CA1257447A - Thermally stable thermoplastic epoxy resin - Google Patents

Abstract

ABSTRACT

A heat stable thermoplastic epoxy resin is prepared by reacting together in the presence of a catalyst (a) an epoxy resin, (b) optionally, a poly-hydric phenol, and (c) a monohydric phenol or alcohol, monocarboxylic acid or anhydride thereof, aliphatic or aromatic mono-secondary amines, mono-thiol, mono--isocyanate, water or combination thereof. The thermo-plastic resin does not exhibit an excessive viscosity increase at elevated temperatures making it particularly suitable for use in highway marking paint applications.

Description

~:S~7~47 THERMALLY STABLE THERMOPLASTIC RESIN

The present invention concerns thermoplastic resins and coatings prepared therefrom.

Thermoplastic (non-thermoset) epoxy resins have been employed in the formulation of highway, pavement, marking paints as disclosed by J. M. Dale in DEVELOPMENT OF LANE DELINEATION WITH IMPROVED DURABII.ITY, Report No. FHWA-RD-75-70, July 1975. The paint formula-tions are maintained at eleva-ted temperatures, about 450F (232C), during application. While they provide an excellent highway marking paint in -terms of abrasive resistance, they are deficient in terms of applicabi.li-tv since they exhibit a substantial increase in viscosity while being mainta.ined at the application temperature.

The present invention provides a thermo plastic resin which exhibits a much reduced viscosity increase at elevated -temperatures, i.e. more stable.

The present invention pertains to a thermally stable, thermoplastic resin prepared by reacting (A) at least one epoxy resin having an average of more than one vicinal epoxy 33,127A-F -1-~%'57 2~

group per molecule;
(B) optionally, one or more polyhydric phenols; and (C) at least one material selected from . monohydric phenols and alcohols, mono~
carboxylic acids and anhydrides thereof, aliphatic and aromatic mono-second~ry amines, mono-thiols, mono-isocyanates, water and combinations thereof;
lG in the presence of an effective quantity of a suitable catalyst and wherein components (A), (B) and (C) are reacted in quantities which provide an equlvalent ratio of componen-t (B) to component (A) of from 0:1 to 0.95:1, preferably from 0.3:1 to 0.9:1, most preferably from 0.45:1 to 0.85:1 and an equivalent ratio of component (C) to component (A) of from 0.87:1 to 1.1:1, prefer-ably from 0.93:1 to 1.05:1, most preferably from 0.95:1 to 1:1, and wherein the equivalent ratio of components (B-~C) to component (A) is from 0.87:1 -to 1.96:1, prefer-ably from 0.93:1 -to 1.95:1, most preferably from 0.95:1 to 1.85:1.

The thermoplastic resin of the present inven-tion is suitable for incorporation in a pain-t formula-tion comprising (A) the aforementioned thermally stable thermoplastic resin; and (B) at least one of (1) one or more pigments or dyes; and

(2) one or more fillers.

Suitable epoxy resins which can be employed in the process of the present invention include, for example, those represented by the formulas 33,127A-F -2-~.

o (~) ~ o H2C-C-cH2-o{~ o-CH2-C-CH2 33 ,127A-F -3-~,S7~

o o ~C ~C - V -~r O
X.~ ~X

X ~
~0 o ~ ~
o~ ~X

$ $
O ~ (~ i O

~3 0 ~ 0 C~
o , ,_ ~ X
. , . o H H
I

33 ,127A-F -4-wherein each A is independently a divalent hydrocarbyl group having from 1 to 10, preferably from 1 to O O o 6 carbon atoms, -S-, -S-S-, -S-, -S-, -C-, -O-C-O-o or -O ; each A' is independently a divalent hydrocarbyl group having from 1 to 10, preferably from 1 to 6 carbon atoms; each R is independently hydrogen or a hydrocarbyl group having from 1 to 4 carbon atoms; R' i5 hydrogen or a hydrocarbyl ~roup having from l to 10, preferably from 1 to 6 carbon atoms; each X is inde-penden-tly hydrogen, a halogen, preferably chlorine or bromine, o. a hydrocarbyl group having from l to i2 carbon atomsi n has a value of zero or 1; n' has an average value of from zero to 15, preferably from zero to 11.5; m has an average value of from 0.001 to 6, preferably from 0.1 to 3; and m' has an average val.ue of from zero to 4, preferably from 0.1 to 2.

Particularly suitable epoxy resins include, for example, the glycidyl ethers of p~lyhydric phenols such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol E', bisphenol K, tris-hydroxyphenyl methane, and mixtures thereof.

Suitable polyhydric phenolic compounds ~hich can be employed herein include, for example, those represented by the formulas ~.~X)~

V. HO. ~ ~ OH

33,127A-F -5-~2~ 4~

(X)4 (2~)4 VI . HO~(A)n~ OH

OH ~ OH OH

[~ n (X)4 (X)3 VIII. OH OH

10 (X)~ C _~--(X)4 ~OH

( X ) 4 wherein A, A', R', X, n and m are as hereinbefore defined.

Particularly suitable polyhydric phenol.ic materi.als include, for example, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol K, tris-hydroxyphenyl methane, and mixtures thereof.

Suitable monohydric phenol.ic compounds include, 20 for example, -those represented by the formula IX. OH
(X)5~
and each X ls as hereinbefore defined.

33,127A-F -6-. ~

~ Z ~7~ 7 Particulariy suitable monohydric phenolic materials include, for example, phenol, alkylphenols, such as nonylphenol and t-butylphenol, cresol, and mix-tures thereof.

Suitable monohydric alcohols which can be employed herein include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, ethylene glycol monomethyl e-ther, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and com-binations thereof.

Sul-table monocarboxylic acids whi.ch can be employed herein include, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, phenyl-acetic acid, toluic acid, and combinations thereof.

Suitable anhydrides of monocarboxylic acids which can be employed herein include, for example, acetic anhydride, propionic anhydride, buty:ric anhy-dride, valeric anhydride, and combinations thereof.

Suitable mono-secondary amines which can be employed herein include, for example, dimethyl amine, diethyl amine, methyl ethyl amine, dibutyl amine, methyl butyl amine, ethyl butyl amine, and combinations thereof.

Suitable mono-thiols which can be employed herein include, for example, propanthiol, butanethiol, pentanethiol, hexanethiol, dodecanethiol, thiocresol, and combinations thereof.

33,127A-F -7-. , .

~ZS7~

Sui-table mono-isocyanates which can be employed herein include, for example, ethyl isocyanate, propyl isocyanate, butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and combinations thereoE

Suitable catalysts for effectiny the reaction between the epoxy resin and -the phenolic hydroxyl-containing materials include, for example, those disclosed in U.S. Pa-t. Nos. 3,306,872; 3,341,580; 3,379,684;

3,477,990; 3,547,881; 3,637,590; 3,843,605; 3,948,855;
3,956,237; 4,048,141; 4,093,650; 4,131,633; 4,132,7~6;

4,171,420; 4,177,216 and 4,366,295.

Particularly suitable catalysts are those quaternary phosphoni.um and ammonium compounds such as, for example, ethyltriphenylphosphonium chloride, ethyl-triphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium ace-tate, ethyl-triphenyl-phosphonium diacetate (ethyltriphenylphosphonium acetate-acetic acid complex), tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphos-phonium iodide, tetrabutylphosphonium acetate, tetra-butylphosphonium diacetate (tetrabu'ylphosphonium acetate-acetic acid complex), butyltriphenylphosphonium tetrabromobisphenate, butyltriphenylphosphonium bisphenate, butyltriphenylphosphonium bicarbonate, benzyltrimethyl-ammonium chloride and tetramethylammonium hydroxide.

Qther suitable catalysts include tertiaryamines such as, for example, triethylamine, tripropylamine, tributylamine, 2-methylimidazole, benzyldimethylamine, N-methyl morpholine, and mixtures thereof.

33,127A-F -8-.:
. :

7~
_9_ Suitable pigments which can be employed herein include any which ~ill provide the coating with the desired color such as, for example, titanium dioxide, lead chromate, zinc chromate, chome green, pthalocyamine green and blue, iron oxide, and combinations thereof.

Suitable fillers which can be employed herein include, for example, calcium carbonate, talc, glass beads, powdered or flaked zinc or alumina, powdered or flaked glass, colloidal silica, and combinations thereof.

The following examples are illustrative of the presen-t invention, but are not to be construed as to limiting the scope thereof in any manner.
I

A. Preparation of Cap~ed Epoxy Resin To a reaction vessel equipped with a means for stirring and temperature control was added 37.1 lbs (16.8 kg, 10.2 gram epoxy equiv.) of a diglycidyl e-ther of biaphenol A having an average epoxide equivalen-t weight (EEW) of 1646, 18 lbs (8.2 kg, 43.8 gram epoxy equivalents) of a diglycid~l ether of bisphenol A
having an average EEW of 187, 23 lbs (10.4 kg, 47.3 gram hydroxyl equiv.) of nonyl phenol and 0.077 lbs (0.169 kg) of a 70 percent solution of ethyltriphenyl phosphonium acetate-acetic acid complex in methanol.
The mixture was heated to 160C at a rate of 1.5C/min.
(0.025C/s) and main-tained -thereat for 2 hours (7200 s).
The resultant product was a colorless to pale yellow resin, solid at room temperature.

33,127A-E' -9-., ,................ :- ::
- ~ .

~s7a~7 B. Prepara-tion of Traffic r~arking Paint A mixture was prepared at 200C o~ the follow-ing components:

1. 100 parts by weight of the resin from (A) above 2. 20 parts by weight of Tio2 3. 20 parts by weight of CaCO3 4. 28 parts by weight of 200 mesh (0.074 mm sieve - opening) glass beads Componen-ts 1, 2 and 3 were mixed under high shear conditions. Component 4 was mixed at low speeds.

The properties of the traffic paint formula-tion are given in the following Table.

For comparative purposes, a similar paint formulation was prepared from an epoxy resin mixture without nonyl phenol capping. The formula-tion was as follows:

1. 40 parts by weight of a diglycidyl ether of bisphenol A (DGEBA) having an epoxy equivalent weight (EEW) between 186 and 192 2. 60 parts by weigh-t of a DGEBA having an EEW
between 1600 and 2000 3. 20 parts by weight of Tio2 4. 20 parts by weight of CaCO3

5. 28 parts by weight of 200 mesh (0.074 mm sieve opening) glass beads The properties are given in the following Table.
.

33,127A-F ~10-;.: :

- : ~. - : . :

:

~2~7447 TABLE

Formulation Formulation 1-B l-C
Present Invention Comparative Mettler Softening Point, C 89 77 Cold flow at 25C No ~es Initial Viscosity @ 450F
(232C), cps/pa s 505/0.505 480/0.480 Viscosity after 8 hours (28800 s) at 450F
(232C), cps/pa s 510/0.51 1500/1.5 Condition after 24 hours (86400 s) at 450~ (232C) slight gelled, yellowiny brown A. Preparation of Non-Capped Epoxy Resin Blend (Epoxy Resin Blend) To a reaction vessel equi.pped with a means for stirring, nitrogen purge and temperature control was added 725.2 g (3.9 epoxy equiv.) of a diglycidyl ether of bisphenol A having an average epoxide equiva-lent weight (EEW) of 186 and 374.8 g (3.29 equiv.) of bisphenol A. The mixture was then heated to 90C at which time 1.69 g (0.003 mole) of a 70 percent solution of ethyltriphenyl phosphonium acetate-acetic acid complex in methanol was added. The temperature was increased to 150C and then the reaction mass exothermed to 206C. The temperature was maintained at 190C for 1 hour (3600 s). The percent epoxide was 2.48. To this material was added 528.4 g (2.84 epoxy equiv.) of a diglycidyl ether of bisphenol A having an average EEW
of 186. The temperature of the mixture was decreased to 150C. This product had a percent epoxide of 9.1 (473 EEW)-33,127A-F -11-, ~` ~
~ , :

~a2~;74~

B. Prepara-t1on of Capped EpoxY Resin To a reaction vessel equipped with a means for stirring and -temperature control was added 180 g (0.38 epoxy equiv.) of epoxy resin blend prepared in A
above and 76.2 g (0.38 mole) of lauric acid. The mixture was hea-ted to 90C whereupon 0.21 g (0.0004 mole) of a 70 percent solution of ethyltriphenyl phos-phonium ace-tate acetic acid complex in methanol was added. The temperature was increased to 156C and maintained at about 155C for 1.5 hours (5400 s). The product was dried in a vacuum oven at 160C for 2 hours (7200 s). The product had a viscosity of 74.5 cps (0.0745 pa s) at 450F (232C) and a softening point of 60.1C.

To a reaction vessel equipped with a means for stirring and temperature control was added 150 g (0.32 epoxy equiv.) of epoxy resin blend prepared in Example 2A and 100 g (1.35 mole) of n-butanol. The mixture was heated to 50C whereupon 0.3 g (0.002 mole) of boron trifl~oride etherate was added. The temper-ature was increased to 60C and maintained between 60 and 63C for 3.17 hours (11412 s), heated to 200C and vacuum stripped for 2.08 hours (7488 s). The product was dried in a vacuum oven at 160C for 2 hours (7200 s).
The product had a viscosity of 189.5 cps (0.1895 pa s) at 450F (232C) and a softening point of 78C.

To a high pressure reaction vessel equipped with a means for stirring, nitrogen purge and tempera-ture control was added 200 g (0.42 epoxy equiv.) of epoxy resin blend prepared in Example 2A, 200 g (2.77 moles) of ~ethyl ethyl ketone, 43 g (2.39 moles) of 33,127A-F -12-~ . .
. :.
... . ' ~, ., ' .~.' , ~ ' ~25~ 7 water, 1.7 g (0.003 mole) of a 70 percen-t solution of e-thyltriphenyl phosponium acetate acetic acid complex in methanol and 2.09 g (0.016 mole~ of oxalic acid 2H2O.
Reactor was purged with ni-trogen and then pressure increased to 80 psig (552 kPa gage). The reactor temperature was increased to 135C and maintained for about 4.5 hours (16200 s) then the temperature was increased to 145C and maintained for 5 hours (18,000 s).
The excess volatiles were removed in the reaction vessel at a tempera-ture of about 200C for about 0.25 hour (900 s). The product was dried in a vacuum oven at 160C for 2 hours (7200 s). The product had a viscosity of 362 cps (0.362 pa-s) at 450F (232C) and a softening point of 106.6C.

To a reaction vessel equipped with a means for sti.rring and temperature control was added 50 g of propylene glycol monomethyl ether acetate and 13.6 g (0.105 mole) of dibutylamlne. Over a perlod of 1 hour 20 (3600 s) added 100 g (0.106 epoxy equiv.) of a 50 percent solutiorl of epoxy resin blend prepared in Example 2A. The temperature was increased to 140C and maintained for 2 hours (7200 s). The temperature was increased to abou-t 200C for about 0.25 hour (900 s) to remove the solvent. The product was dried in a vacuum oven at 160C for 2 hours (7200 s). The product had a viscosity of 100.5 cps (0.1005 pa-s) at ~50F (232C) and a softening point of 72.4C.

To a reaction vessel equipped with a means for stirring and temperature control was added 97 g of propylene glycol monomethyl ether acetate, 8 g (0.078 33,127A-F -13-,, mole) of acetic anhydride, 70 g (0.074 epoxy equiv.) of a 50 percent solution of epoxy resin blend prepared in Example 2A in propylene glycol monomethyl ether acetate and 0.25 g (0.0009 mole) of a 70 percent solution of ethyltriphenyl phosphonium acetate acetic acid complex in methanol. The temperature was increased to 120C and maintained for 5.2 hours (18,720 s). A portion of the solvent was removed by heating at 145C for about 0.5 hour (1800 s). The resultant material was then placed on a hot plate for 1 hour (3600 s) at 206C. The product was dried in a vacuum o~en at 160C for 2 hours (7200 g). The product had a viscosity of 154 cps (0.154 pa-s) at 450F (232C) and a softening point of 79.5C.

To a reaction vessel equipped with a means for stirring and temperature control was added 84 g of Dowanol~ PM acetate, 8.5 g (0.082 mole) of 1-pentane-thiol, 70 g (0.074 epoxy equiv.) of a 50 percentsolution of epo~y resin blend prepared in Example 2A in propylene glycol monomethyl ether acetate and 0.25 g (0.0009 mole) of a 70 percent solution of ethyltri-phenyl phosphonium acetate-acetic acid complex in methanol. The temperature was increased to 100C and maintained for 3.55 hours (12,780 s). An additional 2 g (0.019 mole) of 1-pentanethiol and 0.25 g (0.0009 mole) of ethyltriphenyl phosphonium acetate-acetic acid complex solution was added. After 2.5 hours 3 (9000 s) an additional 0.25 g (0.0009 mole) of ethyltriphenyl phosphonium acetate-acetic acid complex solution was added. After l hour (3600 s) an additional 2 g (0.019 mole) of 1-pentanethiol and 0.25 g (0.0009 mole) of ethyltriphenyl phosphonium acetate-acetic acid complex 33,127A-F -14-~:2~;744L'7 was added. The temperature was maintained for 1 hour (3600 s) at 100C and then increased to a~ou-t 150C for about 1 hour (3600 s) to remove solvent. The product was dried in a vacuum oven at 160C for 2 hours (7200 s).
S The product had a viscosity of 119 cps (0.119 pa-s) at 450F (232C) and a softening point of 72.4C.

_XAMPLE 8 To a reaction vessel e~uipped with a means for stirring, nitrogen purge and temperature control was added 200 g (0.423 epoxy equivalent) of epoxy resin blend prepared in Example 2A, 49.5 g (0.416 mole) of phenyl isocyanate. The temperature was maintained between 130 and 145C. The phenyl isocyanate addition took 0.73 hour (2628 s). After 0.77 hour (2772 s), , 0.75 g (0.0022 mole) tetrabutylphosphonium bromide in 2.5 g of methanol was added. The temperature was increased to 155C and maintained between 155 and 160C for 6.75 hours (24,300 s). The product was dried in a vacuum oven at 160C for 2 hours (7200 s). The product had a viscosity of 670 cps (0.67 pa s) at 450F
(232C) and a softening point of 123.5C.

To a reaction vessel e~uipped with a means for stirring, condensing and temperature control was added 50 g (0.106 epoxy equivalent) of epoxy resin blend prepared in Example 2A and 150 g (1.531 mole) of cyclohexanone. The temperature was increased to 90C
to dissolve the epoxy resin blend then cooled -to 45C, whereupon 12 g (0.375 mole) of methanol was added. The temperature was decreased to 33C in 0.75 hour (2700 s) then 12.2 g (0.103 mole) of phenyl isocyanate was added. The temperature was increased to 45C, -then 33,127A-F -15-~.2~

0.12 g (0.0004 mole) of tetrabutylphosphonium brom1de in l g (0~031 mole) of methanol was added. The tem-perature was increased to 145C and maintained for 2.17 hours (7812 s). Then solvent was removed at 150C for 0.75 hour (2700 s). The resultant material was placed on a hot plate for 1.5 hours (5400 s) at 208C. The product was dried in a vacuum oven at 160C for 2 hours (7200 s). The product had a viscosity of 2520 cps (2.52 pa-s) at 450F (232C) and a softening point of 128.3C.

The uncapped epoxy resin blend of Example 2A
and the capped epoxy resins prepared in ~xamples 5, 6 and 8 were subjected to a thermal stabllity test. The results are given in the following Table.

THERMAL STABILITY TEST
Test Temperature 450F (232C) VISCOSITY
EPOXY RESIN TIME AT 450F ~32C) cps/pa-s Epoxy Resin Blend Initial 211/0.211 8 hours (28,800 s) 4~5/0.495 Example 5 Initial 100.5/0.1005 7.5 hours (27,000 s) 133.5/0.1335 Example 6 Initial 154/0.154 7 hours (25,200 s) 173/0.173 Example 8 Initial 670/0.670 8 hours (28,800 s) 684/0.684 33,127A-F -16-.~ ~ .

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:

1. A thermally stable, thermoplastic resin prepared by reacting in the presence of an effective quantity of a suitable catalyst (A)at least one epoxy resin having an average of more than one vicinal epoxy group per molecule; and (B)at least one material selected from monohydric phenols and alcohols, monocarboxylic acids and anhydrides thereof, aliphatic and aromatic mono-secondary amines, mono-thiols, mono-isocyanates, water and combinations thereof;
wherein components (A) and (B) are reacted in quantities which provide an equivalent ratio of component (B) to component (A) of from 0.87:1 to 1.1:1.

2. A thermally stable thermoplastic resin of Claim 1 wherein (C) at least one polyhydric phenol is reacted with components (A) and (B) and wherein components (A), (B) and (C) are reacted in quantities which provide an equivalent ratio of component (C) to component (A) of from 0.1 to 0.95:1 and wherein the equivalent ratio of component (B+C) to component (A) is from 0.87:1 to 1.96:1.

3. A resin composition of Claim 2 wherein (i) the epoxy groups contained in component (A) are glycidyl ether groups;
(ii) the equivalent ratio of component (B) to component (A) is from 0.93:1 to 1.05:1;
(iii) the equivalent ratio of component (C) to component (A) is from 0.3:1 to 0.9:1; and (iv) the equivalent ratio of components (A+C) to component (A) is from 0.93:1 to 1.95:1.

4. A resin composition of Claim 3 wherein (i) the equivalent ratio of component (B) to component (A) is from 0.95:1 to 1:1;
(ii) the equivalent ratio of component (C) to component (A) is from 0.45:1 to 0.85:1, and (iii) the equivalent ratio of component (B+C) to component (A) is from 0.95:1 to 1.85:1.

5. A thermoplastic resin of Claim 1 or 2 wherein (i) component (A) is an epoxy resin or a mixture of epoxy resins represented by formulas (I), (II), (III) or (IV) wherein each A is independently a divalent hydrocarbyl group having from 1 to 10 carbon atoms, -S-, -S-S-, , , , or -O-;
each A' is independently a divalent hydrocarbyl group having from 1 to 10; each R is independently hydrogen or a hydrocarbyl group having from 1 to 4 carbon atoms; R' is hydrogen or a hydrocarbyl group having from 1 to 10 carbon atoms; each X is independently hydrogen, a halogen, or a hydrocarbyl group having from 1 to 12 carbon atoms; n has a value of zero or 1; n' has an average value of from zero to 15; m has an average value of from 0.001 to 6; and m' has an average value from 0 to 4 (ii)component (B) is selected from monohydric phenolic compounds represented by formula (IX) IX. each X is as defined above, aliphatic alcohols, monocarboxylic acids, water, or combinations thereof.

6. A thermoplastic resin of Claim 2 wherein component (C) is at least one polyhdyric phenolic compound represented by formulas (V), (VI), (VII) or (VIII) V. VI. VII. VIII. wherein A, A', R', X, n and m are as defined above.

7. A thermoplastic resin of Claim 6 wherein (i) component (A) is one or more epoxy resins represented by formula (II) wherein A is a divalent hydrocarbon group having from 1 to 10 carbon atoms, each X is hydrogen or a halogen atom, n has a value of 1 and n' has an average value from 0.035 to 12;
(ii) component (C) is one or more polyhydric phenolic compounds represented by the formula VI; and (iii) component (C) is selected from nonyl phenol, n-butyl alcohol, lauric acid, water or combinations thereof.

8. A thermoplastic resin of Claim 7 wherein (i) component (A) is a mixture of an epoxy resin wherein n' has an average value of from 0.01 to 0.05 and an epoxy resin wherein n has an average value of from 2 to 15;
(ii) component (C) is bisphenol A; and (iii) component (B) is nonyl phenol.

9. A paint formulation comprising (A) a thermally stable resin of Claim 1; and (B) at least one of (1) one or more pigments or dyes; and (2) one or more fillers.