CA1090946A - Process for the manufacture of crystalline, crosslinked epoxide resins - Google Patents
Process for the manufacture of crystalline, crosslinked epoxide resinsInfo
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- CA1090946A CA1090946A CA251,030A CA251030A CA1090946A CA 1090946 A CA1090946 A CA 1090946A CA 251030 A CA251030 A CA 251030A CA 1090946 A CA1090946 A CA 1090946A
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- 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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Abstract
Abstract of the Disclosure The invention relates to the manufacture of crystalline epoxide resins which have at least two crystallite melt temperatures.
The cause of the crystallites are molecule blocks which arc derived from aliphatic polyesterpolycarboxylic acids. According to the invention, at least two aliphatic polyester-polycarboxylic acids (D and E), which bear a special relation to each other in respect of the number of -CH2 groups in the primary chain member.
are reacted under very specific quantitative conditions with epoxide compounds which contain at least 2 epoxide groups and optionally with curing agents. The synthetic resins thereby obtained are particularly suitable for use as storage material in latent heat accumulators.
The cause of the crystallites are molecule blocks which arc derived from aliphatic polyesterpolycarboxylic acids. According to the invention, at least two aliphatic polyester-polycarboxylic acids (D and E), which bear a special relation to each other in respect of the number of -CH2 groups in the primary chain member.
are reacted under very specific quantitative conditions with epoxide compounds which contain at least 2 epoxide groups and optionally with curing agents. The synthetic resins thereby obtained are particularly suitable for use as storage material in latent heat accumulators.
Description
1~ 09~
.
The invention relates to crystalline, crosslinked epoxide resins in which the crystallite-forming elements are essentially aliphatic polyester chains and which have at least two different crystallite melting points.
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 polyes-ter-polycarboxylic acid, are already known. In this connection, British Patents 1,164,~84 and 1,283,653 should be mentioned in particular. These products are crystalline synthetic resins which exhibit relatively high elongations a-t break below their crystallite melting point. If they are warmed to a temperature above the crystal]isation transition temperature, they then exhibit rubbery-elastic properties. In this rubbery-elastic state, their dimensional stability is too low for many appli-cations, for example as constructional materials. However, this means that these synthetic resins which have a low crystallite melting point (for example 20 to 50C) cannot be used for such applications at the customary average tempera-tures. If the synthetic resins have higher crystallite melt-ing points (for example of ~70C), their toughness rapidly decreases at room temperature. For this reason, synthetic resins of this type also are not very suitable for certain applications, for example as constructional materials or bui'ding materials.
.
The invention relates to crystalline, crosslinked epoxide resins in which the crystallite-forming elements are essentially aliphatic polyester chains and which have at least two different crystallite melting points.
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 polyes-ter-polycarboxylic acid, are already known. In this connection, British Patents 1,164,~84 and 1,283,653 should be mentioned in particular. These products are crystalline synthetic resins which exhibit relatively high elongations a-t break below their crystallite melting point. If they are warmed to a temperature above the crystal]isation transition temperature, they then exhibit rubbery-elastic properties. In this rubbery-elastic state, their dimensional stability is too low for many appli-cations, for example as constructional materials. However, this means that these synthetic resins which have a low crystallite melting point (for example 20 to 50C) cannot be used for such applications at the customary average tempera-tures. If the synthetic resins have higher crystallite melt-ing points (for example of ~70C), their toughness rapidly decreases at room temperature. For this reason, synthetic resins of this type also are not very suitable for certain applications, for example as constructional materials or bui'ding materials.
- 2 -10~0~
The object of the invention is to provide crystalline, crosslinked epoxide resins which do not exhibit this adverse behaviour of the plastics according to the prior art discussed above. They must, there~ore, have an adequate dimensional stability, and in particular be sufficientl.y tough and flexible,ov~ wide temperature ranges.
The subject of the invention is a process for the manufacture of crystalline, crosslinked epoxide resins, which is characterised in that epoxide compounds, containing two or more epoxide groups, are reacted a) with polyester-polycarboxylic acids D which essentially contain segments of the formula I
-[O-(CH2)n-o-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 con-tains at least 30 -CH2- groups, and b) with polyester-polycarboxylic acids E which essentially contain segments of the formula II
-[O~(CH2)s-o-co-(cH2)r-co~q- (II) in which s and r are identical or different and denote 2 or a higher number than 2, and to which the condition s + r + 2 c==n + m applies, and in which q represents a number from 6 to 30, which, however, is sufficiently large that the segment contains at least 30 -CH2- groups, and c) if appropriate~ with curing agents C, and, if appropriate, in the presence of accelerators, in a ratio such tha-t 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 poiyester-polycarboxylic acid D and `the remaining 9/10 to 1/10 to the polyester-polycarboxylic acid E, and that up to 0.6 equivalent of curing agent C is present per equivalent of epoxide co~pound, with the proviso that, in the cases in which only difunctional epoxide com-pounds and difunctional polyester-polycarboxylic acids D and E 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 = 8 to 24 applies in the formula I.
The epoxide resins obtained according to the invention are distingulshed by a feature which was previously not kno~n for synthetic resins. This is that they e~hibit several pronounced crystallite melting poin~ts,preferably two (Tml and Tm2j- Tml is in the range from 20 to 70C, preferably 25 to 60C, and Tm2 is in the range from 50 to 120C, preferably 50 to 100C. The crystallite-forming elements for Tml and Tm2 are the polyester-polycarboxylic acids D
and E employed in the manufacturing process. Sometimes, the particular crystallite melting point is split. This means that in such cases the crystallite melting point mani-fests itself as a two-stage melt'ng point.
It is surprising that when two polyester segments of similar structure are employed in crystalline~ crosslinked polymers, two different crystallites are formed and, even when the content of one component is relatively low, the melting point of this component is only slightly influenced.
Preferably, the procedure followed according to the invention is such that 0.7 to 1.2, especially O.9 to 1.1, equivalents of polyester-carboxylic acid are present per equivalent of epoxide compound.
The polyester-polycarboxylic acids D and E used in the reaction can for practical purposes be manufactured by the same basic process, by esterification of corresponding ali-phatic dialcohols and aliphatic dicarboxylic acids or by forming esters of 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 D and E are obtained. The use of the latter in the reaction according to the invention is also a preferred form of the invention. Branched polyester-polycarboxylic acids D and E which are obtained if small amounts of polycarboxylic acids, or their anhydrides, with at least 3 carboxyl groups (such as, for example, trimellitic acid) are also present ``" ~.0909' ~
during the manufac-ture of the polyester~polycarboxylic acids, are equally suitable for -the reaction according to the invention.
However, it is also possible to employ brancned pol-y-ester-polycarboxylic acids D and E, which are obtainable by esterification of the terminal OH groups of long-chain poly-ester-polyols, especial].y of polyester-diols, with poly-carboxylic acids ~hich contain at least 3 -CO.OH groups, such as, for example, trimellitic acid, or with corresponding anhydrides.
The basic rules for the manufacture of the polyester-polycarboxylic acids D and E used according to the present invention in other respects entirely correspond to those which have to be observed for the manufàcture 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 manu-facture of such long-chain, aliphatic polyester-polycarboxylic 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 D
are those based on the following polyalcohols and polycarboxy-lic acids:
11 mols of adipic acid - 10 mols of hexanediol 11 mols of sebacic acid - 10 mols of hexanediol ~ mols of decanedicarboxyllc acid - 4 mols of dodecanediol ~,0~309~'j 11 mols of dodecanedicarboxylic acid - 10 mols of butanediol 16 mols of adipic acid - 1~ mols of hexanediol 11 mols of dodecanedicarboxylic acid - 10 mols of hexanediol 11 mols of dodecanedicarboxylic acid - 10 mols of propane-1,3-diol 11 mols of dodecanedicarboxylic acid - 10 mols of dodecane-1,12-diol 5 mols of dodecanedicarboxylic acid - 4 mols of dodecane-1,12-dioî
11 mols of sebacic acid - 10 mols of butanediol 11 mols of sebacic acid - 10 mols of dodecanediol 5 mols of sebacic acid - 4 mols of dodecanediol Examples of suitable polyester-polycarboxylic acids are those based on the following polyalcohols and poly-carboxylic acids:
11 mols of sebacic acid - lO mols of hexanediol 11 mols of adipic acid - 10 mols of hexanediol 11 mols of succinic acid - 10 mols of butanediol 17 mols of succinic acid - 14 mols of butanediol 21 mols of succinic acid - 20 mols of butanediol 22 mols of succinic acid - 21 mols of butanediol Glycerol - succinic acid - butanediol (1:24:21) Trimethylolpropane - succinic acid - butanediol (1:30:27) Glycerol - succinic acid - butanediol (1:17:14) Glycerol - succinic acid - butanediol (1:30:27) 31 mols of succinic acid - 30 mols of butanediol 16 mols of adipic acid - 15 mols of hexanediol 11 mols of sebacic acid - 10 mols of butanediol 1030~
11 mols of dodecanedicarboxylic acid - 10 mols of propanediol 7 mols of dodecanedicarboxylic acid - 6 mols of propanedlol 7 mols of dodecanedicarboxylic acid - 6 mols of butanediol 5 mols of sebacic acid - 5 mols of hexanediol In principle, it is also possible~ according to the invention, to use a procedure such that the reaction is allowed to proceed in the presence of at least one further aliphatic polyester-polycarboxylic acid, which although it is similar to the polyester-polycarboxylic acids D and E differs from these in respect of structure and molecular weight.
This results in the development of at least one further (third) crystallite melting point in the end product.
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
C~l CH
O ~3 ~ ~ - CH3 /
C~2 CH-C~12-N~N-CH2-C~-C~12-N~Y-CH2-CH--CH2 ~
~ 2 (III) CH . .
I ~O
C~12 - . . . . .
iO'~ ~3 are particularly suitable.
In principle, the reaction according to the invention 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 D,and E are employed, it is possible, for example 5 to carry out the reaction in 1 stage, that is to say to start from a reaction mixture ~hich contains all the reactants simul-taneously. 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 D and E which have at least 3 carboxyl groups are employed. In the converse case~ that is to say when using polyester-polycarboxylic acids D and E containing at least ~ carboxyl groups, and using diepoxy compounds, working in 1 stage is again possible and is the normal method of react on for such cases.
If only diepoxide compounds and only polyester-dicarboxylic,acids are employed, it is only possible to work in one stage if an excess of epoxide compounds is 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 D and/or E, preferably using 0.5 to 1 equivalent of polyester-polycarboxylic acid per 2 equivalents of epoxide compounds. In a second reac-tion stage, the crosslinking is then carried out 9 by reaction of the adducts wi+h the ~o9o~
remainder of the polyester-polycarboxyllc acids D and/or E.
It is also possible to proceed by carrying out the cross-linking in 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 ~or epoxide resins it is, according to the invention, possible to employ all the sub-stances 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, polycarboxylic acids and their anhydrides, acid amides, polyesters, phenol-formaldehyde con-densates and amino-resin precondensates. Tertiary amines and imidazoles may be mentioned as examples of suitable accelerators.
The reaction according to the inven-tion is preferably carried out in the melt. For this, preferably temperatures 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 according to the invention, a blowing agent for the manufacture of ~oams can also be added. -' The crystalline, crosslinked plastic products are asa rule manufactured according to the invention with si,mul-~ 0~3~ ~
taneous shaping, to give castings, foamed articles, pressings,lacquer films, laminates, adhesive bonds, granules and the like.
Of course, other customary additives, such as fillers, reinforcing agents, mould release agents, agents to protect 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 conduct-ivity can sometimes 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 accelera-ted development of the crystal structure of the polymers it is also advisable to add nucleat~ing agents, such as phthalocyanines, carbon black, ~-naphthoic acid or the like.
Because of their good properties, which have already been mentioned above, and especially because of the out-standing toughness over a wide temperature range, the epoxide resins which can be manufactured according to the invention are particularly suitable as constructional materials fortechn~l 10909~>
applications It is surprising that the good properties which are exhibited by these synthetic resins below the lower crystallite melting point (Tml) are retained even at higher temperatures, that is to say above Tml. In contrast, after the crystallite melting point has been exceeded, the synthetic resins of the state of the art, which have been discussed above, change into the state of a valueless "limp"
rubber, which precludes their use as a constructional material. It mustalso be emphasisedthattheadvantageous properties exhibited above Tml by the products manufactured according to the invention can be further improved by employing those polyester-polycarboxylic acids E which result in a particularly high T~2.
A controlled variation of the toughness and the flexibility can be realised in this way.
The epoxide resins which can be manufactured according to the invention also exhibit a further special characteristic.
This is that, below the two crystallite melting points they are distinguished by a particularly advantageous resilience of about 70%. They are therefore suitable for the manufacture of golf balls and the like.
One use of the crystalline, crosslinked epoxide resins manufactured according to the invention is as a storage material i~ so-called latent heat stores. As is kno~n, those installations in which the phenomenon of the absorption and re-release of latent heat during melting or crystallisation of bodies or during boiling or condensation of liquids is utilised for the storage of heat energy are termed latent ~.~90'3"~
heat accumulator3.
For latent heat accum~rs,in ~hkhthe heat of fusion is stored, it has hitherto been primarily salt solutions and salt mixtures which are used as the storage medium. How-ever, when salt solutions and salt melts are used there are always severe corrosion problems. For this reason, it is predominant]y corrosion-resistant metal containers which are used to contain the salts, but these containers are heavy and conduct heat well; this is a disadvantage, quite apart from the fact that such containers make the total installations expensive. Furthermore, fractures and leaks of the salt containers and pipes must always be expected, and this results in extremely undesirable exudation of the solutions or melts.
The literature states that practically any desired melting point can be obtained by appropriate choice of the salt or by mixing different salts. In reality, however, the situation is no-t quite so favourable, because if a salt mixture ~hich does not correspond to a eutectic composition is chosen, demixing phenomena always occur when the melt solidifies. Only purely eutectic mixtures crystallise in a constant composition. They are, therefore, for practical purposes the only storage material used a-t the present time. However, eutectic melts have a great tendency to supercooling and must therefore be seeded. m is in turn, however, has the consequence that here again demixing phenomena gradually manifest themselves. It is not poss-ihle to rea-iseS by continuous progression, any desired meit 109(1~
temperature by choosing eutec-tic salt mixtures, if only because the number of eutectics is limited. Furthermore, some eutectic melt temperatures can only be obtained by choosing unusual expensive sal-ts, which a priori precludes the practical realisation of such eutectics.
l~hen the crystalline, crosslinked epoxide resins manufactured according to the invention are used as the storage material in latent heat accumulators none of these disad-vantageous properties and phenomena of the kno~n storage materials arise and the melting point of the particular storage material can be varied in a controlled manner. To this extent, the present invention represents a very particular enrichment of the art.
The crystalline, crosslinked epoxide resins manu-factured according to the invention are of particular interest . ~ .
as heat rectifiers, in which the enthalpy of fusion of the polyester segment which has the lower melting point is used ~or storage, that is to say for heat insulation and subsequent release of heat, and -the crystallites which have -the higher melting point are used to maintain the mechanical strength.
The invention also relates to the crys-talline, cross-linked epoxide resins which can be manufactured by the process according to the invention, especially those resins which have a lower crystallite melting point in the range from 20 to ~0C and an upper crystallite melting point in the range from 50 to 120C.
1090.'34~
Example 1 108 g (0.1 equivalent) of an acid polyester, prepared from 11 mols of adipic acid and 10 mols of hexanediol and 155 g of an acid polyester prepared from 11 mols of sebacic acid and 10 mols of hexanediol (both prepared by the melt process) are warmed to 100C and mixed well with 22 g (0.2 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 pre--treated with a silicone mould-release agent and have been pre-warmed to 120C. The mixture is cured for 16 hours at 140C. Crystalline, tough mouldings with the following properties are obtained:
Tensile strength according to 2 VSM 77,101 (moulding No. 1)~ = 18 N/mm Elongatior. at break = 520%
Crystallite melting point Tml~ = 27C
Crystallite melting point Tm2 = 50C
The mouldings are punched from -the 1 mm thick sheet using a punching tool. The tensile -test also corresponds to ~ Determined with a differential scanning calorimeter (heat--ing rate = 10C/minute).
The sheet has two melting points which are ascribed to the two polyesters used. Above the melting points, the moulding is soft and rubbery-elastic.
~a~ple ?
a) 252 g (0.1 equivalen-t) of an adduct of 2.0 equivalents 1090~3'1~
of tetral~ydrophthalic acid di.glycidyl ester and 1.0 equivalent of an aeid polyester obtained from 21 mols of succinic an-hydride and 20 mols of butanediol are warmed, together with 16.0 g of hexahydropht;halic acid diglycidyl ester, to 120C
and mixed well with 108 g (0.1 equivalent) of an adipic acid -hexanediol polyester (11:10) and 26.6 g of dodecenylsuccinic anhydride (0.1 mol), the system is evacuated and the mixture is poured into the moulds according to Example 1.
After curi.ng for 16 hours a-t 140C, crystalline, tough mould-ings with the following characteristics are obtained:
Tml : 45C
Tm2 : 102C
b) When the same molar amounts of hexahydrophthalic a~hydride are used in place of dodecenylsuccinic anhydride and the composition and processing are otherwise identical to those in Example 2a 5 mouldings with the following character-isties are obtained:
Tml : 40C
Tm2 : 101C
Example_3 140 g (0.9 equivalent) ofan 11:10 sebacic acid/hexane-diol polyester and 15.4 g (0.01 equivalent) of an acid (21:20) suecinie aeid/butanediol polyester are warmed to 120C and mixed well with 11 g (0.1 equivalent) of triglyeidyl isoeyan-urate and the mixture is proeessed analogously to Example 1.
The resulting mouldings had the following characteristics:
Tml : 58CC
Tm2 : 100C.
~o~o9~;
In accordance with the relatively small amount of succinic acid-butanediol polyester, the peak for the melting point at 100C, in the DSC, was only small compared with that of the sebacic acid polyester at 58C.
Example 4 0.1 equivalent of an acid polyester obtained from 11 mols of adipic acid and 10 rnols of hexanediol (equivalent weight = 1,080), 0.1 equivalent of a branched acid polyester obtained from 17 mols of succinic acid, 14 mols of butane-1,4-diol and 1 mol of glycerol (equivalent weight = 1,460) and 0.2 equivalent of a hexahydrophthalic acid diglycidyl ester with an epoxide equivalent weight of 160 are warmed and mixed well. After adding 0.3% = 0.9 g of l-methylimidazole, -the mixtureis evacuated and poured into aluminium tubes. After heating to 140 for 16 hours, crystalline, crosslinked mould-ings with the following characteristics are obtained:
Tml = 34 and 43 C (that is a two-stage melting point) Tm2 = 85C.
Example 5 The procedure is as in Example 4, but with the differ-ence that 0.2 equivalent of the triepoxide compound of the formula III with an equivalent weight of 167 are employed in place of hexahydrophthalic acid diglycidyl ester and that, in addition, 40 g of aluminium powder and 0.6 g of ~-Cu phthalo cyanine blue are added to the melt as a nucleating agen-t and dyestuff respectively. Very tough, blue mouldings with the follo~ring crystallite melting points are obtained:
~0 Tml = 38C
Tm2 ~ 76C
Example 6 When 3 g of a-naphthoic acid are used in place of 0,6 g of ~-Cu phthalocyanine blue and otherwlse the composition and processing are identical to those in Exampl.e 5, mouldings with the following characteristics are obtained:
Tml = 40C
Tm2 = 75C
Example ?
. Three layers of a glass mat are laid in an Anticorodalmould, which has internal dimensions of 8 x 200 x 200 mm and has been treated with a silicone mould--release agent, and a.re impregnated hot with the resin mixture described in Example 5, but without aluminium powder and ~-Cu phthalocyanine blue.
After evacuating the system for a short time, the mixture is cured at 140C for 16 hours. A soft, flexible but extremely tough laminate which has the following characteristics is obtained:
Tml = 37 and 48C (two-stage melting point) Tm2 = 79C.
Example 8 ~ .62 g (= 0.005 equivalent) of an adduct of 2 mols of hexahydrophthalic acid diglycidyl ester and 1 mol of an acid polyester obtained from 11 mols of sebacic acid and 10 mols of ~ hexanediol and 13.15 g (= 0.005 equivalent) of an adduct of 2.2 mols of -tetrahydrophthal~c acid diglycidyl est.er and l.Q mol iO90~3~ti of an acid polyester obtained from 22 mols of succi.nic anhydride and 21 mols of butane-1,4-diol and also 1.54 g (= 0.01 mol) of hexahydrophthalic anhydride are mixed well whilst hot (about 130C) and, after adding 0.07 g of l-methyl-imidazole, the mixture is poured into tubes and cured for 16 hours at 140C. The mouldings are very tough and have the following crystallite mel-ting points:
Tml = 52C
Tm2 = 84C.
Example 9 8.32 g of an acid polyester ob-tained from 5 mols of decanedicarboxylic acid and 4 mols of dodecanediol (equivalent weight = 832) and 10.8 g (= 0.01 equivalent) of the adipic acid - hexanediol polyester used in Example 1 and 3.~ g (= 0.02 equivalent) of the triepoxide compound used in Example 5 are mixed well at 120C and, after adding 0.07 g of l-methyl-imidazole, the system is evacuated and the mixture is poured into an aluminium tube. Again, opaque, tough mouldings, which have the following crystallite melting points, are obtained:
Tml = 49C
Tm2 = 54C
xample 10 9.62 g (= 0.005 equivalent) of the sebacic acid -hexanediol polyester adduct described in Example 8 and 1~.5 g (= 0.005 equivalent) of the succinic acid - butanediol poly-ester adduct, which is also described in Example 8, and also ~9 0~3~ ~ .
5.4 g (= 0.005 e~uivalent) of an (11:10) adi ic acid - hexane~
diol polyester and 0.8 g (=0~005 equivalent) o~ hexahydro-phthalic anhydride and 0.09 g of l-methylimidazole are mixed at 130C and the mixture is poured into an aluminium tube.
After curing for 16 hours at 140, mouldings with -the follo~ing crystallite melting points are obtained:
Tml = 37 Tm2 = 52 Tm~ = 76 m e three melting points show that, even in crosslinked polymers, each polyester aggregates on its o~m to form crystallites.
The object of the invention is to provide crystalline, crosslinked epoxide resins which do not exhibit this adverse behaviour of the plastics according to the prior art discussed above. They must, there~ore, have an adequate dimensional stability, and in particular be sufficientl.y tough and flexible,ov~ wide temperature ranges.
The subject of the invention is a process for the manufacture of crystalline, crosslinked epoxide resins, which is characterised in that epoxide compounds, containing two or more epoxide groups, are reacted a) with polyester-polycarboxylic acids D which essentially contain segments of the formula I
-[O-(CH2)n-o-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 con-tains at least 30 -CH2- groups, and b) with polyester-polycarboxylic acids E which essentially contain segments of the formula II
-[O~(CH2)s-o-co-(cH2)r-co~q- (II) in which s and r are identical or different and denote 2 or a higher number than 2, and to which the condition s + r + 2 c==n + m applies, and in which q represents a number from 6 to 30, which, however, is sufficiently large that the segment contains at least 30 -CH2- groups, and c) if appropriate~ with curing agents C, and, if appropriate, in the presence of accelerators, in a ratio such tha-t 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 poiyester-polycarboxylic acid D and `the remaining 9/10 to 1/10 to the polyester-polycarboxylic acid E, and that up to 0.6 equivalent of curing agent C is present per equivalent of epoxide co~pound, with the proviso that, in the cases in which only difunctional epoxide com-pounds and difunctional polyester-polycarboxylic acids D and E 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 = 8 to 24 applies in the formula I.
The epoxide resins obtained according to the invention are distingulshed by a feature which was previously not kno~n for synthetic resins. This is that they e~hibit several pronounced crystallite melting poin~ts,preferably two (Tml and Tm2j- Tml is in the range from 20 to 70C, preferably 25 to 60C, and Tm2 is in the range from 50 to 120C, preferably 50 to 100C. The crystallite-forming elements for Tml and Tm2 are the polyester-polycarboxylic acids D
and E employed in the manufacturing process. Sometimes, the particular crystallite melting point is split. This means that in such cases the crystallite melting point mani-fests itself as a two-stage melt'ng point.
It is surprising that when two polyester segments of similar structure are employed in crystalline~ crosslinked polymers, two different crystallites are formed and, even when the content of one component is relatively low, the melting point of this component is only slightly influenced.
Preferably, the procedure followed according to the invention is such that 0.7 to 1.2, especially O.9 to 1.1, equivalents of polyester-carboxylic acid are present per equivalent of epoxide compound.
The polyester-polycarboxylic acids D and E used in the reaction can for practical purposes be manufactured by the same basic process, by esterification of corresponding ali-phatic dialcohols and aliphatic dicarboxylic acids or by forming esters of 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 D and E are obtained. The use of the latter in the reaction according to the invention is also a preferred form of the invention. Branched polyester-polycarboxylic acids D and E which are obtained if small amounts of polycarboxylic acids, or their anhydrides, with at least 3 carboxyl groups (such as, for example, trimellitic acid) are also present ``" ~.0909' ~
during the manufac-ture of the polyester~polycarboxylic acids, are equally suitable for -the reaction according to the invention.
However, it is also possible to employ brancned pol-y-ester-polycarboxylic acids D and E, which are obtainable by esterification of the terminal OH groups of long-chain poly-ester-polyols, especial].y of polyester-diols, with poly-carboxylic acids ~hich contain at least 3 -CO.OH groups, such as, for example, trimellitic acid, or with corresponding anhydrides.
The basic rules for the manufacture of the polyester-polycarboxylic acids D and E used according to the present invention in other respects entirely correspond to those which have to be observed for the manufàcture 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 manu-facture of such long-chain, aliphatic polyester-polycarboxylic 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 D
are those based on the following polyalcohols and polycarboxy-lic acids:
11 mols of adipic acid - 10 mols of hexanediol 11 mols of sebacic acid - 10 mols of hexanediol ~ mols of decanedicarboxyllc acid - 4 mols of dodecanediol ~,0~309~'j 11 mols of dodecanedicarboxylic acid - 10 mols of butanediol 16 mols of adipic acid - 1~ mols of hexanediol 11 mols of dodecanedicarboxylic acid - 10 mols of hexanediol 11 mols of dodecanedicarboxylic acid - 10 mols of propane-1,3-diol 11 mols of dodecanedicarboxylic acid - 10 mols of dodecane-1,12-diol 5 mols of dodecanedicarboxylic acid - 4 mols of dodecane-1,12-dioî
11 mols of sebacic acid - 10 mols of butanediol 11 mols of sebacic acid - 10 mols of dodecanediol 5 mols of sebacic acid - 4 mols of dodecanediol Examples of suitable polyester-polycarboxylic acids are those based on the following polyalcohols and poly-carboxylic acids:
11 mols of sebacic acid - lO mols of hexanediol 11 mols of adipic acid - 10 mols of hexanediol 11 mols of succinic acid - 10 mols of butanediol 17 mols of succinic acid - 14 mols of butanediol 21 mols of succinic acid - 20 mols of butanediol 22 mols of succinic acid - 21 mols of butanediol Glycerol - succinic acid - butanediol (1:24:21) Trimethylolpropane - succinic acid - butanediol (1:30:27) Glycerol - succinic acid - butanediol (1:17:14) Glycerol - succinic acid - butanediol (1:30:27) 31 mols of succinic acid - 30 mols of butanediol 16 mols of adipic acid - 15 mols of hexanediol 11 mols of sebacic acid - 10 mols of butanediol 1030~
11 mols of dodecanedicarboxylic acid - 10 mols of propanediol 7 mols of dodecanedicarboxylic acid - 6 mols of propanedlol 7 mols of dodecanedicarboxylic acid - 6 mols of butanediol 5 mols of sebacic acid - 5 mols of hexanediol In principle, it is also possible~ according to the invention, to use a procedure such that the reaction is allowed to proceed in the presence of at least one further aliphatic polyester-polycarboxylic acid, which although it is similar to the polyester-polycarboxylic acids D and E differs from these in respect of structure and molecular weight.
This results in the development of at least one further (third) crystallite melting point in the end product.
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
C~l CH
O ~3 ~ ~ - CH3 /
C~2 CH-C~12-N~N-CH2-C~-C~12-N~Y-CH2-CH--CH2 ~
~ 2 (III) CH . .
I ~O
C~12 - . . . . .
iO'~ ~3 are particularly suitable.
In principle, the reaction according to the invention 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 D,and E are employed, it is possible, for example 5 to carry out the reaction in 1 stage, that is to say to start from a reaction mixture ~hich contains all the reactants simul-taneously. 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 D and E which have at least 3 carboxyl groups are employed. In the converse case~ that is to say when using polyester-polycarboxylic acids D and E containing at least ~ carboxyl groups, and using diepoxy compounds, working in 1 stage is again possible and is the normal method of react on for such cases.
If only diepoxide compounds and only polyester-dicarboxylic,acids are employed, it is only possible to work in one stage if an excess of epoxide compounds is 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 D and/or E, preferably using 0.5 to 1 equivalent of polyester-polycarboxylic acid per 2 equivalents of epoxide compounds. In a second reac-tion stage, the crosslinking is then carried out 9 by reaction of the adducts wi+h the ~o9o~
remainder of the polyester-polycarboxyllc acids D and/or E.
It is also possible to proceed by carrying out the cross-linking in 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 ~or epoxide resins it is, according to the invention, possible to employ all the sub-stances 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, polycarboxylic acids and their anhydrides, acid amides, polyesters, phenol-formaldehyde con-densates and amino-resin precondensates. Tertiary amines and imidazoles may be mentioned as examples of suitable accelerators.
The reaction according to the inven-tion is preferably carried out in the melt. For this, preferably temperatures 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 according to the invention, a blowing agent for the manufacture of ~oams can also be added. -' The crystalline, crosslinked plastic products are asa rule manufactured according to the invention with si,mul-~ 0~3~ ~
taneous shaping, to give castings, foamed articles, pressings,lacquer films, laminates, adhesive bonds, granules and the like.
Of course, other customary additives, such as fillers, reinforcing agents, mould release agents, agents to protect 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 conduct-ivity can sometimes 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 accelera-ted development of the crystal structure of the polymers it is also advisable to add nucleat~ing agents, such as phthalocyanines, carbon black, ~-naphthoic acid or the like.
Because of their good properties, which have already been mentioned above, and especially because of the out-standing toughness over a wide temperature range, the epoxide resins which can be manufactured according to the invention are particularly suitable as constructional materials fortechn~l 10909~>
applications It is surprising that the good properties which are exhibited by these synthetic resins below the lower crystallite melting point (Tml) are retained even at higher temperatures, that is to say above Tml. In contrast, after the crystallite melting point has been exceeded, the synthetic resins of the state of the art, which have been discussed above, change into the state of a valueless "limp"
rubber, which precludes their use as a constructional material. It mustalso be emphasisedthattheadvantageous properties exhibited above Tml by the products manufactured according to the invention can be further improved by employing those polyester-polycarboxylic acids E which result in a particularly high T~2.
A controlled variation of the toughness and the flexibility can be realised in this way.
The epoxide resins which can be manufactured according to the invention also exhibit a further special characteristic.
This is that, below the two crystallite melting points they are distinguished by a particularly advantageous resilience of about 70%. They are therefore suitable for the manufacture of golf balls and the like.
One use of the crystalline, crosslinked epoxide resins manufactured according to the invention is as a storage material i~ so-called latent heat stores. As is kno~n, those installations in which the phenomenon of the absorption and re-release of latent heat during melting or crystallisation of bodies or during boiling or condensation of liquids is utilised for the storage of heat energy are termed latent ~.~90'3"~
heat accumulator3.
For latent heat accum~rs,in ~hkhthe heat of fusion is stored, it has hitherto been primarily salt solutions and salt mixtures which are used as the storage medium. How-ever, when salt solutions and salt melts are used there are always severe corrosion problems. For this reason, it is predominant]y corrosion-resistant metal containers which are used to contain the salts, but these containers are heavy and conduct heat well; this is a disadvantage, quite apart from the fact that such containers make the total installations expensive. Furthermore, fractures and leaks of the salt containers and pipes must always be expected, and this results in extremely undesirable exudation of the solutions or melts.
The literature states that practically any desired melting point can be obtained by appropriate choice of the salt or by mixing different salts. In reality, however, the situation is no-t quite so favourable, because if a salt mixture ~hich does not correspond to a eutectic composition is chosen, demixing phenomena always occur when the melt solidifies. Only purely eutectic mixtures crystallise in a constant composition. They are, therefore, for practical purposes the only storage material used a-t the present time. However, eutectic melts have a great tendency to supercooling and must therefore be seeded. m is in turn, however, has the consequence that here again demixing phenomena gradually manifest themselves. It is not poss-ihle to rea-iseS by continuous progression, any desired meit 109(1~
temperature by choosing eutec-tic salt mixtures, if only because the number of eutectics is limited. Furthermore, some eutectic melt temperatures can only be obtained by choosing unusual expensive sal-ts, which a priori precludes the practical realisation of such eutectics.
l~hen the crystalline, crosslinked epoxide resins manufactured according to the invention are used as the storage material in latent heat accumulators none of these disad-vantageous properties and phenomena of the kno~n storage materials arise and the melting point of the particular storage material can be varied in a controlled manner. To this extent, the present invention represents a very particular enrichment of the art.
The crystalline, crosslinked epoxide resins manu-factured according to the invention are of particular interest . ~ .
as heat rectifiers, in which the enthalpy of fusion of the polyester segment which has the lower melting point is used ~or storage, that is to say for heat insulation and subsequent release of heat, and -the crystallites which have -the higher melting point are used to maintain the mechanical strength.
The invention also relates to the crys-talline, cross-linked epoxide resins which can be manufactured by the process according to the invention, especially those resins which have a lower crystallite melting point in the range from 20 to ~0C and an upper crystallite melting point in the range from 50 to 120C.
1090.'34~
Example 1 108 g (0.1 equivalent) of an acid polyester, prepared from 11 mols of adipic acid and 10 mols of hexanediol and 155 g of an acid polyester prepared from 11 mols of sebacic acid and 10 mols of hexanediol (both prepared by the melt process) are warmed to 100C and mixed well with 22 g (0.2 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 pre--treated with a silicone mould-release agent and have been pre-warmed to 120C. The mixture is cured for 16 hours at 140C. Crystalline, tough mouldings with the following properties are obtained:
Tensile strength according to 2 VSM 77,101 (moulding No. 1)~ = 18 N/mm Elongatior. at break = 520%
Crystallite melting point Tml~ = 27C
Crystallite melting point Tm2 = 50C
The mouldings are punched from -the 1 mm thick sheet using a punching tool. The tensile -test also corresponds to ~ Determined with a differential scanning calorimeter (heat--ing rate = 10C/minute).
The sheet has two melting points which are ascribed to the two polyesters used. Above the melting points, the moulding is soft and rubbery-elastic.
~a~ple ?
a) 252 g (0.1 equivalen-t) of an adduct of 2.0 equivalents 1090~3'1~
of tetral~ydrophthalic acid di.glycidyl ester and 1.0 equivalent of an aeid polyester obtained from 21 mols of succinic an-hydride and 20 mols of butanediol are warmed, together with 16.0 g of hexahydropht;halic acid diglycidyl ester, to 120C
and mixed well with 108 g (0.1 equivalent) of an adipic acid -hexanediol polyester (11:10) and 26.6 g of dodecenylsuccinic anhydride (0.1 mol), the system is evacuated and the mixture is poured into the moulds according to Example 1.
After curi.ng for 16 hours a-t 140C, crystalline, tough mould-ings with the following characteristics are obtained:
Tml : 45C
Tm2 : 102C
b) When the same molar amounts of hexahydrophthalic a~hydride are used in place of dodecenylsuccinic anhydride and the composition and processing are otherwise identical to those in Example 2a 5 mouldings with the following character-isties are obtained:
Tml : 40C
Tm2 : 101C
Example_3 140 g (0.9 equivalent) ofan 11:10 sebacic acid/hexane-diol polyester and 15.4 g (0.01 equivalent) of an acid (21:20) suecinie aeid/butanediol polyester are warmed to 120C and mixed well with 11 g (0.1 equivalent) of triglyeidyl isoeyan-urate and the mixture is proeessed analogously to Example 1.
The resulting mouldings had the following characteristics:
Tml : 58CC
Tm2 : 100C.
~o~o9~;
In accordance with the relatively small amount of succinic acid-butanediol polyester, the peak for the melting point at 100C, in the DSC, was only small compared with that of the sebacic acid polyester at 58C.
Example 4 0.1 equivalent of an acid polyester obtained from 11 mols of adipic acid and 10 rnols of hexanediol (equivalent weight = 1,080), 0.1 equivalent of a branched acid polyester obtained from 17 mols of succinic acid, 14 mols of butane-1,4-diol and 1 mol of glycerol (equivalent weight = 1,460) and 0.2 equivalent of a hexahydrophthalic acid diglycidyl ester with an epoxide equivalent weight of 160 are warmed and mixed well. After adding 0.3% = 0.9 g of l-methylimidazole, -the mixtureis evacuated and poured into aluminium tubes. After heating to 140 for 16 hours, crystalline, crosslinked mould-ings with the following characteristics are obtained:
Tml = 34 and 43 C (that is a two-stage melting point) Tm2 = 85C.
Example 5 The procedure is as in Example 4, but with the differ-ence that 0.2 equivalent of the triepoxide compound of the formula III with an equivalent weight of 167 are employed in place of hexahydrophthalic acid diglycidyl ester and that, in addition, 40 g of aluminium powder and 0.6 g of ~-Cu phthalo cyanine blue are added to the melt as a nucleating agen-t and dyestuff respectively. Very tough, blue mouldings with the follo~ring crystallite melting points are obtained:
~0 Tml = 38C
Tm2 ~ 76C
Example 6 When 3 g of a-naphthoic acid are used in place of 0,6 g of ~-Cu phthalocyanine blue and otherwlse the composition and processing are identical to those in Exampl.e 5, mouldings with the following characteristics are obtained:
Tml = 40C
Tm2 = 75C
Example ?
. Three layers of a glass mat are laid in an Anticorodalmould, which has internal dimensions of 8 x 200 x 200 mm and has been treated with a silicone mould--release agent, and a.re impregnated hot with the resin mixture described in Example 5, but without aluminium powder and ~-Cu phthalocyanine blue.
After evacuating the system for a short time, the mixture is cured at 140C for 16 hours. A soft, flexible but extremely tough laminate which has the following characteristics is obtained:
Tml = 37 and 48C (two-stage melting point) Tm2 = 79C.
Example 8 ~ .62 g (= 0.005 equivalent) of an adduct of 2 mols of hexahydrophthalic acid diglycidyl ester and 1 mol of an acid polyester obtained from 11 mols of sebacic acid and 10 mols of ~ hexanediol and 13.15 g (= 0.005 equivalent) of an adduct of 2.2 mols of -tetrahydrophthal~c acid diglycidyl est.er and l.Q mol iO90~3~ti of an acid polyester obtained from 22 mols of succi.nic anhydride and 21 mols of butane-1,4-diol and also 1.54 g (= 0.01 mol) of hexahydrophthalic anhydride are mixed well whilst hot (about 130C) and, after adding 0.07 g of l-methyl-imidazole, the mixture is poured into tubes and cured for 16 hours at 140C. The mouldings are very tough and have the following crystallite mel-ting points:
Tml = 52C
Tm2 = 84C.
Example 9 8.32 g of an acid polyester ob-tained from 5 mols of decanedicarboxylic acid and 4 mols of dodecanediol (equivalent weight = 832) and 10.8 g (= 0.01 equivalent) of the adipic acid - hexanediol polyester used in Example 1 and 3.~ g (= 0.02 equivalent) of the triepoxide compound used in Example 5 are mixed well at 120C and, after adding 0.07 g of l-methyl-imidazole, the system is evacuated and the mixture is poured into an aluminium tube. Again, opaque, tough mouldings, which have the following crystallite melting points, are obtained:
Tml = 49C
Tm2 = 54C
xample 10 9.62 g (= 0.005 equivalent) of the sebacic acid -hexanediol polyester adduct described in Example 8 and 1~.5 g (= 0.005 equivalent) of the succinic acid - butanediol poly-ester adduct, which is also described in Example 8, and also ~9 0~3~ ~ .
5.4 g (= 0.005 e~uivalent) of an (11:10) adi ic acid - hexane~
diol polyester and 0.8 g (=0~005 equivalent) o~ hexahydro-phthalic anhydride and 0.09 g of l-methylimidazole are mixed at 130C and the mixture is poured into an aluminium tube.
After curing for 16 hours at 140, mouldings with -the follo~ing crystallite melting points are obtained:
Tml = 37 Tm2 = 52 Tm~ = 76 m e three melting points show that, even in crosslinked polymers, each polyester aggregates on its o~m to form crystallites.
Claims (22)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the manufacture of crystalline, cross-linked epoxide resins, characterised in that epoxide com-pounds, containing two or more epoxide groups, are reacted a) with polyester-polycarboxylic acids D which essentially contain segments of the formula I
-[O-(CH2)n-O?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 E which essentially contain segments of the formula II
-[O-(CH2)s-O?CO-(CH2)r-CO]q- (II) in which s and r are identical or different and denote 2 or a higher number than 2, and to which the condition s + r + 2 ? n + m applies, and in which q denotes a num-ber from 6 to 30, which, however, is sufficiently large that the segment contains at least 30 -CH2- groups, and c) if appropriate, with curing agents C, and, if appro-priate, 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 equiva-lents are attributable to the polyester-polycarboxylic acid D and the remaining 9/10 to 1/10 to the polyester-poly-carboxylic acid E, 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 compounds and difunctional polyester-polycarboxy-lic acids D and E are employed, the epoxide groups must be present in excess and the reaction with a curing agent C is essential.
-[O-(CH2)n-O?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 E which essentially contain segments of the formula II
-[O-(CH2)s-O?CO-(CH2)r-CO]q- (II) in which s and r are identical or different and denote 2 or a higher number than 2, and to which the condition s + r + 2 ? n + m applies, and in which q denotes a num-ber from 6 to 30, which, however, is sufficiently large that the segment contains at least 30 -CH2- groups, and c) if appropriate, with curing agents C, and, if appro-priate, 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 equiva-lents are attributable to the polyester-polycarboxylic acid D and the remaining 9/10 to 1/10 to the polyester-poly-carboxylic acid E, 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 compounds and difunctional polyester-polycarboxy-lic acids D and E 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 dihydro-uracil groups.
7. Process according to Claim 1, characterised in that polyester-dicarboxylic acids D and E are employed.
8. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids D and E which are em-ployed are those which contain at least 3 carboxyl groups.
9. Process according to Claim 1, characterised in that at least one adduct containing epoxide groups is manufac-tured, in a 1st stage, from the epoxide compounds and the polyester-polycarboxylic acids D and E using 0.5 to 1 equi-valent of polyester-polycarboxylic acid per 2 equivalents of epoxide compounds, and, in a second stage, is crosslin-ked with the remaining polyester-polycarboxylic acids and/or curing agents, optionally after the addition of further epoxide compounds.
10. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids D and E employed are polyester- dicarboxylic acids and the epoxide compounds employed are those containing at least 3 epoxide groups.
11. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids D and E employed are those containing at least 3 carboxyl groups and the epoxide compounds employed are diepoxide compounds.
12. Process according to Claim 10 or 11, characterised in that the reaction is carried out using a ratio such that approximately 1 equivalent of polyester-carboxylic acid as present per equivalent of epoxide compound and in that no curing agent C is employed.
13. Process according to Claim 10 or 11, 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 cross-linking reaction of the excess epoxide groups.
14. Process according to Claim 1, characterised in that the polyester-polycarboxylic acids D and E employed are polyester-dicarboxylic acids and the epoxide compounds employed are those containing 2 epoxide groups.
15. Process according to Claim 14, 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 also used in an amount which is required for the cross-linking reaction of excess epoxide groups, as the curing agent.
16. Process according to Claim 14, characterised in that at least one adduct containing epoxide groups is manufac-tured, in a first stage, from the epoxide compounds and the polyester-polycarboxylic acids D and E using 0.5 to 1 equivalent of polyester-polycarboxylic acid per 2 equi-valents of epoxide compound, and, in a second stage, is crosslinked by reaction with customary curing agents.
17. Process according to Claim 1, characterised in that a blowing agent for the manufacture of foams is added before or during the reaction.
18. Process according to Claim 1, characterised in that the reaction is allowed to proceed in the presence of at least one further aliphatic polyester-polycarboxylic acid, which differs from the polyester-polycarboxylic acids D
and E and which causes at least one further (third) cry-stallite melting point to develop.
and E and which causes at least one further (third) cry-stallite melting point to develop.
19. Porcess 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 promote the conductivity of heat are added to the reaction mixture before or during the reaction.
21. Crystalline, crosslinked epoxide resins, characte-rised by two crystallite melting points and manufactured by the process according to Claim 1.
22. Epoxide resins according to Claim 21, characterised in that they have a lower crystallite melting point in the range from 20° to 70°C and an upper crystallite melting point in the range from 50° to 120°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH544475A CH596249A5 (en) | 1975-04-28 | 1975-04-28 | |
| CH5444/75 | 1975-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090946A true CA1090946A (en) | 1980-12-02 |
Family
ID=4293679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA251,030A Expired CA1090946A (en) | 1975-04-28 | 1976-04-26 | Process for the manufacture of crystalline, crosslinked epoxide resins |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS607649B2 (en) |
| CA (1) | CA1090946A (en) |
| CH (1) | CH596249A5 (en) |
| DE (1) | DE2618147A1 (en) |
| ES (1) | ES447355A1 (en) |
| FR (1) | FR2309579A1 (en) |
| GB (1) | GB1538536A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3064094D1 (en) * | 1979-05-08 | 1983-08-18 | Ciba Geigy Ag | Crystalline epoxy resin based one component systems and their application |
| JPS60186578A (en) * | 1984-03-07 | 1985-09-24 | Toray Ind Inc | Heat-resistant adhesive |
-
1975
- 1975-04-28 CH CH544475A patent/CH596249A5/xx not_active IP Right Cessation
-
1976
- 1976-04-26 DE DE19762618147 patent/DE2618147A1/en not_active Withdrawn
- 1976-04-26 CA CA251,030A patent/CA1090946A/en not_active Expired
- 1976-04-27 GB GB1693776A patent/GB1538536A/en not_active Expired
- 1976-04-27 ES ES447355A patent/ES447355A1/en not_active Expired
- 1976-04-27 FR FR7612380A patent/FR2309579A1/en active Granted
- 1976-04-28 JP JP4933176A patent/JPS607649B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS607649B2 (en) | 1985-02-26 |
| JPS51131598A (en) | 1976-11-16 |
| GB1538536A (en) | 1979-01-24 |
| DE2618147A1 (en) | 1976-11-18 |
| FR2309579A1 (en) | 1976-11-26 |
| CH596249A5 (en) | 1978-03-15 |
| ES447355A1 (en) | 1977-07-01 |
| FR2309579B1 (en) | 1979-04-20 |
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