CA1183642A - Curable epoxy resin containing compositions - Google Patents

Abstract

CURABLE EPOXY RESIN
CONTAINING COMPOSITIONS
ABSTRACT OF THE DISCLOSURE

Described herein are curable compositions com-prising a cycloaliphatic oxide and a compatible amount of a polyol. These compositions can be cast into articles characterized by an excellent balance of physical properties and excellent electrical properties.

S P E C I F I C A T I O N

Description

~ 13,0?3 This ~nvention is directed to a curable com-position of a cycloallphatic epoxide and a compatible amount of a polyol.
~ Cycloaliphatic epoxide resins have inheren~ly good electrical properties. Unmodified cycloaliphatic epoxide resins when cured, however, produce inherently brittle material~. Thus, modifications must be made in ~he cycloaliphatic epoxide resin systems ~o decrease their brittleness as well as provide tough ~ystems in order to provide the necessary thermal shock resis~ance (TSR). Also, resin systems with good electrical pro-perties at elevated temperatures ~re required in many applications.
The problem, thens becomes one of developing cycloaliphatic epoxide sys~ems with adequate thermal shock resistance while retaining their excellent electrical properties and high heat distortion temperature.
Modification of the cycloaliphatic epoxides with low (~20Q0) molecular weight flexibilizers showed an averaging effect betweerl the so~tening polnt o~ the un-modified resin and that of the flexibilizer. The result was a moderate improvement in the TSR accompanied by a ra~her large redution in the heat distortion tempera-ture.
Thus, a need exists to develop a cycloaliphatic epoxide system with a high TSR, a high heat distor~ion temperature which retains the excellent electrical properties of the systems.

~,

2.

13,023 ~ ~ ~ 3 THE INVENTION
_ . . .

The curable cycloaliphatic containing com positions of this lnven~ion which when cas~ into articles are characterized by an excellent b~lance of physical properties, high TSR, high heat distortio~
temperature and good electrical proper~ies.
The compositions of this invention are useful in making elec~rical components such as, for example, outdoor insulation pplications and coil and trans-former encap~ulation.
The curable cycloaliphatic composition of this invention comprise a cycloalipha~ic epoxide and a polyol having a molecular weigh~ of from about 1000 to that mQlecular weight which does not form a two phase system wi~h the epoxide.
Suit:able cycloaliphatic epoxides for purposes of ~his invention are those having an average of more than one vicinal epoxy group per molecule. The epoxy groups can be terminal epoxy groups or internal epoxy groups as exemplified by the cycloaliphatic epoxides which are subsequently described. Particularly desir-able cyc~oaliphatic epoxides are the cyclohexane diepoxides, that ls epoxides having at least one cyclohexane ring to which is attached at least one .
vicinal epoxy group.
Illustrative of suitable cycloaliphatic epoxides are the following:

~ ~ 3~ 3,~23 FORMULA I
Diepoxides of cyclo~lipha~ic es~ers of dicarboxylic ac~ds h~ing the formul~:

0~~~ 0 R8 R7 R7, R8 wherein Rl through Rg, which can be ~he sa~e or different are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive and preferably containing one to three carbon atoms inclusive as for example methyl, ethyl, n-pr~pyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl and ~he like; R is a valence bond or a divalent hydro-carbon radical generally containing one ~o nine ~arbon atoms inclusive and preferably containing four to six carbon atoms inclusive, as for e~ample, alkylene radicals, such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, nonamethylene, and the like; cyclo-aliphatic radical~, 6uch as 1,4-cyclohexane, 1,3-cyclohexane, 1,2-cyclohexane, and the like.
Par~icularly desirable epoxides, falling within the scope of Formula I, are those wherein R

4.

~ ~364~ 13,023 through Rg are hydrogen and R is alkylene containing four to 6iX car~on atoms.
Among speclfic diepoxide~ of cycloaliphatic esters of dicarboxylie acids ar the following:
bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis~3,4-epoxy-6-methylcyclohexylmethyl)adipate, bis(3,4-epoxycyclohexylmethyl)pi~elate, ~nd the like. Other suitable compounds are described in U.S. Pat. No. 2,750,395 to B. Phillips et al.

FORMULA II

A 3,4-epoxycyclohexylmethyl 3,4-epoxyeyclo-hexane carboxylate havlng the formula:

wherein Rl through R9 which can be the same or different are as defined for Rl in formula I.
Particularly desirable compounds are those wherein Rl ~hrough R9 are hydrogen.
Among specific compounds falling within the

3~;42 D-13, 023-C

. scope of Fc~rmuls II are the following: 3,4-epoxy-cyc`loh~ylme~hy~, 3, 4-ep~ys~yclollexanecarboxylate, 3, 4-epoxy-l-methyl cyr~ ohe~ylmethyl, 3, 1~-epoxy-l-methyleyclohexylmethyl, 3, 4-epoxv-1-methylcvclo-hexanecarboxylate, 6-methyl-3,4-epoxycyclohexyl-methyl, 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl, 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methyl-cyclohexylmethyl, 3,4-epoxy-5 methylcyclohexanecar-boxylate. Other suitable compounds are described in U.S. Pat. No. 2,890,194 to B. Phillips et al.

FO~M~LA III

Diepoxides having the formula:

Rl' ~ 3'R /

~ 1~ 0 CH2 R I ~
Rg~ ~ \ R5, 8R / ~ ~R4"
8'R7,R6' 71'R / R5"

wherein the R ~ingle end double p~imes, which can be t~e ~ame or different, are monov21ent substituents ~uch as hydrogen, halogen, i.e. chlorine, bromine, iodine or flusri~e~ or monovalent hydrocarbon radicals, or radicals as further defined in U.S. Pat No.
3,3189822 to Rans Batzer et al. issued May 9, 1967.

13,023 ~ 3~ ~ ~

Particularly desirable compound~ ~re those wherein all the R' 5 are hydrogen.
Other suitable cycloaliphatic epoxides are the following:
~ ~

~f~

and the like.
The preferred cycloaliphatic epoxides are the following:
3,4 Epoxycyclohexylmethyl-3,4-Epoxy-cyclohexane caboxylate ~0 ~ C -~ ~o Bi~(3,4-Epoxycyclohexylmethyl)Adipate a ~~ -C4H8-C-~

2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane ~o~{~

~ ~ ~ 3~ 39~23 Vinyl cyolohexene Dioxide or mixtures thereof .
Epoxides with six menibered ~ing structures may also be used, such as diglycidyl esters of ph~halic acid, partially hydrogenated ph~halic ~cid or fully hydrogena~ed phtha:Lic acid. Diglycidyl esters of hexahydrophthalic aeids being preferredO
The glyeol suitable for use in thi inven-tlon has a molecular weight of from about 1000 to that molecular weigh~ which does not form a two phase system with the epoxide, which is about 4000.
The glycols include polycaprolac~one polyols as well as alk:ylene oxide adducts of polyhydroxyalkanes.
Illustrative of the polycaprolactone polyols that can be u~ed one can mention the reaction pro-ducts of a polyhydroxyl compound having from 2 to 6 hydroxyl groups with caprolactone. The manner in whieh these polycaprolactone polyol compositions are produced is shown in U.S. 3,169,945 and many such compositions are commercially available. In the following table there are listed illustrative poly-caprolactone polyol~. The first column lists the organic functional initiator that is reacted wlth the caprolactone and the average molecular weight of the polycaprolactone polyol is shown in the second column.

8.

3~,9L;~ 139 0~3 Knowing the molecular weights of 'che initiator and of the polycaprolactone polyol one can readily dPtermine the average number of molecules of caprolactone (CPL Units) that reacted to produce - the compound; thi~ figure ls ~hown in the third co lumn .

9.

13,023 Average No.
~er ge MW of CPL Units Initineor . ~ in moleeules 1 Ethylene glycol 290 2 2 Ethylene glycol ~ ~ 803 6~5 3 Ethylene glycol 2,114 18

4 Propylene glycol 874 7

5 Octylene glycol 602 4

6 Deca~ence glycol 801 5,5

7 Diethylene glycol 527 3.7

8 Dieth~lene ~lycol ~47 6.5

9 Dlethylene ~lycol 1,246 10 Diethylene glycol 1,998 16,6 11 Diethylene glycol 3j526 30 12 Triethylene glycol 754 5.3 13 Polyethylene glycol (MW 20n~* 713 4.5 14 Polyethylene glycol ~M~ 600)* 1,396 Polyethylene glycol (MW 1500)* 2,868 12 16 1,2-Propylene glycol 646 5 17 1~3-Propylene glycol 988 18 Dipropylene glycol 476 3 19 ~Polypropylene glycol ~MW 425~*824 3~6 20 Polypropylene glycol (MW 1000)*1,684 6 21 Polypropylene glycol (MW 200Q)*29456 4 22 Hexylene ~lycol 916 7 23 2 Ethyl-1,3-hexanediol 602 4 24 l,S-Pentanediol 446 3 25 1,4-Cyclohexanediol 629 4.5 26 1,3-Bis(hydroxyethyl)-benzene 736 5 27 Glycer~l 548 4 28 1,2,6-Hex~metriol 476 3 29 Tr~methylolpropane 590 4 30 Trimethylolpropane 761 5,4 31 Trimethylolpropane 1,103 8, 5 32 Triethanolamine 890 6. S
33 Erythritol 920 7 34 Pentaerythr~tol 1,219 9.5 Avera~e molecular weight~of glycol~

The structures of the compounds in the above ~abul~tion are obvious to one skilled in the art ba~ed on the informa~ion given. The structure of compound ~o. 7 is:

10.

13, 023 O O
.~ ..
HC) [ ~CH2) sC~ rCH2CH20~H2CH2 [ OC (CH2~ 5 ] rOH

wherein the variable r is an ~nteger, the su~ of r +
r has an avera~e value of 3 7 and ~he average molecular weight is 527. The ~tructure of compound No. 20 is:
O O '' H0[(CH2~C0]~(C3H6~n C3H61o~H2)s]roH

wherein the sum of r ~ r has an average value of 6 and the average molecular weight i~ 1,684. This explanation makes explicit ~he s~ructural formulas of compounds 1 l:o 34 set forth above.
Il:Lustrative alkylene oxide adducts of polyhydroxya:Lkanes incll~de, among others, the alkylene oxide adducts o ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxy-butane~ 1,4-1,5~ and 1,6~dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6-, and 1,8-dihydroxyoctane, l,10-dihyd-roxy-decane~ glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxyhexane, l,l,l-trimethylolethane, 1,1,1-trimethylolpropane, pentaçrylthritol~ caprolackone~
polycaprolactone, xylitol, arabitol, sorbitol, mannitol, and the like; preferably the adducts of ethylene oxide, propylene oxide, epoxybutane, or mixtures thereof. A
preerred cl~ss of alkylene oxide adducts of poly-hydroxyalkanes are the ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, adduets of trihydroxyalkanes.

11.

13,0?3 3~2 The preferred alkylene oxide adducts of polyhydroxyalkan~s are c~f 'che following formula:

~10~O~CH2o~H-o~nH] 3 wherein ~10 is ~ll~ne of 3 to 10 carbon ~toms, prefer ably 3 carbon atoms, and n is an lnteger of from ~bout 4 to abs)u~ 25.
The polyols constitu'ce from about 10 to about 2S weight percent, preferably from about 10 ~to ~bout 20 weight percent.
It is customary ~ dd appropriate hardeners to epoxide compositions to effect cure.
Among suitable hardeners ~re khe ollowing:
1. phenolic hardeners ha~ing at least 2 phenolic hydroxyl groups and preferably having at least 3 phenolic hydroxyl groups per molecule.
2. polybasic acids having at least 2 carboxylic acid groups per molecule.
3. anhydrides o~ acids having at least 2 carboxylic acid groups per molecul~.
Exemplary of suitable phenolic hardeners are the following polyhydric phenols: catechol, hydro-quinone, llydroxyhydroquinone, phloroglucinol, resorcinol and pyrogallol; the di and polynuclear phenols such as the bisphenol is described in Bender et al., U.S. Pat. No. 2,506,~86 and polyphenylols

12.

13,023 ~ ~ 3~ ~ ~

such as novolac condensates of a phenol and a satura~ced or unsatura~ced aldehyde containing an average of from three to 20 or more phenylol groups per molecule ~cf. book by T. S. Carswell entitled "Phenoplasts, tl published in 1947 by Interscience Publishers of New York).
Examples of suitable polyphenylols derived from a phenol and an unsaturated aldehyde such as ' acroleln are the triphenylols, pentaphenylols ~nd heptaphenylols described in U.S. Pat. No. 2,885,385 to A.G. Farnham, issued May 5, 1959.
The phenols may eontain alkyl or ryl ring substituents or halogens, as exemplified by the alkyl resorcinols, the tribromo reso~cinol and the dlphenols containing alkyl and halogen substituent~ on the aromatic ring (Bender et al., U.S. Pat. No. 2,506,486).
The polyhydric phenols can consist of two or more phenols connected by such groups as methylene, alkylene, ether, ketone, or sulfone. The connecting groups are further exemplified by the following com~
pounds: bis(p-hydroxyphenyl)ether; bis(p-hydrox-yphenyl)ketone, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)dimethyl methane, bis(p-hydroxyphen-yl)sulfone and the like.
For purposes of stoichiometric calculations with rPspect to phenolic hardeners, one phenolic hydroxyl group is deemed to react with one epoxy group.

13.

13,023 ~ ~3~ ~ ~

Illustrat~ve of ~uitable polybasic acids are the p~lycarboxylic acids of the formula:

HOOC-(CH2)f-COOH

wherein is an integer generally having a value of rom 1 to 20 inclusive, as for example, malonic, glu~aric, adipie, p~melic, suberic, azelaic, sebacic and the like. Other examples of ~uitable aci~s are phthalic acid, isophtha~ic acid, terephthalic acid and the like. Further acids are enumerated in U.S.
Pat. No. 2,91~,444 to ~. Phillips et al., issued Dec. 22, 1959.
Among ~ther suitable polybasic acids, having at least two carboxylic group~ per molecule, can be noted the following: tricarballylic acid, trimellitic acid and the l~ke. Other ~uch sui~able polybasic acids, ineluding polyesters thereof, are described in U.5. Pat. No. 2,921,925 to B. Phillips et al.
Suitable anhydrides ~re the anhydride~ of the acids listed above.
2~ For purposes of stoichiometric calculations wit~ re~pect to acids, one carboxyl group is deemed to react with one epoxy group; with respect to anhydrides, one anhydride group is deemed to react with one epoxy group.
Preferred hardeners include methyltetra-hydrophthalie anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

14.

3~ ~ ~
13~023 In an embodiment of this invention, the hardener such as the anhydride may be reacted with the glycol and this reacted product added to the epoxide.
It is to be understood that other addi-tives can be added to the compositions of this invention as is well known in the epoxy art. These addi-tives include the following: catalysts or accelerators, such as amines including (2~hydroxy ethyl)trimethyl ammonium hydroxide t45 percent con-centration in methanol, known as choline base, benzyl dimethyl amine, 2-methyl imidazole, metallic compounds, such as stannous octanoate, peroxides or ethylene glycol; modifiers such as dimer acid (made from unsaturated C18 fatty acids and is a mixture of 3 percent mono basic acids, 75 percent dimer acid and 22 percent trimer acid and sold under the name of Empol* 1022 by Emery Industries), a carboxyl terminated butadiene acrylonitrile (80~20) random copolymer having a molecular weight of about 3300; fillers such as clay, silica or aluminum tri-hydride which may be coated with, for example, silanes, which fillers may be added in amounts of up to about 60 percent; pigments such as carbcn black;
mold release agents, and the like.
The compositions of this invention are prepared by simply mixing the epoxide, glycol, hardener and other ingredients at room or higher .
*Trademark. 15.
i~

13, 023 3~

temperatures in a suitable eontainer. Also, the epoxide and glycol may be mixed ln one container and the hardener, catalyst and/or accelerator in another container and these two mixed. The composi~
tion is then heated in order to effect it~ cure.
The temperature to which the composition of this inven~cion are heated to effect cure will, of course, vary snd depend, in part upon the exac~ formulations of the composition. Generally, temperatures in the range of about 100C to about 200C are used for a period of time ranging fxom about 1 '~o about ~ hours.
~ 7 /

16 .

13,023 ~ ~ 36 EXAMPLES

The following Examples serve to give ~pecific illustrstion of the practice of thls inYentisn but they are not ~ntended in any way to act to lim~t the ~cope of - this inventionO
The following design2tions used in the Examples have the following meaning-Epoxy 1: 394-epoxycyclohexylmethyi-3,4 epoxycyclohexane carboxylate Epoxy 2: bis(3,4-ep3xycyclohexylmethyl) adipate Epoxy 3: 2~(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-meta-dioxane HHPA: hexahydrophthalic anhydride MTHP~: methyltetrahydrophthalic anhydride Choline base: (2-hydroxy ethyl~ trimethyl ammonium hydrox-ide, 45 percent concentra~ion in methanol.
Polyol 1: R-EO~CH2 ~

R ~ropane~ having a molecular weight of 6000.
Polyol 2: same formula as Polyol 1 but having a molecular weight of 5,000, Polyol 3: same formula as Polyol 1 but having a molecular weight of 4,200.
Polyol 4: same formula as Polyol 1 but having a molecular weight of 2,500.
Poly~l 5: same formula as Polyol 1 but having a molecular weight of 1,500.
Polyol ~: same ~ormula as Polyol 1 but having a molecular weight of 710.

1~3~ 13, 023 The procedures llsed to test ~che cured composi~
tion were as follows:
Physical Property Test Method Heat distortion temperature ASTM D648~72 Thermal shock resls~ance (TSR) Union Carbide Corpor-~'cion Publica~cion F~44429 Tensile strength Elongation at break3 ASTM D-638 Tens ile modulus Dielectric constant, 60 hertz ~t 100C} ASTM D-150 Dissipation Fac~or, 60 hertz at 100 C
Examples 1 and 2 and Controls A to D
In these Examples and Controls, the type and amount of epoxicle (grams) and type and amount of polyol (grams) as shown in Table I were mixed in a container at abou~ 25C. In a separate container the amount (grams) of hexahydrophthallc anhydrid2 and the amount (grams) of choline base as shown in Table I were mixed at about 55C.
The contents of the two containers were combined and poured into appropriate molds. The contents of the moLds were then heated for 2 hours at 100C and then for our hours at 160C~
The cured composition ~as then cut into test ~amples and tested for heat distortion temperature3 TSR, tensile strength, elongation, tensile modulus, dielectric constant and dissipation factor. The appearance of the cured composition was noted. An appearance of opacity indicates that a second phase has been formed.
The results are shown in Table I.

18.

36~

.
~ 0~ ~
.a fD 3 ~ ~ J ~ o o ~ ~ O O t~
fD ~ ~ ~ P ~~ ~ O ~ O O ~e ~o n ,~ ~ ~~ ~ ~ r~
P It . ID r~ ~D
~- n g ~ ~~ ~ ~ ~ ~ ,_ ::

3 ~ D
O
F~ 00 'U

C~
~I
O ~ ~ O ~ 1~ ~ P
OD ~ o ~ O O p It O
S-o ~ :a o o ,a 0 o O ~ 9 ~ :~ ~;
~1 ~-- O p~ O ~ I I I t~ I I O ~
'~ Co O H
O ~I g ~ n ~ ~ I~~
~ ~ O

O ~ ~ ~ ~ 1 ~ ~ D O ~a I ~ ~ I t ~ o I
~ ~ o ~ P
0~ Ln ~ I' ' O
~I tD O ~ ~ ~ 9 ~ ~ I O ~
O ,~ , P ,~ O

19 .

36~t~ 13, ~23 amples 3 and 4 and Controls F to H

In ~chese Examples and Controls, the ~ype and amount of epoxide (grams) ~nd type and amount of polyol (grams) ~s ~hown ill Table II wer mixed in ~ contairle~
at about 25C. In a separate container ~he amount (grams) of hexahydrophthalic anhydrlde and ~che amount (grams) of choline ba~e as ~hown irl Table II
were mixed at about 55 C . me contents o the two con-tainers were combined and poured into appropriate molds.
The contents of the molds were then heated for 2 hours at 100C and then for four hours at 160C.
The cured composition was ~hen cut lnto test samples and tested for heat distortion temperature, TSR, tensile strength9 elongation; tensile modulus, dielectric constant and di ssipation factor. The appeara~ce of the cured composition was noted.
The results are shown in Table II.

20.

3~ 13,023 .
p ~ ~ ~
D 'O ~ Y t~ O O ~g ~ a ~D O ~ ~ æ
.. ~ ~ ~ ~ ~ P ~ ~ O O O C~ ~ O
, .. ~ ~ p g~
r P
S-h O
P
O ~ ~ rt 4, ~" o -n C~
O
C o ~
O o ~ , 3 o I~ O CS~ 3 ~_ , O ~-~ ~ ~ ~ It 0 3!~ 0 ~ O I O
. ~ o ~ Z ~ X ~_ ~n o ~ V~
~n O
oo ~

~ ~ ~ o ,- a~ ,. ~ r O ~ O~ ~ W O t1 ~
Ln ~ O C~ ~ C~

C~
O ~ ~ ~
~ W O ~D ~ ~ I ~n I I I ~ IW
O ~ ~ ~ ~ ~ O~ O
O . ~ W Go W ~ O
O

O ~D o~D W ~ ~ O
O t~ " .~ ~ ~ 00 i~ (Jl O

n ~ a o ~ Cl~ 3 ., , ~ . Ç~ ~1~ . ~ ~ ~ O r~
O ~U ~ ~ ;~
~-,~ O :~:
2 ~ .

~ ~ ~3~

In these Examples ~ a mixture of epoxides of the type and amount (grams j and Polyol 4 in the amount (grams) as ~hown in Ta~le III were mixed ~t about 25C.
In a separate container the amount (grams) of hexahydrophthalic anhydride and ~he amount (~rams) of choline base as shown in Table III were mixed at about 25 C . The contents o the ltWQ containers were combined and poured into appropriate molds. The con~ents of the mol.d were then heated for 3 hours at 100C and then for our hours at 160 C~
The cured composition was then cut ints test samples and tested for heat distortion temperature7 TSR, tensile strength, elongation, tensile modulus, dielectric constant and dissipation factor. The appear~nce of the cured composi~ion w~s noted.
The results are sh~wn in Table IIIo 22.

3~ 13, 023 g ~ O ~ ~ o t~ t~ 0 ~
rt rD ~ ~_ ~ ~ X ~ ~
C: ~ ~ ~ tD
~_ rt r~ (D ~ P r ~ ~ 3 o ~o ~ ' co ~ o o :3 rt O
" ~ ~ rD t n>
~h O
~ r~ ~
O P ~ rt ~ ~o ~ 3 D

I_ O W `' ~ o O ~D 1~ 0 0 ~-- ~ It *`
cs`
~n W W ~ O~ D ~I O 10 o ~ ~ D ~ ~ ~ O
g :~

~ c~ ~
o ~ ~ ~J ~ ~ ~ ~ ~
o ~ `~ ~ ~ cs' rD ~ w ~ ~ ~ l~J
o `~ ~ . . .
o o~ c~ o 1~~I CJ' ~S cr ~ ~ ~ :~
~ r ~n ~ 1~1l W I~ D ~ H
O ~ ~0 ~ ~ ~ O ~ ~ I 0 o ~ o ~ o ~I
cr o o o ~ ~ ~ D W ~ ~ ~-- ~ 1`
~ ~ 8 ~n o ~ ~ ~
oo O W W ~ O ~ ~ C~ ~ W
o ~ ~ ~
~_ ~n O O ~ P' O
O ~ ~n Go o ?~
w ~J ~ o I ~
~ W o o ~ . . ~ . . . o~. ,,_ W ~ O
o ~

\
3 6 ~ 13;023 ~ Y~ Z t~ l9 In these examples9 Epoxy 2 and Polyol 4 in the amounts (grams) shown ~n Table IV were mixed ln ~ con-tainer at about 25C, In a sep rate eontainer the amount (~rams) of hexahydrophthali.c anhydrlde ~r methyl-~etr~hydrophthalic anhydride ~nd amount (grams) of choline base as shown in Table IY were mixed at about 25C. The contents of the two containers were combined and poured into ~ppropriate molds. The contents of the molds were then heated for 2 hours at 100C and ~hen for four hours a~ 160C.
The cured composition was then cut into test ~amples and tested for heat di~tortion temperature, TSR, tensile strength, elongation~ tensile modulus, dielectric constan~ and dissipation factor~ The appearance of the cured composition was noted. The percent of polyol 4 in the formulation is also shown.
The results arP shown in Table IV.

1~3~2 ., , ,13; 0~3 . ~ 3 ~ ~ o ~ 1~ ~
~ ~ ., ~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~ a o ~ ~ O
~ o ~ ~ 8 ~ R ~ ~ ~

~ O ~ ~ 5 Z~ ~"
g~ It p ~

P~ ~
ô
~ C~

Pg ~ , ~3 ~ n o ~ o ~ O ~
O C~ ~ ~ ~J ~ ~ O ~D
~ 1-- 0 .,. ~ C~

~ ~n n ~- w o ~ ~ ~ o 1_ ~ ~ ~ , 1 ~ ~ ~n C~ C~7 OD

o ~ O ~ ,~ o ~ ~ ~ 1'--,~, ~ O O C~
~ .

O ~ O ~ 1~9 ~0 ~

25 . . - .

Claims (16)

WHAT IS CLAIMED IS:

1. A curable composition comprising a cyclo-aliphatic epoxide, a polyether polyol having a molecular weight of from about 1000 to that molecular weight which does not form a two-phase system with the epoxide, and a hardener.

2. A curable composition as in claim 1 wherein the cycloaliphatic epoxide has the formula:

wherein R1 through R9, which can be the same or different are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive; R is a valence bond or a divalent hydrocarbon radical generally containing one to nine carbon atoms inclusive.

3. A curable composition as in claim 1 wherein the cycloaliphatic epoxide has the formula:

wherein R1 through R9, which can be the same or different are hydrogen or alkyl radicals generally containing one 26.

to nine carbon atoms inclusive.

4. A curable composition as in claim 1 wherein the cycloaliphatic epoxide has the formula:

wherein the R groups are the same or different and are monovalent substituents or monovalent hydrocarbon radicals.

5. A curable composition as in claim 1 wherein the cycloaliphatic epoxide is 3,4-epoxycyelohexylmethyl-3,4-epoxy-cyclohexane carboxylate.

6. A curable composition as is claim 1 wherein the cycloaliphatic epoxide is bis(3,4-epoxycyclohexylmethyl)-adipate.

7. A curable composition as in claim 1 wherein the cycloaliphatic epoxide is 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane.

8. A curable composition as in claim 1 wherein the cycloaliphatic epoxide is a mixture of bis(3,4-epoxy-cyclohexylmethyl)adipate and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-meta-dioxane.

9. A curable composition as in claim 1 wherein the polyether polyol has a molecular weight of from about 1000 to about 4000.

27.

10. A curable composition as in claim 1 wherein the polyether polyol is an alkylene oxide adduct of a polyhydroxyalkane.

11. A curable composition as in claim wherein the polyether polyol has the following formula:

wherein R10 is alkane of 3 to 10 carbon atoms and n is an integer of from about 4 to about 25.

12. A curable composition as in claim 11 wherein R is propane.

13. A curable composition as in claim 1 wherein the polyether polyol is present in amounts of from about 10 to about 20 weight percent.

14. The cured product of the composition de-fined in claim 1.

15. A curable composition as in claim 1 wherein the hardener is an anhydride of a polybasic acid having at least 2 carboxylic groups per molecule.

16. A curable composition comprising a cyclo-aliphatic epoxide, a polyether polyol having a molecular weight of from about 1000 to that molecular weight which does not form a two-phase system with the epoxide and a hardener selected from phenolic hardeners having at least two carboxylic groups per molecule and anhydrides of such polybasic acids.

28.