CA1091377A - Process for the manufacture of crystalline, crosslinked, elastomeric epoxide resins - Google Patents
Process for the manufacture of crystalline, crosslinked, elastomeric epoxide resinsInfo
- Publication number
- CA1091377A CA1091377A CA251,053A CA251053A CA1091377A CA 1091377 A CA1091377 A CA 1091377A CA 251053 A CA251053 A CA 251053A CA 1091377 A CA1091377 A CA 1091377A
- Authority
- CA
- Canada
- Prior art keywords
- polyester
- epoxide
- process according
- polycarboxylic acids
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure The invention relates to the manufacture of crystalline epoxide resins which exhibit a marked crystallite melt tem-perature. me formation of the crystallites is caused by mole-cule blocks which are derived from aliphatic polyester-polycar-boxylic acids. According to the invention, two aliphatic poly-ester-polycarboxylic acids (A and B) are reacted under very specific quantitative conditions with epoxide compounds which contain at least 2 epoxide groups and optionally with curing agents. The polyester-polycarboxylic acids A are purely n-ali-phatic in character, whereas the polyester-polycarboxylic acids B are not. They contain, for example, neopentyl radicals which are derived from neopentyl alcohol during the ester formation.
These crystalline synthetic resins are particularly suitable for use as material for absorbing solar energy in solar energy collectors.
These crystalline synthetic resins are particularly suitable for use as material for absorbing solar energy in solar energy collectors.
Description
.
The invention relates to crys~alline, crosslinked, elastomeric epoxide resins, in which the flexible and rigid blocks essentially consist of aliphatic molecule chains and which are distinguished by their special morphological propertiès. In the present document and in accordance with the present invention, a crystalline epoxide resin is to be understood as a product which is usually partially ~ crystalline.
`- Various epoxide resins, all of which contain, as crystallites, the radicals of a long-chain aliphatic polyester-polycarboxylic acid, are already known. In this connect-ion, British Patents 1,164,584 and 1,283,653 should be men-tioned in particular. These products are crystalline synthetic resins which, because they can be stretched, exhibit very high elongations at break at room temperature. If r they are warmed to a temperature above the crystallisation transition temperature, they then exhibit soft rubbery-elastic properties and have only a low mechanical strength. How-ever, they exhibit a relatively low reversible extensibility . :;
and, at the same time, fairly high modulus values. Be-cause of these properties, which manifest themselves in the form of stiffness and brittleness, these resins are less suitable as materials for use together with a material of a different type, for example for laminates with glass, metal, carbon, plastics of a different type~ and the like (especially in the form of fibres). Particularly in the case of their -use for potting, for example around glass or metal, with i ~ ~ - 2 -.; ,. . :
.
-.
i;``
~ 7'~
which it is not possible to avoid a certain atnount of therrQal cycling, considerable dllatation stresses result which, when the casting is cooled, lead -to a disadvantageous perma-nent deformation or even to the forma-tion of cracks.
The object of the lnvention is to provide crystalline, elastomeric epoxide resins which, do~n to relatively 1O-YJ
temperatures, do not exhibit -these adverse properties of the plastics according to the prior art discussed above.
They must, therefore, exhibit a greater reversible extensi-bility and lower mo~uli and these properties should be retained up to relatively high temperatures and, a' the same . .
' time, down to temperatures which are as low as possible.
-; By means of these desired properties it would then be possibleto avoid heat-dependent dilatation s-tresses in connection with the other type of material in a laminate and to avoid increased : formation of cracks which is associated therewith.
- The subject of the invention is a process for the :f manufacture of crystalline, crosslinked, elastomeric epoxide ; resins, which is characterised in that epoxide compounds, , . . .
containing two or more epoxide groups, are reacted :~ a) with polyester-polycarboxylic acids A which essentially .
~-~ contain segments of the formula I
`:
~ -[O-(CH2)n-0-CO-(CH2)m-CO]p- (I) ~:' in which n and m are identical or different and denote 2 or a higher number than 2, and to which the condition n + m = 6 to 30 applies, and in which p denotes a n~mber from 2 to 40 which, . . .
;~
,~ ' . ~.
,..... . .
~'. . ' , ' ~ :.
,~ ,.. .
~ ' ' ' however, is sufficiently large that the segment contains at least 30 -CH2- groups, and b) with polyester-polycarboxylic acids B which essentially contains segments of the formula II
-[O-Rl-0.cO-R2_co] _ (II) in which Rl and R2 are identical or different and denote an alkylene radical with at least 2 C atoms in the chain and in which, per 0 bridge, an average of at least 3.5 and at most 30 C atoms, without taking into account the C atoms of the -CO.0-radicals, are present in the chain, and wherein the radicals Rl and R together contain at least one alkyl group or cyclo-alkyl group or one aryl group as a substituent for one H atom, and in which q denotes a number from 2 to 40, which~ however, is sufficiently large that the segment contains at least 30 C
atoms, without taking into account the C atoms of the -C0.0-radicals, in the chain, and c) if appropriate, with curing agents C, and, if appropriate, in the presence of accelerators, in a ratio such that 0.5 to 1.2 equivalents of polyester-polycarboxylic acid are present :, per equivalent of epoxide compound, that 1/10 to 9/10 of these :.~ 0.5 to 1.2 equivalents are attributable to the polyester-:j .; polycarboxylic acid A and the remaining 9/10 to 1/10 to the `;~. polyester-polycarboxylic acid B, and that up to 0.6 equivalent of curing agent C is ~;' ;
, '.`- ' ~ ' :
' ' ' ' ` ~ ' ' , ' '7 . ` .
`'-present per equivalent of epoxide compound, with the proviso that, in the cases in which only difunctional epoxide com-pounds and difunctional polyester-polycarboxylic acids A and - B are employed, the epoxide groups must be present in excess and the reaction with a curing agent C is essential.
;~ Preferably, the condition n + m = 6 to 24 applies to the formula I.
In the epoxide resins obtained according to the . .
` invention, the radicals of the polyester-polycarboxylic acids ; A represent the rigid molecule blocksand are in the form of ~` crystallites with crystallite melting points between 40 and 120C. The radicals of the polyester-polycarboxylic acids ;
.- -,~ B, on the other hand, are incorporated as flexible blocks in ` the crosslinked molecule and in practice these form the matrix in which the crystallites are incorporated. It is partic-ularly surprising that a relatively large proportion of the , polyester-polycarboxylic acids B, that is to say up to 9/10 of ;; the total amount of polyester-polycarboxylic acid employed, can be incorporated in the crosslinked epoxide resin without this resulting in crystallisation being prevented.
..,~, Preferably, the procedure followed according to the invention is such that 0.7 to 1.2, especially 0.9 to 1.1, ~, equivalents of polyester-carboxylic acid are present per .. ~
equivalent of epoxide compound.
~ .
The polyester-polycarboxylic acids A and B used in the ~' reaction can for practical purposes be manufactured by the same basic process, by esterification of corresponding ali-~,..
~',. . .
.; .
~` '' . ' ' :
`; ~
.
~ 7'~
phatic dialcohols and aliphatic dicarboxylic acids or by esterification between suitable derivatives of these alcohols and dicarboxylic acids, such as, for example, the anhydrides, acid chlorides and the like. The dicarboxylic acids must - be present in excess.
- Where minor amounts of aliphatic polyalcohols with at ;
least 3 OH groups, especially glycerol, are also used, branched, that is to say at least 3-functional, polyester-polycarboxylic acids A and B are obtained. The use of the latter in the ; reacti~n according to the invention is also a preferred form of i' the invention. Branched polyester-polycarboxylic acids A
and B which are obtained if small amounts of polycarboxylic acids, or their anhydrides, with at least ~ carboxyl groups (such as, for example, trimellitic acid) are also present during the manufacture of the polyester-polycarboxylic acids, are equally suitable for the reaction according to the invention.
However, it is also possible to employ branched poly-ester-polycarboxylic acids A and B, which are obtainable by . .
esterification of the terminal OH groups of long-chain poly-. . - .
ester-polyols, especially of polyester-diols, with poly-, carboxylic acids which contain at least 3 -CO.OH groups, such - as, for example, trimellitic acid, or with corresponding anhydrides.
When manufacturing polyester-po~ycarboxylic acids B
it is necessary, in contrast to the manufacture of poly-ester-polycarboxylic acids A, for either the dicarboxylic acids . .
' ' .
: .
.
- - , ~ ' ' ~
~ ~ .
:', - - ~ ' : ~ ' .
' : ' - , 7'i' (or the derivatives thereof which are suitable for forming the ester) or the diols (or the derivatives) or for both reactants to contain at least one alkyl, cycloalkyl or aryl group as a substituent for one H atom or one ring-forming, optionally substituted alkylene group as a substituent for two H atoms of a chain. Preferred reactants to be mentioned here in this connection are neopentylglycol, hexahydrophthalic an-hydride and dimerised mono-unsaturated or di-unsaturated fatty acids. Examples of such dimerised fatty acids which may be mentioned are the known dicarboxylic acids which are formed by dimerisation of linoleic acid or of ricinoleic acid.
The basic rules for the manufacture of the polyester-, ~ .
, polycarboxylic acids A and B used according to the present , invention in other respects entirely correspond to those which have to be observed for the manufacture of the "long-chain dicarboxylic acids" employed according to British Patent ~, 1,164,584, and which are described in detail in this British patent. Further data on the basic principles of the , manuf,acture of such long-chain, aliphatic polyester-polycarboxy-lic acids are also to be found in a publication by Hans Batzer ~ et al. in "Die Angewandte Makromolekulare Chemie" 1973, page !., 349-412.
~;, Examples of suitable polyester-polycarboxylic acids A
~,~, , are those based on the following polyalcohols and polycarboxylic acids:
, 16 mols of adipic acid - 15 mols of hexane-1,6-diol 21 mols of succinic acid - 20 mols of butane-1,4-dio' ,. .
.
~: ~
'. " ' . . , 11 mols of sebacic acid - 10 mols of hexane-1,6-diol Glycerol - succinic acid - butanediol (1:24:21) 11 mols of succinic acid - 10 mols of butanediol 11 mols of dodecanedicarboxylic acid - 10 mols of hexanediol 11 mols of dodecanedicarboxylic acid - 10 mols of butanediol 11 mols of dodecanedicarboxylic acid - 10 mols of propane-1,3-diol 7 mols of dodecanedicarboxylic acid - 6 mols of hexanediol 7 mols of dodecanedicarboxylic acid - 6 mols of dodecanediol 7 mols of sebacic acid - 6 mols of dodecanediol 11 mols of sebacic acid - 6 mols of dodecanediol Trimethylhexanediol - succinic anhydride - butanediol (1:30:27) 11 mols of dodecanedicarboxylic acid - 10 mols of ethylene glycol 5 mols of decanedicarboxylic acid - 4 mols of dodecanediol 11 mols of decanedicarboxylic acid - 10 mols of hexanediol Examples of suitable polyester-polycarboxylic acids B
are those based on the following polyalcohols and poly-carboxylic acids:
11 mols of sebacic acid - 10 mols of neopentylglycol 8 mols of adipic acid - 7 mols of neopentylglycol 13 mols of adipic acid - 12 mols of neopentylglycol 8 mols of adipic acid - 7 mols of trimethylhexanediol 8 mols of trimethyladipic acid - 7 mols of neopentylglycol 14 mols of adipic acid - 13 mols of neopentylglycol 4 mols of dimerised fatty acid - 3 mols of diethylene glycol 4 mols of dimerised fat-ty acid - 3 mols of hexanediol . :,.. :- , : , .
.. " ' ' ~
, , ' .
':
.
lOIJ~
; 3 mols of dimerised fatty acid - 2 mols of hexanediol Glycerol ~ adipic acid - butanediol - neopentylglycol (1:9:3:3) Trimethylhexanediol - adipic acid - hexanediol - neopentyl-glycol (1:8:2:3) . .
14 mols of succinic acid - 13 mols of neopentylglycol 4 mols of hexahydrophthalic anhydride - 3 mols of neopentyl-glycol.
As epoxide compounds containing two or more epoxide ..:
groups it is possible to employ practically all the polyepoxy compounds known,to those skilled in the art, from publications and patent specifications. According to the invention, one or more different epoxide compounds can be reacted. Tri-; .~ .
glycidyl isocyanurate and triglycidyl compounds which contain one or more hydantoin groups and/or dihydrouracil groups, especially epoxide compounds of the formula III
', . .
I CH~ CH~
O CH3 ~ ~ 3 / \
The invention relates to crys~alline, crosslinked, elastomeric epoxide resins, in which the flexible and rigid blocks essentially consist of aliphatic molecule chains and which are distinguished by their special morphological propertiès. In the present document and in accordance with the present invention, a crystalline epoxide resin is to be understood as a product which is usually partially ~ crystalline.
`- Various epoxide resins, all of which contain, as crystallites, the radicals of a long-chain aliphatic polyester-polycarboxylic acid, are already known. In this connect-ion, British Patents 1,164,584 and 1,283,653 should be men-tioned in particular. These products are crystalline synthetic resins which, because they can be stretched, exhibit very high elongations at break at room temperature. If r they are warmed to a temperature above the crystallisation transition temperature, they then exhibit soft rubbery-elastic properties and have only a low mechanical strength. How-ever, they exhibit a relatively low reversible extensibility . :;
and, at the same time, fairly high modulus values. Be-cause of these properties, which manifest themselves in the form of stiffness and brittleness, these resins are less suitable as materials for use together with a material of a different type, for example for laminates with glass, metal, carbon, plastics of a different type~ and the like (especially in the form of fibres). Particularly in the case of their -use for potting, for example around glass or metal, with i ~ ~ - 2 -.; ,. . :
.
-.
i;``
~ 7'~
which it is not possible to avoid a certain atnount of therrQal cycling, considerable dllatation stresses result which, when the casting is cooled, lead -to a disadvantageous perma-nent deformation or even to the forma-tion of cracks.
The object of the lnvention is to provide crystalline, elastomeric epoxide resins which, do~n to relatively 1O-YJ
temperatures, do not exhibit -these adverse properties of the plastics according to the prior art discussed above.
They must, therefore, exhibit a greater reversible extensi-bility and lower mo~uli and these properties should be retained up to relatively high temperatures and, a' the same . .
' time, down to temperatures which are as low as possible.
-; By means of these desired properties it would then be possibleto avoid heat-dependent dilatation s-tresses in connection with the other type of material in a laminate and to avoid increased : formation of cracks which is associated therewith.
- The subject of the invention is a process for the :f manufacture of crystalline, crosslinked, elastomeric epoxide ; resins, which is characterised in that epoxide compounds, , . . .
containing two or more epoxide groups, are reacted :~ a) with polyester-polycarboxylic acids A which essentially .
~-~ contain segments of the formula I
`:
~ -[O-(CH2)n-0-CO-(CH2)m-CO]p- (I) ~:' in which n and m are identical or different and denote 2 or a higher number than 2, and to which the condition n + m = 6 to 30 applies, and in which p denotes a n~mber from 2 to 40 which, . . .
;~
,~ ' . ~.
,..... . .
~'. . ' , ' ~ :.
,~ ,.. .
~ ' ' ' however, is sufficiently large that the segment contains at least 30 -CH2- groups, and b) with polyester-polycarboxylic acids B which essentially contains segments of the formula II
-[O-Rl-0.cO-R2_co] _ (II) in which Rl and R2 are identical or different and denote an alkylene radical with at least 2 C atoms in the chain and in which, per 0 bridge, an average of at least 3.5 and at most 30 C atoms, without taking into account the C atoms of the -CO.0-radicals, are present in the chain, and wherein the radicals Rl and R together contain at least one alkyl group or cyclo-alkyl group or one aryl group as a substituent for one H atom, and in which q denotes a number from 2 to 40, which~ however, is sufficiently large that the segment contains at least 30 C
atoms, without taking into account the C atoms of the -C0.0-radicals, in the chain, and c) if appropriate, with curing agents C, and, if appropriate, in the presence of accelerators, in a ratio such that 0.5 to 1.2 equivalents of polyester-polycarboxylic acid are present :, per equivalent of epoxide compound, that 1/10 to 9/10 of these :.~ 0.5 to 1.2 equivalents are attributable to the polyester-:j .; polycarboxylic acid A and the remaining 9/10 to 1/10 to the `;~. polyester-polycarboxylic acid B, and that up to 0.6 equivalent of curing agent C is ~;' ;
, '.`- ' ~ ' :
' ' ' ' ` ~ ' ' , ' '7 . ` .
`'-present per equivalent of epoxide compound, with the proviso that, in the cases in which only difunctional epoxide com-pounds and difunctional polyester-polycarboxylic acids A and - B are employed, the epoxide groups must be present in excess and the reaction with a curing agent C is essential.
;~ Preferably, the condition n + m = 6 to 24 applies to the formula I.
In the epoxide resins obtained according to the . .
` invention, the radicals of the polyester-polycarboxylic acids ; A represent the rigid molecule blocksand are in the form of ~` crystallites with crystallite melting points between 40 and 120C. The radicals of the polyester-polycarboxylic acids ;
.- -,~ B, on the other hand, are incorporated as flexible blocks in ` the crosslinked molecule and in practice these form the matrix in which the crystallites are incorporated. It is partic-ularly surprising that a relatively large proportion of the , polyester-polycarboxylic acids B, that is to say up to 9/10 of ;; the total amount of polyester-polycarboxylic acid employed, can be incorporated in the crosslinked epoxide resin without this resulting in crystallisation being prevented.
..,~, Preferably, the procedure followed according to the invention is such that 0.7 to 1.2, especially 0.9 to 1.1, ~, equivalents of polyester-carboxylic acid are present per .. ~
equivalent of epoxide compound.
~ .
The polyester-polycarboxylic acids A and B used in the ~' reaction can for practical purposes be manufactured by the same basic process, by esterification of corresponding ali-~,..
~',. . .
.; .
~` '' . ' ' :
`; ~
.
~ 7'~
phatic dialcohols and aliphatic dicarboxylic acids or by esterification between suitable derivatives of these alcohols and dicarboxylic acids, such as, for example, the anhydrides, acid chlorides and the like. The dicarboxylic acids must - be present in excess.
- Where minor amounts of aliphatic polyalcohols with at ;
least 3 OH groups, especially glycerol, are also used, branched, that is to say at least 3-functional, polyester-polycarboxylic acids A and B are obtained. The use of the latter in the ; reacti~n according to the invention is also a preferred form of i' the invention. Branched polyester-polycarboxylic acids A
and B which are obtained if small amounts of polycarboxylic acids, or their anhydrides, with at least ~ carboxyl groups (such as, for example, trimellitic acid) are also present during the manufacture of the polyester-polycarboxylic acids, are equally suitable for the reaction according to the invention.
However, it is also possible to employ branched poly-ester-polycarboxylic acids A and B, which are obtainable by . .
esterification of the terminal OH groups of long-chain poly-. . - .
ester-polyols, especially of polyester-diols, with poly-, carboxylic acids which contain at least 3 -CO.OH groups, such - as, for example, trimellitic acid, or with corresponding anhydrides.
When manufacturing polyester-po~ycarboxylic acids B
it is necessary, in contrast to the manufacture of poly-ester-polycarboxylic acids A, for either the dicarboxylic acids . .
' ' .
: .
.
- - , ~ ' ' ~
~ ~ .
:', - - ~ ' : ~ ' .
' : ' - , 7'i' (or the derivatives thereof which are suitable for forming the ester) or the diols (or the derivatives) or for both reactants to contain at least one alkyl, cycloalkyl or aryl group as a substituent for one H atom or one ring-forming, optionally substituted alkylene group as a substituent for two H atoms of a chain. Preferred reactants to be mentioned here in this connection are neopentylglycol, hexahydrophthalic an-hydride and dimerised mono-unsaturated or di-unsaturated fatty acids. Examples of such dimerised fatty acids which may be mentioned are the known dicarboxylic acids which are formed by dimerisation of linoleic acid or of ricinoleic acid.
The basic rules for the manufacture of the polyester-, ~ .
, polycarboxylic acids A and B used according to the present , invention in other respects entirely correspond to those which have to be observed for the manufacture of the "long-chain dicarboxylic acids" employed according to British Patent ~, 1,164,584, and which are described in detail in this British patent. Further data on the basic principles of the , manuf,acture of such long-chain, aliphatic polyester-polycarboxy-lic acids are also to be found in a publication by Hans Batzer ~ et al. in "Die Angewandte Makromolekulare Chemie" 1973, page !., 349-412.
~;, Examples of suitable polyester-polycarboxylic acids A
~,~, , are those based on the following polyalcohols and polycarboxylic acids:
, 16 mols of adipic acid - 15 mols of hexane-1,6-diol 21 mols of succinic acid - 20 mols of butane-1,4-dio' ,. .
.
~: ~
'. " ' . . , 11 mols of sebacic acid - 10 mols of hexane-1,6-diol Glycerol - succinic acid - butanediol (1:24:21) 11 mols of succinic acid - 10 mols of butanediol 11 mols of dodecanedicarboxylic acid - 10 mols of hexanediol 11 mols of dodecanedicarboxylic acid - 10 mols of butanediol 11 mols of dodecanedicarboxylic acid - 10 mols of propane-1,3-diol 7 mols of dodecanedicarboxylic acid - 6 mols of hexanediol 7 mols of dodecanedicarboxylic acid - 6 mols of dodecanediol 7 mols of sebacic acid - 6 mols of dodecanediol 11 mols of sebacic acid - 6 mols of dodecanediol Trimethylhexanediol - succinic anhydride - butanediol (1:30:27) 11 mols of dodecanedicarboxylic acid - 10 mols of ethylene glycol 5 mols of decanedicarboxylic acid - 4 mols of dodecanediol 11 mols of decanedicarboxylic acid - 10 mols of hexanediol Examples of suitable polyester-polycarboxylic acids B
are those based on the following polyalcohols and poly-carboxylic acids:
11 mols of sebacic acid - 10 mols of neopentylglycol 8 mols of adipic acid - 7 mols of neopentylglycol 13 mols of adipic acid - 12 mols of neopentylglycol 8 mols of adipic acid - 7 mols of trimethylhexanediol 8 mols of trimethyladipic acid - 7 mols of neopentylglycol 14 mols of adipic acid - 13 mols of neopentylglycol 4 mols of dimerised fatty acid - 3 mols of diethylene glycol 4 mols of dimerised fat-ty acid - 3 mols of hexanediol . :,.. :- , : , .
.. " ' ' ~
, , ' .
':
.
lOIJ~
; 3 mols of dimerised fatty acid - 2 mols of hexanediol Glycerol ~ adipic acid - butanediol - neopentylglycol (1:9:3:3) Trimethylhexanediol - adipic acid - hexanediol - neopentyl-glycol (1:8:2:3) . .
14 mols of succinic acid - 13 mols of neopentylglycol 4 mols of hexahydrophthalic anhydride - 3 mols of neopentyl-glycol.
As epoxide compounds containing two or more epoxide ..:
groups it is possible to employ practically all the polyepoxy compounds known,to those skilled in the art, from publications and patent specifications. According to the invention, one or more different epoxide compounds can be reacted. Tri-; .~ .
glycidyl isocyanurate and triglycidyl compounds which contain one or more hydantoin groups and/or dihydrouracil groups, especially epoxide compounds of the formula III
', . .
I CH~ CH~
O CH3 ~ ~ 3 / \
2 CH2 ~ CH2-cH-cH2-N ~ N-cH2-c~ CH2 , j ~;, I
~ CH
`,': I~o ' CH
' are particularly suitable.
In principle, the reaction according to the invention ,,.' - _ g _ . :~. -... .
~; . , , . ~, ,:
~':
, .
7'i' can be carried out either in 1 stage or in several stages.
If the epoxide compounds used have at least 3 epoxide groups, and polyester-dicarboxylic acids A and B are employed, it is possible, for example, to carry out the reaction in 1 s~age, that is to say to start from a reaction mixture which contains all the reactants simultaneously. It is possible to pro-ceed in exactly the same way (that is to say in 1 stage) if, instead of the dicarboxylic acids, polyester-polycarboxylic acids A and B which have at least ~ carboxyl groups are empIoyed. In the converse case, that is to say when using polyester-carboxylic acids A and B containing at least
~ CH
`,': I~o ' CH
' are particularly suitable.
In principle, the reaction according to the invention ,,.' - _ g _ . :~. -... .
~; . , , . ~, ,:
~':
, .
7'i' can be carried out either in 1 stage or in several stages.
If the epoxide compounds used have at least 3 epoxide groups, and polyester-dicarboxylic acids A and B are employed, it is possible, for example, to carry out the reaction in 1 s~age, that is to say to start from a reaction mixture which contains all the reactants simultaneously. It is possible to pro-ceed in exactly the same way (that is to say in 1 stage) if, instead of the dicarboxylic acids, polyester-polycarboxylic acids A and B which have at least ~ carboxyl groups are empIoyed. In the converse case, that is to say when using polyester-carboxylic acids A and B containing at least
3 carboxyl groups, and using diepoxy compounds, working in 1 stage is again possible and is the nor~al method of reaction for such cases.
If only diepoxy compounds and only polyester-dicarboxylic acids are employed, it is only possible to work ih one stage if an excess of epoxide compoundsis used and at the same time a polycarboxylic acid anhydride is added.
In the multi-stage method, an adduct containing epoxide groups is initially manufactured, in a first stage, from the epoxide compounds and the polyester-polycarboxylic acids A and/or B, preferably using 0.5 to 1 equivalent of polyester-polycarboxylic acid per 2 equivalents of epoxide compounds. In a second reaction stage, the crosslinking is then carried out, by reaction of the adducts with the remainder of the polyester-polycarboxylic acids A and/or B. It is also possible to proceed by carrying out the crosslinking in .
;"... , ,. - . . : ~ : :
. . .
.: ' . - :
"', ' ., ' .. -- ~ ~
7~' the second stage in the presence of customary curing agents.
It is also possible additionally to add yet further monomeric epoxide compounds and correspondingly larger amounts of curing agents.
- As customary curing agents for epoxide resins it is possible to employ all the substances which are described in .,;
the numerous publications and patents relating to epoxide resins. Inter alia, the following substances may be listed here: compounds with amino groups, polyalcohols, poly-carboxylic acids and their anhydrides, acid amides, polyesters, phenol-formaldehyde condensates and amino-resin precondensates.
Tertiary amines and imidazoles may be mentioned as examples `: -of suitable accelerators.
The reaction according to the invention is preferably ;"~
~' carried out in the melt. For this, preferably tempera-tures ; of between 50 and 200C and reaction times of more than 1 hour and up to about 20 hours are required. In principle, the reaction according to the invention can also be carried out in solution.
Before or during the reaction, a blowing agent for - the manufacture of foams can also be added.
- The crystalline, crosslinked plastic products are as a rule manufactured with simultaneous shaping, to give ~ castings, foamed articles, pressings, lacquer films, laminates, `i~ adhesive bonds and the like.
Of course,furth~rcustomary additives, such as fillers, reinforcing agents, mould release agents, agents to protect . , .
. .
:
;
.
. . .
'".,.,' lV~ ;7~7 against aging, flameproofing substances, dyestuffs or pigments, can be added to the moulding compositions.
Suitable fillers or reinforcing agents are fibrous or pulverulent inorganic or organic substances. Quartz powder, aluminium oxide trihydrate, mica, aluminium powder, iron oxide, ground dolomite, chalk powder, gypsum, slate powder, unburnt kaolin (bolus), burnt kaolin, glass fibres, boron fibres and asbestos fibres may be mentioned. A content of materials, in the form of fibres and powders, which assist the heat conductivity can prove particularly advantageous.
Examples of such materials are metals (for example aluminium powder), carbon, such as carbon black and graphite in powder form, and carbon fibres.
For the purpose of optimum and accelerated development of the crystal structure of the polymers it is also advisable to add nucleating agents, such as phthalocyanines, carbon black, a-naphthoic acid or the like.
The epoxide resins which can be manufactured according , .
to the invention can also be used, apart from for the manu-facture of mouldings and laminates with glass, metal or the like, for the manufacture of foamed articles.
A particular use for the new epoxide resins is as material which absorbs solar energy in collectors for the storage of solar energy. In such solar collectors, very severe thermal cycling arises, which, in the collectors of the state of the art, can lead, as a result of the different materials having ~ifferent coefficients of thermal exuansion~
. .; .
.,.,:, . .
.
, .- . .
:
.. . .
.... . . .
~.. . .
' ......
to dilatation stresses, deformations and the formation of - cracks. When the epoxide resins manufactured according to .~
;~ the invention are used, for example, as a potting .
~! material for metallic tubes and fins, such as are used in heat exchangers, these disadvantages do not arise.
For this special application, the crystalline, cross- -linked, elastomeric epoxide resins are preferably dyed black (with at most up to 20/o by weight of colorant, preferably ~: carbon black).
li~ , The crystalline, crosslinked, elastomeric epoxide resins which can be manufactured by the process according to the invention are also a further subject of the invention.
Example 1 77 g (0.05 equivalent) of an acid polyester prepared, by the melt process, from 21 mols of succinic anhydride and 20 mols of butanediol and 35 g (0.05 equivalent) of an acid polyester prepared, by the melt process, from 8 mols of adipic acid and 7 mols of neopentylglycol are warmed to 120C
and mixed well with 11.0 g (0.1 equivalent) of triglycidyl isocyanurate and the mixture is poured into Anticorodal moulds which have internal dimensions of 150 x 150 x 1 mm, have been ,~ .
'r'' treated with a silicone mould-release agent and have been pre-warmed to 140C. After removing the air, the mixture is cured in vacuo for 16 hours at 140C. Crystalline, : soft and tough mouldings are obtained, for whick the following , characteristics are determined:
,,:
".. ' ' , ....
... -.
.
.: .
Tensile strength according to VSM 77,101 2 tmoulding No. 1)~{ = 7.3 N/mm Elongation at break according to VSM 77,101 = 350%
Crystallite melting point (Tm)~E = 100 C
x The mouldings are punched from the 1 mm thick sheet using a punching tool. (The tensile test also corresponds to IS0 R 527) Determined with a differential scanning calorimeter (heat-ing rate = 10/minute) Exam~le 2 52.6 g (0.02 equivalent) of an adduct obtained from 2.0 equivalents of tetrahydrophthalic acid diglycidyl ester and 1.0 equivalent of an acid polyester obtained from 21 mols of succinic anhydride and 20 mols of butanediol, together with 1.6 g (0.01 equivalents) of hexahydrophthalic acid diglycidyl ester and 8.3 g (0.01 equivalent) of an adduct obtained from 2.5 equivalents of 3',4'-epoxyhexahydrobenzal-3,4-epoxy-cyclohexane-l,l-dimethanol and 1.0 equivalent of an acid poly-ester obtained from 11 mols of sebacic acid and 10 mols of neopentylglycol, are warmed to 130C. The mixture is mixed well with 10.6 g (0.04 mol) of dodecenylsuccinic anhydride and several drops of dimethylbenzylamine and is cast and cured analogously to Example l; Mouldings with the following characteristics are obtained:
Tensile strength = 13.8 N/mm2 Elongation at break = 85q~
Yield stress = 13.1 N/mm2 Elongation up to l"he yield point = 29%
Tm = g5 C
.. . . s .. ~ ~ . . ..
.
~ 77 Without the addition of the sebacic acid-neopentyl-glycol polyester adduct, an elongation up to ~he yield point of less tha~ 10% is measured at a Tm value of 98C. The main advantage of the new block copolymers is thus that ~heir reversible extensibility is increased several fold at abou-t the same crystallite melting point.
Example 3 155 g (0.1 equivalent) of an acid polyester obtained from 11 mols of sebacic acid and 10 mols of hexanediol and
If only diepoxy compounds and only polyester-dicarboxylic acids are employed, it is only possible to work ih one stage if an excess of epoxide compoundsis used and at the same time a polycarboxylic acid anhydride is added.
In the multi-stage method, an adduct containing epoxide groups is initially manufactured, in a first stage, from the epoxide compounds and the polyester-polycarboxylic acids A and/or B, preferably using 0.5 to 1 equivalent of polyester-polycarboxylic acid per 2 equivalents of epoxide compounds. In a second reaction stage, the crosslinking is then carried out, by reaction of the adducts with the remainder of the polyester-polycarboxylic acids A and/or B. It is also possible to proceed by carrying out the crosslinking in .
;"... , ,. - . . : ~ : :
. . .
.: ' . - :
"', ' ., ' .. -- ~ ~
7~' the second stage in the presence of customary curing agents.
It is also possible additionally to add yet further monomeric epoxide compounds and correspondingly larger amounts of curing agents.
- As customary curing agents for epoxide resins it is possible to employ all the substances which are described in .,;
the numerous publications and patents relating to epoxide resins. Inter alia, the following substances may be listed here: compounds with amino groups, polyalcohols, poly-carboxylic acids and their anhydrides, acid amides, polyesters, phenol-formaldehyde condensates and amino-resin precondensates.
Tertiary amines and imidazoles may be mentioned as examples `: -of suitable accelerators.
The reaction according to the invention is preferably ;"~
~' carried out in the melt. For this, preferably tempera-tures ; of between 50 and 200C and reaction times of more than 1 hour and up to about 20 hours are required. In principle, the reaction according to the invention can also be carried out in solution.
Before or during the reaction, a blowing agent for - the manufacture of foams can also be added.
- The crystalline, crosslinked plastic products are as a rule manufactured with simultaneous shaping, to give ~ castings, foamed articles, pressings, lacquer films, laminates, `i~ adhesive bonds and the like.
Of course,furth~rcustomary additives, such as fillers, reinforcing agents, mould release agents, agents to protect . , .
. .
:
;
.
. . .
'".,.,' lV~ ;7~7 against aging, flameproofing substances, dyestuffs or pigments, can be added to the moulding compositions.
Suitable fillers or reinforcing agents are fibrous or pulverulent inorganic or organic substances. Quartz powder, aluminium oxide trihydrate, mica, aluminium powder, iron oxide, ground dolomite, chalk powder, gypsum, slate powder, unburnt kaolin (bolus), burnt kaolin, glass fibres, boron fibres and asbestos fibres may be mentioned. A content of materials, in the form of fibres and powders, which assist the heat conductivity can prove particularly advantageous.
Examples of such materials are metals (for example aluminium powder), carbon, such as carbon black and graphite in powder form, and carbon fibres.
For the purpose of optimum and accelerated development of the crystal structure of the polymers it is also advisable to add nucleating agents, such as phthalocyanines, carbon black, a-naphthoic acid or the like.
The epoxide resins which can be manufactured according , .
to the invention can also be used, apart from for the manu-facture of mouldings and laminates with glass, metal or the like, for the manufacture of foamed articles.
A particular use for the new epoxide resins is as material which absorbs solar energy in collectors for the storage of solar energy. In such solar collectors, very severe thermal cycling arises, which, in the collectors of the state of the art, can lead, as a result of the different materials having ~ifferent coefficients of thermal exuansion~
. .; .
.,.,:, . .
.
, .- . .
:
.. . .
.... . . .
~.. . .
' ......
to dilatation stresses, deformations and the formation of - cracks. When the epoxide resins manufactured according to .~
;~ the invention are used, for example, as a potting .
~! material for metallic tubes and fins, such as are used in heat exchangers, these disadvantages do not arise.
For this special application, the crystalline, cross- -linked, elastomeric epoxide resins are preferably dyed black (with at most up to 20/o by weight of colorant, preferably ~: carbon black).
li~ , The crystalline, crosslinked, elastomeric epoxide resins which can be manufactured by the process according to the invention are also a further subject of the invention.
Example 1 77 g (0.05 equivalent) of an acid polyester prepared, by the melt process, from 21 mols of succinic anhydride and 20 mols of butanediol and 35 g (0.05 equivalent) of an acid polyester prepared, by the melt process, from 8 mols of adipic acid and 7 mols of neopentylglycol are warmed to 120C
and mixed well with 11.0 g (0.1 equivalent) of triglycidyl isocyanurate and the mixture is poured into Anticorodal moulds which have internal dimensions of 150 x 150 x 1 mm, have been ,~ .
'r'' treated with a silicone mould-release agent and have been pre-warmed to 140C. After removing the air, the mixture is cured in vacuo for 16 hours at 140C. Crystalline, : soft and tough mouldings are obtained, for whick the following , characteristics are determined:
,,:
".. ' ' , ....
... -.
.
.: .
Tensile strength according to VSM 77,101 2 tmoulding No. 1)~{ = 7.3 N/mm Elongation at break according to VSM 77,101 = 350%
Crystallite melting point (Tm)~E = 100 C
x The mouldings are punched from the 1 mm thick sheet using a punching tool. (The tensile test also corresponds to IS0 R 527) Determined with a differential scanning calorimeter (heat-ing rate = 10/minute) Exam~le 2 52.6 g (0.02 equivalent) of an adduct obtained from 2.0 equivalents of tetrahydrophthalic acid diglycidyl ester and 1.0 equivalent of an acid polyester obtained from 21 mols of succinic anhydride and 20 mols of butanediol, together with 1.6 g (0.01 equivalents) of hexahydrophthalic acid diglycidyl ester and 8.3 g (0.01 equivalent) of an adduct obtained from 2.5 equivalents of 3',4'-epoxyhexahydrobenzal-3,4-epoxy-cyclohexane-l,l-dimethanol and 1.0 equivalent of an acid poly-ester obtained from 11 mols of sebacic acid and 10 mols of neopentylglycol, are warmed to 130C. The mixture is mixed well with 10.6 g (0.04 mol) of dodecenylsuccinic anhydride and several drops of dimethylbenzylamine and is cast and cured analogously to Example l; Mouldings with the following characteristics are obtained:
Tensile strength = 13.8 N/mm2 Elongation at break = 85q~
Yield stress = 13.1 N/mm2 Elongation up to l"he yield point = 29%
Tm = g5 C
.. . . s .. ~ ~ . . ..
.
~ 77 Without the addition of the sebacic acid-neopentyl-glycol polyester adduct, an elongation up to ~he yield point of less tha~ 10% is measured at a Tm value of 98C. The main advantage of the new block copolymers is thus that ~heir reversible extensibility is increased several fold at abou-t the same crystallite melting point.
Example 3 155 g (0.1 equivalent) of an acid polyester obtained from 11 mols of sebacic acid and 10 mols of hexanediol and
4.6 g (0.03 equivalent) of hexahydrophthalic anhydride are warmed to 100C and mixed well with 165 g (0.13 equivalent) of an adduct obtained from 100 parts by weight of an acid poly-ester obtained from 8 mols of adipic acid and 7 mols of neo-pentylglycol and 50 parts by weight of a bisphenol A diglycidyl ether with an epoxide equivalent weight of 185 and the mixture is processed, and cured, analogously to Example 1. Mould-ings with the following characteristics are obtained:
Tensile strength = 10.8 N/mm2 Elongation at break = 690%
Stress at the yield point = 5.0 N/mm2 Elongation at the yield point = 30%
Tm = 58C
An analogous experiment without the addition of the adipic acid-neopentylglycol adduct (using only 0.13 equivalent of bisphenol A diglycidyl ether) gives a Tm value of 59C.
In this case also, the flexibility (reversible deformability) is increased, whilst maintaining the crystallite melting point, by adding an amorphous polyester.
Example 4 76.7 g (0.1 equivalent) of a branched (trivalent) polyester, prepared from glycerol, succinic anhydride and butanediol and having an acid equivalent weight of 767, are melted and warmed to 110C and then mixed well, at this temperature, with 127 g (0.1 equivalent) of the adipic acid-polyester adduct described in Example 3 and the mixture is processed, and cured, analogously to Example 1. Mouldings with the following characteristics are obtained:
Tensile strength = 4.9 N/mm2 Elongation at break = 179%
Tm = 61C
Example 5 When 146 g (0.1 equivalent) of a branched polyester obtained from glycerol, succinic anhydride and butanediol and having an acid equivalent weight of 1,460 are used in place of the shorter-chain polyester, mouldings with the following characteristics are obtained analogously to Example 4:
Tensile strength . = 13.4 N/mm2 Elongation at break = 588%
Tm - ~ = 77 C
Example 6 (use in solar collectors) 259 g (0.24 equivalent) of an acid polyester obtained from 11 mols of succinic anhydride and 10 mols of butanediol and 165 g (0.2~ equivalent) of an acid polyester obtained from 8 mols of adipic acid and 7 mols of neopentylglycol were , ~
- : ~
. -`:`
warmed to 120C and mixed well with 15 g of carbon black,2,6 g of a light stabiliser ~ p-tert.-butylphenol derivative) and 80 g (0.48 equivalent) of the triglycidyl compound of the formula III and the mixture is processed, and cured, analogous-ly to Example 1. However, in this case an Anticorodal mould having ~ thickness of 10 mm was used. m e mould also contained a 130 cm long copper spiral, but no lamellae.
After curing, a black collector which was tough at room tempera-ture and had a crystallite melting point of 91C was obtained.
Three collector panels manufactured in this way were arranged in series, connected together and exposed to the sun.
A separate vessel containing 700 cm3 of water at 18C was warmed by means of a copper spiral. ~fter three hours, the water temperature was 71C, whilst the circulating water had a temperature of 74C.
( me test was carried out on 21.2.1975 in Basel).
No indication whatsoever of the formation of cracks could be found even after repeated use of the collectors, during which temperature variations between 5 and 80C arose.
Example 7 21.9 g of an acid polyester obtained from 5 mols of decanedicarboxylic acid and 4 mols of dodecanediol (equivalent weight = 832) and 16.8 of an acid polyester obtained from 4 mols of dimerised ricinoleic acid and 3 mols of hexanediol (equivalent weight 1,280) and 3.5 g of dodecenylsuccinic anhydride are warmed to 120C and mixed well with 7.4 g of . . .
~V~ i'7 .
the cycloaliphatic diepoxide compound of the following structure:
~CH2~
(equivalent weight 141) and 0.1 g of dlmethylbenzylamine and the mixture is poured into the pre-warmed moulds, analogously to Example 1. (Equivalent ratio = 1.0:0.5:0.5:2.0).
After curing for 16 hours at 140C, mouldings with the following properties are obtained:
Tensile strength = 8 N/mm2 Elongation at break = 141%
Tm = 55 C
Resistance to tear propagation . = 101 N (DIN
53,~63)-Example 8 49.3 g of an acid polyester obtained from 11 mols of decanedicarboxylic acid and 10 mols of~hexanediol (equivalent weight 1,415) and 2.6 g of an acid polyester obtained from 4 mols of hexahydrophthalic anhydride and 3 mols of neopentyl-glycol are warmed to 120C and, after adding 6.1 g of the epoxide compound of the following structure:
O
CH~ _ CHCH2CCCH2C~12 ~ J ~ ~ -',H2CH2COCH2CH~ o ~(~H2 CH~ - CHCH20CC~2Ch2 ~ ~
~ ~ ~ CH2CH2COCH2cH~ ~ H2 o .
lU5~ 7'~
(equivalent weight 123) and 0.01 g of dimethylbenzylamine, mixed well and cast, and cured, analogously to Example 1.
(Equivalent ratio = 1.0:0,2:1.2).
The mouldings have the following properties:
Tensile strength = 49 N/mm2 Elongation at break = 18%
Tm = 57C, Example 9 The procedure according to Example 8 is followed but with the difference that 1.2 equivalents of the triepoxide compound of the formula III are employed in place of 1.2 equivalents of the epoxide compound used in Example 8. The mouldings have the following characteristics:
Tensile strength = 30 N/mm Elongation at break = 320%
Resistance to tear propagation = 150 N
Tm = 49C
Tensile strength = 10.8 N/mm2 Elongation at break = 690%
Stress at the yield point = 5.0 N/mm2 Elongation at the yield point = 30%
Tm = 58C
An analogous experiment without the addition of the adipic acid-neopentylglycol adduct (using only 0.13 equivalent of bisphenol A diglycidyl ether) gives a Tm value of 59C.
In this case also, the flexibility (reversible deformability) is increased, whilst maintaining the crystallite melting point, by adding an amorphous polyester.
Example 4 76.7 g (0.1 equivalent) of a branched (trivalent) polyester, prepared from glycerol, succinic anhydride and butanediol and having an acid equivalent weight of 767, are melted and warmed to 110C and then mixed well, at this temperature, with 127 g (0.1 equivalent) of the adipic acid-polyester adduct described in Example 3 and the mixture is processed, and cured, analogously to Example 1. Mouldings with the following characteristics are obtained:
Tensile strength = 4.9 N/mm2 Elongation at break = 179%
Tm = 61C
Example 5 When 146 g (0.1 equivalent) of a branched polyester obtained from glycerol, succinic anhydride and butanediol and having an acid equivalent weight of 1,460 are used in place of the shorter-chain polyester, mouldings with the following characteristics are obtained analogously to Example 4:
Tensile strength . = 13.4 N/mm2 Elongation at break = 588%
Tm - ~ = 77 C
Example 6 (use in solar collectors) 259 g (0.24 equivalent) of an acid polyester obtained from 11 mols of succinic anhydride and 10 mols of butanediol and 165 g (0.2~ equivalent) of an acid polyester obtained from 8 mols of adipic acid and 7 mols of neopentylglycol were , ~
- : ~
. -`:`
warmed to 120C and mixed well with 15 g of carbon black,2,6 g of a light stabiliser ~ p-tert.-butylphenol derivative) and 80 g (0.48 equivalent) of the triglycidyl compound of the formula III and the mixture is processed, and cured, analogous-ly to Example 1. However, in this case an Anticorodal mould having ~ thickness of 10 mm was used. m e mould also contained a 130 cm long copper spiral, but no lamellae.
After curing, a black collector which was tough at room tempera-ture and had a crystallite melting point of 91C was obtained.
Three collector panels manufactured in this way were arranged in series, connected together and exposed to the sun.
A separate vessel containing 700 cm3 of water at 18C was warmed by means of a copper spiral. ~fter three hours, the water temperature was 71C, whilst the circulating water had a temperature of 74C.
( me test was carried out on 21.2.1975 in Basel).
No indication whatsoever of the formation of cracks could be found even after repeated use of the collectors, during which temperature variations between 5 and 80C arose.
Example 7 21.9 g of an acid polyester obtained from 5 mols of decanedicarboxylic acid and 4 mols of dodecanediol (equivalent weight = 832) and 16.8 of an acid polyester obtained from 4 mols of dimerised ricinoleic acid and 3 mols of hexanediol (equivalent weight 1,280) and 3.5 g of dodecenylsuccinic anhydride are warmed to 120C and mixed well with 7.4 g of . . .
~V~ i'7 .
the cycloaliphatic diepoxide compound of the following structure:
~CH2~
(equivalent weight 141) and 0.1 g of dlmethylbenzylamine and the mixture is poured into the pre-warmed moulds, analogously to Example 1. (Equivalent ratio = 1.0:0.5:0.5:2.0).
After curing for 16 hours at 140C, mouldings with the following properties are obtained:
Tensile strength = 8 N/mm2 Elongation at break = 141%
Tm = 55 C
Resistance to tear propagation . = 101 N (DIN
53,~63)-Example 8 49.3 g of an acid polyester obtained from 11 mols of decanedicarboxylic acid and 10 mols of~hexanediol (equivalent weight 1,415) and 2.6 g of an acid polyester obtained from 4 mols of hexahydrophthalic anhydride and 3 mols of neopentyl-glycol are warmed to 120C and, after adding 6.1 g of the epoxide compound of the following structure:
O
CH~ _ CHCH2CCCH2C~12 ~ J ~ ~ -',H2CH2COCH2CH~ o ~(~H2 CH~ - CHCH20CC~2Ch2 ~ ~
~ ~ ~ CH2CH2COCH2cH~ ~ H2 o .
lU5~ 7'~
(equivalent weight 123) and 0.01 g of dimethylbenzylamine, mixed well and cast, and cured, analogously to Example 1.
(Equivalent ratio = 1.0:0,2:1.2).
The mouldings have the following properties:
Tensile strength = 49 N/mm2 Elongation at break = 18%
Tm = 57C, Example 9 The procedure according to Example 8 is followed but with the difference that 1.2 equivalents of the triepoxide compound of the formula III are employed in place of 1.2 equivalents of the epoxide compound used in Example 8. The mouldings have the following characteristics:
Tensile strength = 30 N/mm Elongation at break = 320%
Resistance to tear propagation = 150 N
Tm = 49C
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the manufacture of crystalline, crosslinked, elastomeric epoxide resins, characterised in that epoxide com-pounds, containing two or more epoxide groups, are reacted a) with polyester-polycarboxylic acids A which essentially contain segments of the formula I
-[O-(CH2)n-0?CO-(CH2)m-CO]p- (I) in which n and m are identical or different and denote 2 or a higher number than 2, and to which the condition n ? m = 6 to 30 applies, and in which p denotes a number from 2 to 40 which, however, is sufficiently large that the segment contains at least 30 -CH2- groups, and b) with polyester-polycarboxylic acids B which essentially contain segments of the formula II
-[O-R1-O?CO-R2-CO]q- (II) in which R1 and R2 are identical or different and denote an alkylene radical with at least 2 C atoms in the chain and in which, per O bridge, an average of at least 3.5 and at most 30 C atoms, without taking into account the C atoms of the -CO?O- radicals, are present in the chain, and wherein the radicals R1 and R2 together contain at least one alkyl group or cycloalkyl group or one aryl group as a substituent for one H atom, and in which q denotes a number from 2 to 40,which,however, is sufficiently large that the segment contains at least 30 C atoms without taking into account the C atoms of the -CO?O- radicals, in the chain, and c) if appropriate, with curing agents C, and, if appropriate, in the presence of accelerators, in a ratio such that 0.5 to 1.2 equivalents of polyester-polycarboxylic acid are present per equivalent of epoxide compound, that 1/10 to 9/10 of these 0.5 to 1.2 equivalents are attributable to the polyester-polycarboxylic acid A and the remaining 9/10 to 1/10 to the polyester-polycarboxylic acid B, and that up to 0.6 equivalent of curing agent C is present per equivalent of epoxide compound, with the proviso that, in the cases in which only difunctional epoxide com-pounds and difunctional polyester-polycarboxylic acids A and B are employed, the epoxide groups must be present in excess and the reaction with a curing agent C is essential.
-[O-(CH2)n-0?CO-(CH2)m-CO]p- (I) in which n and m are identical or different and denote 2 or a higher number than 2, and to which the condition n ? m = 6 to 30 applies, and in which p denotes a number from 2 to 40 which, however, is sufficiently large that the segment contains at least 30 -CH2- groups, and b) with polyester-polycarboxylic acids B which essentially contain segments of the formula II
-[O-R1-O?CO-R2-CO]q- (II) in which R1 and R2 are identical or different and denote an alkylene radical with at least 2 C atoms in the chain and in which, per O bridge, an average of at least 3.5 and at most 30 C atoms, without taking into account the C atoms of the -CO?O- radicals, are present in the chain, and wherein the radicals R1 and R2 together contain at least one alkyl group or cycloalkyl group or one aryl group as a substituent for one H atom, and in which q denotes a number from 2 to 40,which,however, is sufficiently large that the segment contains at least 30 C atoms without taking into account the C atoms of the -CO?O- radicals, in the chain, and c) if appropriate, with curing agents C, and, if appropriate, in the presence of accelerators, in a ratio such that 0.5 to 1.2 equivalents of polyester-polycarboxylic acid are present per equivalent of epoxide compound, that 1/10 to 9/10 of these 0.5 to 1.2 equivalents are attributable to the polyester-polycarboxylic acid A and the remaining 9/10 to 1/10 to the polyester-polycarboxylic acid B, and that up to 0.6 equivalent of curing agent C is present per equivalent of epoxide compound, with the proviso that, in the cases in which only difunctional epoxide com-pounds and difunctional polyester-polycarboxylic acids A and B are employed, the epoxide groups must be present in excess and the reaction with a curing agent C is essential.
2. Process according to Claim 1, characterised in that the reactants are reacted in a ratio such that 0.7 to 1.2 equivalents of polyester-polycarboxylic acids are present per equivalent of epoxide compound.
3. Process according to Claim 1, characterised in that the reaction is carried out for 1 to 20 hours in the melt at temperatures between 50° and 200°C.
4. Process according to Claim 1, characterised in that a single epoxide compound is reacted.
5. Process according to Claim 1, characterised in that several epoxide compounds are reacted.
6. Process according to Claim 1, characterised in that the epoxide compounds employed are those of the group com-prising triglycidyl isocyanurate and triglycidyl compounds which contain one or more hydantoin groups and/or dihydrouracil groups.
7. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids B which are employed are those which contain, as R1 in formula II, the radical
8. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids B which are employed are those which contain, as R2 in formula II, a radical which is derived from a dimerised mono-unsaturated or di-unsaturated fatty acid.
9. Process according to Claim 1, characterised in that polyester-dicarboxylic acids are employed as polyester-polycarboxylic acids A and/or B.
10. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids A and/or B which are employed are those which contain at least 3 carboxyl groups.
11. Process according to Claim 1, characterised in that at least one adduct containing epoxide groups is manufactured, in a 1st stage, from the epoxide compounds and the polyester-polycarboxylic acids A and/or B; using 0.5 to 1 equivalent of polyester-polycarboxylic acid per 2 equivalents of epoxide compounds, and, in a second stage, is crosslinked with the remaining polyester-polycarboxylic acids and/or curing agents, optionally after the addition of further epoxide compounds,
12. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids A and/or B employed are polyester-dicarboxylic acids and the epoxide com-pounds employed are those containing at least 3 epoxide groups.
13. Process according to Claim 1, characterised in that the polyester-carboxylic acids A and/or B employed are those containing at least 3 carboxyl groups and the epoxide compounds employed are preferably diepoxide compounds.
14. Process according to Claim 12 or 13, characterised in that the reaction is carried out using a ratio such that approximately 1 equivalent of polyester-carboxylic acid is present per equivalent of epoxide compound and in that no curing agent C is employed,
15. Process according to Claim 12 or 13, characterised in that the reaction is carried out using an excess of epoxide groups, compared with the -CO.OH groups of the polyester-polycarboxylic acids, and that a curing agent is also used in an amount which is required for the crosslinking reaction of the excess epoxide groups,
16. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids A and B employed are poly-ester-dicarboxylic acids and the epoxide compounds employed are those containing 2 epoxide groups.
17. Process according to Claim 16, characterised in that the reaction is carried out in a single stage using a ratio such that approximately 0.6 to 0.9 equivalent of polyester-carboxylic acid is present per equivalent of epoxide compound and in that a carboxylic acid anhydride is used in an amount which is required for the crosslinking reaction of excess epoxide groups, as the curing agent.
18. Process according to Claim 16, characterised in that at least one adduct containing epoxide groups is manufactured, in a first stage, from the epoxide compounds and the polyester-polycarboxylic acids A and/or B, using 1 equivalent of polyester-polycarboxylic acid per 2 equivalents of epoxide compound, and, in a second stage, is crosslinked by reaction with customary curing agents.
19. Process according to Claim 1, characterised in that nucleating agents are added to the reaction mixture, before or during the reaction.
20. Process according to Claim 1, characterised in that fillers which assist the heat conductivity are added to the reaction mixture before or during the reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH5443/75 | 1975-04-28 | ||
| CH544375A CH595405A5 (en) | 1975-04-28 | 1975-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091377A true CA1091377A (en) | 1980-12-09 |
Family
ID=4293663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA251,053A Expired CA1091377A (en) | 1975-04-28 | 1976-04-26 | Process for the manufacture of crystalline, crosslinked, elastomeric epoxide resins |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5942686B2 (en) |
| CA (1) | CA1091377A (en) |
| CH (1) | CH595405A5 (en) |
| DE (1) | DE2618107A1 (en) |
| ES (1) | ES447354A1 (en) |
| FR (1) | FR2309578A1 (en) |
| GB (1) | GB1538534A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0042356A1 (en) * | 1980-06-13 | 1981-12-23 | Ciba-Geigy Ag | Use of partially crystalline polymers as insulating material for cryogenic applications |
| WO2022201985A1 (en) * | 2021-03-23 | 2022-09-29 | 三菱ケミカル株式会社 | Modified epoxy resin, manufacturing method therefor, curable resin composition, cured product thereof, coating material, and adhesive agent |
-
1975
- 1975-04-28 CH CH544375A patent/CH595405A5/xx not_active IP Right Cessation
-
1976
- 1976-04-26 CA CA251,053A patent/CA1091377A/en not_active Expired
- 1976-04-26 DE DE19762618107 patent/DE2618107A1/en not_active Withdrawn
- 1976-04-27 FR FR7612379A patent/FR2309578A1/en active Granted
- 1976-04-27 GB GB1693576A patent/GB1538534A/en not_active Expired
- 1976-04-27 ES ES447354A patent/ES447354A1/en not_active Expired
- 1976-04-28 JP JP4933476A patent/JPS5942686B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5942686B2 (en) | 1984-10-17 |
| FR2309578A1 (en) | 1976-11-26 |
| FR2309578B1 (en) | 1979-04-20 |
| ES447354A1 (en) | 1977-07-01 |
| JPS51131599A (en) | 1976-11-16 |
| CH595405A5 (en) | 1978-02-15 |
| DE2618107A1 (en) | 1976-11-11 |
| GB1538534A (en) | 1979-01-24 |
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