.0
" EC/TMU/IBIB 66.4/59.2/ 90 %
31 58.2
15
" EC/TMU/IBIB 47.4/43.5/ 90 %
?~
/Toluene 42.9/41.9
" EC/TMU/MIBK 64.0/57.4/ 90 %
33 57.3
20
" EC/TMU 106.7/95.7 50 %
34

" PC/TMU/ 1/1/1 100 %

J Toluene
25 "
36 PC/TMU 1/1 95 %

37 " PC/TMU/IBIB 1/1/1 95 %

30
PC/TMU/IBIB 1/1/1/1 95 %
38 /Toluene
" PC/TMU/MIBK 1/1/1/1 90 %
39
/Toluene
35 "
40 PC/TMU/MIBK 1/1/1 75 %

- E,i_nyj.ene u a r o o n a t e ; fc; = p r o p y l e n e C a r b o n a t e ;
MU = T e t r a m e t h y l u r e a ; MIBK = M e t h y l i s o b u t y l k e t o n e ;
[BIB = I s o b u t y l i s o b u t y r a t e .
 EP 0 485 063 A2

Table 3

Ex. Type of Co-Solvent Wt. R a t i o Approximate %

No. Material System of Material
C o a t i n g Rod Components Components Removed
4r Cured P o l y e s t e r EC/TMU/IBIB 73/65.1/64 25 %
Resin

1)2 " TMU 100 % 70 %

43 " EC/TMU/MIBK 67.8/69/ 25 %

59.8
44 " PC/TMU 1/1 10-25 %

EC = E t h y l e n e C a r b o n a t e ; PC = P r o p y l e n e C a r b o n a t e ;
TMU = T e t r a m e t h y l u r e a ; MIBK = M e t h y l i s o b u t y l k e t o n e ;
IBIB = I s o b u t y l i s o b u t y r a t e .

Table 4

Ex. Type of Co-Solvent Wt. R a t i o 1

Approximate %
No. Material System of Material
C o a t i n g Rod Components Components Removed
15 Cured R i g i d TMU 100 % 100 %
U r e t h a n e Foam
46 " PC/TMU 1/2 80 %

1,7 " PC/TMU 1/1 50 %

48 " PC/TMU 2/1 5 %
49 - " PC 100 % 0

l<- - £.tnyj.ene c a r b o n a t e ; PC = P r o p y l e n e C a r b o n a t e ;
CMU = T e t r a m e t h y l u r e a ; MIBK = M e t h y l i s o b u t y l
ketone;
CBIB = I s o b u t y l i s o b u t y r a t e .

fhe cured flexible urethane foam used in Examples 29 to 40 contained the following components:
 EP 0 485 063 A2

Component Parts by Weight

ThanolR SF-55051 60.0
NiaxR 34-28 Polymer Polyol2 40.0
Deionized Water 3.5
Diethanolamine 1.5
Silicon Oil L-53093 1.5
TEXACATR- 33A* (33% TEDA in DPG 0.5
UL-1 organotin in cmp.)5 0.0065
Toluene diisocyanate 44.5
1Arco;
2Union Carbide;
3Union Carbide;
+Texaco Chemical Co.;
5Witco FormezR.

The cured rigid urethane foam used in Examples 45 to 49 contained the following components:

Component Parts by Weight

ThanolR R-350-X 36.9
DC-1931 (silicon surfactant) 0.5
R11 (trichlorofluoromethane) 15.0
TEXACATR TD-33 0.3
Rubinate M2 (polymeric isocyanate) 49.6
1Dow Corning;
2ICI.
30
The cured fibreglass resin used in the Examples 41 to 44 BradcoatR (Bradson Supply Inc.) unsaturated
polyester in styrene, which was cured with methyl ethyl ketone peroxide.

Claims
35
1. A method of dissolving a cured polyester comprising contacting said polyester with a solvent system,
characterized in that said solvent system includes an alkylene carbonate as co-solvent.

2. A method according to Claim 1 characterized in that the alkylene carbonate is ethylene carbonate or
40 propylene carbonate.

3. A method according to Claim 1 or 2 characterized in that the cured polyester is removed from a
substrate by being dissolved.

45 4. A method according to any one of Claims 1 to 3 characterized in that the polyester is dissolved at a
temperature of 50 to 100° C.

5. A method according to any one of Claims 1 to 4 characterized in that a cured polyester resin is
dissolved by a solvent mixture comprising the alkylene carbonate co-solvent and at least one solvent
50 selected from aromatic hydrocarbons, ketones, esters, ethers, glycol ethers, imidazoles, tetramethyl
urea, N,N'-dimethylethylene urea, and N-methylpyrrolidone.

6. A method according to Claim 3 characterized in that a cured polyester resin is removed from a
substrate by a solve nt mixture comprising the alkylene carbonate and tetramethyl urea.
55
7. A method according to Claim 6 characterized in that the alkylene carbonate and tetramethyl urea are
present in the mixture in a weight ratio of alkylene carbonate to tetramethyl urea of 1:4 to 4:1.

7
 EP 0 485 063 A2

A method according to Claim 6 or 7 characterized in that the solvent mixture additionally comprises
toluene, methyl isobutyl ketone, or isobutyl isobutyrate.