Reaction products of polydiolefins, phenols and unsaturated carboxylic acids

A reaction product of a diolefine polymer with a phenol and an olefinically unsaturated carboxylic acid or its anhydride wherein the diolefine polymer is PA0 (a) a homopolymer of a diene having 4 to 10 carbon atoms, PA0 (b) a copolymer of at least two dienes of (a), PA0 (c) a copolymer of at least one diene of (a) with a minor molar amount of at least one copolymerizable monomer, PA0 (d) a combination of at least two of (a) to (c) Wherein the amount of phenol is in the range from 2 to 40% by weight and the amount of the unsaturated carboxylic acid or its anhydride is in the range from 2 to 55% by weight, always referred to the starting polymer, a process for the preparation of said product wherein PA0 (a) a homopolymer of a diene having 4 to 10 carbon atoms, PA0 (b) a copolymer of at least two dienes of (a), PA0 (c) a copolymer of at least one diene of (a) with a minor molar amount of at least one copolymerizable monomer, PA0 (d) a combination of at least two of (a) to (c), PA0 (e) polymerizable unsaturated monomers being the base for one of polymers (a) to (c) either alone or in admixture are polymerized and at the same time the reaction mass Is reacted in one step with an amount of phenol sufficient to cause a content of bound phenol groups in the range from 2 to 40%, and with 2 to 55% by weight of (h) an unsaturated carboxylic acid, (i) an anhydride thereof or (k) of a combination of (h) and (i), referred to the starting polymer, and wherein unreacted phenol is subsequently eliminated and a binding agent comprising said product.

This invention relates to reaction products of diolefin polymers with 
phenols and olefinically unsaturated carboxylic acids or their anhydrides 
and to processes for the preparation thereof. 
It is known that under the action of strong acids or Friedel Crafts 
catalysts olefins can be added to phenols in the ortho- and/or 
para-positions as well as to the hydroxy group itself with ether 
formation. Depending on the reaction conditions in certain circumstances 
diolefins can add on at both double bonds. In addition reaction products 
of diolefin polymers with phenol are known. 
Maleate oils can be produced by reacting maleic anhydride with unsaturated 
natural oils, such as wood oil and linseed oil. In the same way maleic 
anhydride can be reacted under the influence of heat with terpenes, 
unsaturated hydrocarbon resins and polybutadiene oils. The production of 
polybutadiene oil/maleic anhydride adducts is often difficult because 
gelling can easily occur particularly if more than 3% of maleic anhydride 
is added. It is indeed possible to reduce or even prevent gelling by using 
various additives such as hydroquinone, Ionol i.e. 
2,6-di-tert.-butyl-4-methyl-1-phenol, copper powder, copper naphthenate or 
complexing agents, but this is disadvantageous due to the high price of 
the chemicals and the additional working stages necessary e.g. removing 
the additives. In addition, the products are usually darkened by the 
additives or their properties are impaired. 
According to a known process mineral oil resins and phenol formaldehyde 
resins are reacted together in the presence of unsaturated carboxylic 
acids or anhydride such as maleic anhydride and the products obtained 
therefrom are used as binders for printing inks and paints. In this 
process it is firstly necessary to prepare a phenol resin with the desired 
specific characteristics which is only reacted further in the second 
stage. Since the reactive positions of the phenol nuclei in the starting 
phenol resin are substantially occupied as a result of the formaldehyde 
condensation the phenol resin can substantially only react with the 
mineral oil resin at the methylol groups. Consequently the phenol nuclei 
cannot be added to the double bonds of the starting mineral oil resin. 
It has now been found that phenols, olefinically unsaturated carboxylic 
acids and anhydrides and polydiolefins can be reacted together in a single 
stage to yield products suitable as binders for printing inks, adhesives 
and paints. 
Thus according to one feature of the present invention there is provided 
the reaction product of a phenol component, an olefinically unsaturated 
carboxylic acid component comprising an olefinically unsaturated 
monocarboxylic acid containing from 3 to 22 carbon atoms or anhydride 
therefrom and/or an olefinically unsaturated dicarboxylic acid or 
anhydride, and a diolefin polymer selected from: 
(a) a homopolymer of a diene containing from 4 to 10 carbon atoms, 
(b) a copolymer of at least two dienes containing from 4 to 10 carbon 
atoms, 
(c) a copolymer of at least two dienes containing from 4 to 10 carbon atoms 
and a less than equimolar proportion of at least one copolymerisable 
monomer, or 
(d) a combination of at least two of the above-identified homo- and 
copolymers, 
wherein the phenol content is from 2 to 40% by weight, preferably from 3 to 
30% by weight, and the content of the olefinically unsaturated carboxylic 
acid component is from 2 to 55% by weight, preferably from 5 to 30% by 
weight of the initial diolefin polymer weight. 
According to a further feature of the present invention there is provided a 
process for the preparation of a reaction product as herein described 
which comprises reacting in a single stage a diolefin polymer as 
hereinbefore defined with from 2 to 55% by weight, preferably from 5 to 
30% by weight of an olefinically unsaturated carboxylic acid component as 
hereinbefore defined and with a sufficient quantity of a phenol component 
to provide from 2 to 40%, preferably from 3 to 30% by weight, of bound 
phenol radicals in the product, all % weights being referred to the 
initial diolefin polymer weight, and subsequently removing any unreacted 
phenol from the product. 
According to one embodiment of the invention the polymerisable unsaturated 
monomers serving as the basis for the polymers and polymer mixtures (a) to 
(d) are polymerised in the reaction mixture which is simultaneously 
reacted with phenol and with 2 to 55% by weight of an unsaturated 
carboxylic acid and/or its anhydride based on the starting polymer, and 
subsequently the unreacted phenol is removed. 
The products according to the invention can, for example, be obtained if 
the polymers are reacted with the olefinically unsaturated carboxylic 
acids or their anhydrides and, if desired and excess of phenol, optionally 
in the presence of a maximum of 5% by weight based on the starting polymer 
of a Friedel-Crafts catalyst or a mineral acid. The unreacted phenol 
portions as well as any catalyst used are then removed. The reaction can 
also be performed in the presence of a solvent whereby for example the 
unreacted phenol can subsequently be removed together with any solvent 
present. It is thus possible to add the unsaturated acid or its anhydride 
and phenol even in relatively high quantities to a wide variety of 
diolefin polymers in a technically simple process. In comparison with the 
previously known processes there is no partial or complete gel formation. 
Further the additives conventionally used in thermal maleic anhydride 
additions are unnecessary. 
The polydiolefin preferably has a relatively low average molecular weight. 
The term "relatively low molecular weight" when used herein refers to 
polymers with an average molecular weight of up to 15,000 preferably 600 
to 10,000. Preferably the polymers have an average molecular weight of at 
least 300. If the products are to have the properties of hard resins 
generally polymers with an average molecular weight of from 500 to 5000 
are used as starting materials. If soft polymers are desired starting 
polymers with an average molecular weight of up to 1,400 are preferred. It 
is sometimes however also possible to use polymers with higher molecular 
weights e.g. up to 100,000. 
In the reaction products according to the invention the phenol groups are 
bound to the polydiolefins at the ortho- and/or para-positions to the 
phenolic hydroxy group. In addition some of the phenol radicals can be 
bound via ether linkages to C-atoms of the polymer, as proved for example 
by IR analysis. 
The products obtained from low molecular weight polymers are sometimes 
still partly unsaturated depending on the quantity of phenol added and 
unsaturated acids or their anhydrides can therefore undergo further 
addition and/or polymerisation reactions. The unsaturated acid or 
anhydride e.g. maleic anhydride can be added in various ways to the double 
bonds not used up by addition to phenol e.g. by means of Diels Alder 
reactions and/or also by means of a simple addition reaction of the 
olefinic double bonds of the acid to the olefinic double bonds of the 
polydiolefin. In addition the carboxyl groups can add across the 
polydiolefin double bonds with or without catalysts. Residual double bonds 
of the polymers can also be used up by cyclisation reactions. 
As diolefin polymers can be used in addition to 1,4- and 1,2-polybutadiene, 
polyisoprene polymers of cycloaliphatic dienes with 5 to 10 C-atoms, such 
as cyclopentadiene, methylcyclopentadiene, dicyclopentadiene, 
cyclohexadiene and cycloheptadiene. 
The copolymerisable monomers are preferably singly olefinically 
unsaturated. Of the multiply unsaturated compounds those with at least two 
allyl groups are preferred particularly those with two. Suitable 
copolymerisable monomers include for example styrene, 
.alpha.-methylstyrene, the various vinyl toluenes, acrylic acid and 
methacrylic acid or their derivatives such as esters, amides and nitriles, 
as well as vinylpyridine, allyl compounds, such as diallylphthalate and 
unsaturated compounds of petroleum fractions e.g. mixtures of unsaturated 
hydrocarbons particularly those having an average carbon atom content of 
from 5 to 9 C-atoms e.g. piperylene or indene. 
Mono-olefins with a boiling temperature in the range 20.degree. to 
190.degree. C are preferred as copolymerisable monomers. 
Preferred copolymers are those derived from C.sub.4 - to C.sub.9 
-conjugated dienes particularly C.sub.5 - and/or C.sub.9 -dienes, and 
dicyclopentadiene. Preferred copolymers according to the invention are for 
example butadiene-dicyclopentadiene copolymers, styrene-dicylcopentadiene 
copolymers, butadienecyclopentadiene-vinyltoluene copolymers, 
dicyclopentadieneisoprene copolymers, butadiene-styrene copolymers and 
isoprenestyrene copolymers. 
Suitable phenols according to the invention include mono- and polyvalent, 
mono- and polynuclear, substituted and unsubstituted phenols, such as 
phenol, alkylphenols, e.g. the various cresols, xylenols, butyl- and 
nonylphenols, chlorophenols, styrenated phenols, resorcinol, naphthols, 
diphenylolmethanes, diphenylolpropanes and novolaks, as well as esterified 
or etherified phenols, such as anisole, and other phenol derivatives, such 
as phenol carboxylic acids. 
Advantageously the reaction takes place with an excess of phenol based on 
the diolefin polymer weight. It can however also take place with the 
calculated amount. 
The olefinically unsaturated carboxylic acid component comprises 
appropriately, for example dicarboxylic acids, such as maleic, fumaric, 
citraconic, mesaconic and itaconic acid, and mixtures thereof as well as 
their anhydrides, whereby maleic anhydride is preferred. 
According to one embodiment of the invention the reaction products may 
contain in place of or in addition to the unsaturated dicarboxylic acids 
or their anhydrides, olefinically unsaturated monocarboxylic acids 
containing from 3 to 22, preferably from 3 to 18 C-atoms or their 
anhydrides. Reaction products modified by the presence of these 
unsaturated monocarboxylic acids and anhydrides are characterised by a 
particularly light colour which is retained in solution and by a 
substantial uniformity in their molecular weight. By incorporating 
monocarboxylic acids, particularly if they are bound as ester groups, the 
polarity of the products is increased and leads to a better behaviour 
relative to pigments. 
Suitable unsaturated monocarboxylic acids include for example acrylic acid, 
methacrylic acid, phenylacrylic acid, crotonic acid, isocrotonic acid, 
vinylacetic acid, angelic acid, tiglic acid, sorbic acid, undecyclic acid, 
fatty acids of drying or semi-drying oils, such as oleic acid, caster oil 
fatty acid (the fatty acid obtained from dehydrated caster oil), elaidic 
acid, eleostearic acid, erucaic and brassidic acid. Mixed anhydrides can 
be used as the unsaturated carboxylic acid component. 
If both unsaturated monocarboxylic and dicarboxylic acids and/or their 
anhydride are to be reacted with the diolefin they can be added 
simultaneously or separately. 
It is also possible for the reaction products according to the invention to 
contain saturated aromatic and/or araliphatic carboxylic acids with at 
least 3 C-atoms. Thus, for example, mono- and/or polycarboxylic acids as 
well as their substitution products such as hydroxycarboxylic acids and 
halogenocarboxylic acids and/or their derivatives e.g. anhydrides and 
esters including partial esters, can be added to the reaction mixture but 
only however in small quantities. Suitable saturated and/or aromatic acids 
include for example those with up to 18 C-atoms, such as propionic, 
butyric, caproic, heptanoic, isononanoic, decanoic, dodecanoic, lauric, 
palmitic, stearic, malonic, succinic, adipic, chloroacetic, glycollic, 
lactic, citric, phenylacetic, phthalic, isophthalic, terephthalic, 
trimellitic, and pyromellitic acids. These acids may be added in each case 
singly or in admixture. Appropriately their proportion represents a 
maximum of 20% by weight based on the total weight of the unsaturated 
carboxylic acid component. Products modified with saturated carboxylic 
acids are particularly advantageous if it is desired to reduce the degree 
of unsaturation of the end products or to increase the number of acid 
groups bound as esters and therefore the number of functional groups. It 
is found that the presence of saturated carboxylic acids increases the 
solubility of the products in certain solvents e.g. aliphatic hydrocarbons 
and extends the compatibility range with other resin groups. 
The weight ratio of the phenol component to the unsaturated carboxylic acid 
component in the starting mixture is advantageously from 1:28 to 20:1, 
preferably from 1:9 to 9:1, in particular 7:3 to 3:7. 
When used any catalyst can for example be removed by precipitation and/or 
neutralisation and/or by washing out. The separation of the catalyst can 
also take place by neutralisation and subsequently filtration or washing 
out. If sulphuric acid or sulphonic acids are used the separation can also 
take place in per se known manner by reduction e.g. to sulphur dioxide 
(SO.sub.2) by means of the polymer. 
Suitable catalysts include for example Friedel Crafts catalysts, e.g. metal 
compounds, such as halides, e.g. aluminium and zinc chloride or tin 
tetrachloride, as well as borontrifluoride or its complexes, such as 
borontrifluoride etherate or borontrifluoride phenol, mineral acids, such 
as phosphoric acid, hydrochloric acid and preferably sulphuric acid and 
sulphonic acids, such as phenol sulphonic acid, p-toluene sulphonic acid 
or xylene sulphonic acids. The catalyst is generally present during the 
reaction in a proportion of at least 0.2% preferably up to 2%, by weight 
based on the diolefin polymer. It is advantageous to use a relatively 
small quantity of catalyst since the catalyst can be more easily removed 
and the preparation of the products causes less corrosion problems than 
when using larger quantities of catalyst. 
The reaction of the phenol component and the unsaturated mono- or 
dicarboxylic acid or anhydride, for example maleic anhydride, with the 
polymers can take place in various ways, for example in solution or in the 
melt and generally at temperatures of 20.degree. to 220.degree. C, 
preferably 40.degree. to 150.degree. C, particularly at 120.degree. C. The 
polymer can be mixed or fused with the phenol and the acid or anhydride 
and subsequently mixed with the catalyst. It is also possible to first mix 
the phenol, the acid or the anhydride and the catalyst and to subsequently 
add the polydiolefin, particularly when using liquid polymers. When the 
reaction has been completed under appropriate temperature and pressure 
conditions any excess phenol is removed e.g. by distillation under normal 
or reduced pressure. 
According to a preferred embodiment, formaldehyde is added to the reaction 
mixture before, during or after the reaction and is condensed therewith. 
Hereagain it is possible to work in the presence of or in the absence of 
catalysts. The molar ratio of incorporated phenol to incorporated 
formaldehyde is generally from 1:(0.2 to 3.5), or 1:(0.2-0.8) or 
1:(0.8-1.8), preferably from 1:(0.2 to 1.8). 
It was previously thought that formaldehyde could generally only be 
incorporated into phenol resins in a proportion of up to about 2 mol per 
mol of phenol. However according to the present invention there are 
provided phenol resins containing up to 40% by weight of incorporated 
phenol and containing a higher proportion of formaldehyde per mol of 
phenol. The formaldehyde can react in other ways as well as with the 
phenolic component. Thus, for example, the reactive methylol groups 
derived from the formaldehyde can also undergo reactions with the diolefin 
polymers and/or unsaturated terpenes such as colophony present in the 
starting mixture. 
The process according to the invention has the following advantages: Light 
products are obtained in good yield and with much higher proportions of 
phenol and unsaturated carboxylic acid components, particularly maleic 
anhydride, than in the hitherto known processes according to which only 
phenol or only maleic anhydride could be added to the resin. Surprisingly 
no gel formation occurs. Concomitantly used catalysts can be separated 
from the reaction mixture without difficulty. Since the quantity of 
catalyst is very small it can sometimes be allowed to remain in the 
reaction product if the small amount does not have a disadvantageous 
effect depending on the intended use of the products. 
The embodiment of the inventive process according to which unsaturated 
monocarboxylic acids or their anhydrides are used has the advantage that 
the reaction can be performed under milder conditions i.e. at lower 
temperatures and the unreacted volatile component can be removed more 
easily. As a result undesired polymerisation and therefore viscosity rises 
can be avoided. 
The reaction products have the further advantage that their content of 
phenol or unsaturated acids or anhydrides, for example their maleic 
anhydride content, can vary within a wide range. They can simultaneously 
also have a high content of phenol and acids or anhydride which can e.g. 
be determined by IR spectrographic analysis whereby however the 
above-indicated figures are always calculated with reference to the 
starting polymer. 
A further advantage of the formaldehyde-containing reaction products is 
that the products can be prepared without isolation of intermediates. In 
this way it is also possible to obtain products with a high content of 
incorporated phenol. This is made possible by firstly condensing 
formaldehyde with those phenol nuclei which were first added to the diene 
polymer. Via the methylol groups formed from the formaldehyde it is now 
possible to partially condense further quantities of phenol. This leads to 
an increase in the number of phenolic hydroxy groups and reactive 
positions on the phenol nuclei at which further components can be 
introduced. In addition the solubility of the products in various solvents 
as well as the compatibility with a series of other resins or resin 
combinations can be varied leading to a wider utilisation of the products 
according to the invention. 
The viscosity of the products can vary within a very wide range. For 
example the products can be liquids of high or low viscosity or even 
solid. Generally the viscosity rises with increasing content of the 
phenols and carboxylic acids or anhydrides. The hydroxy and acid numbers 
can vary within wide limits. By adjusting the polarity the solubilities in 
polar and non-polar solvents can be controlled. With increasing hydroxy 
number the products have an increasing compatibility with other phenolic 
resins. The products according to the invention are much more stable to 
atmospheric oxidation as well as thermal stressing than the known phenol 
or maleic anhydride adducts. In addition they have improved solubilities 
and compatibilities with a wide variety of resin groups. In addition the 
melting points of the products according to the invention can be varied 
according to the phenol, formaldehyde and carboxylic acid or anhydride 
content. For example the melting points of the products can be increased 
as desired, up to about 240.degree. C increasing the proportion of 
dicarboxylic acids or their anhydrides or of monocarboxylic acids with up 
to 4 C-atoms. It is also possible to lower the melting point by 
incorporating longer chained unsaturated monocarboxylic acids. 
The reaction products according to the invention can be partially 
unsaturated and have iodine numbers exceeding 100. Consequently they can 
undergo further addition and/or polymerisation and/or cyclisation 
reactions. 
The products according to the invention are elastic, soluble in solvents 
such as aliphatic aromatic hydrocarbons chlorinated hydrocarbons such as 
trichlorethylene, carbon tetrachloride, chlorobenzene, as well as in ethyl 
acetate and chloroform. The solubilities are adjustable by means of the 
incorporated phenol and acid or anhydride content. The products according 
to the invention are for example good binders for coatings, adhesives and 
printing inks, but by modifying them, e.g. by esterification of the 
carboxy groups formed by hydrolysis of the anhydrides with mono- and/or 
polyhydric alcohols or by salt formation, they can be used for other 
purposes. Coatings produced from the products have a good lustre, 
adhesion, bending strength, wear-resistance and an excellent compatibility 
with pigments. In particular products with a high phenol content have a 
high resistance to yellowing during stoving. The lower viscosity products 
in particular e.g. those with a phenol content of 3 to 20% by weight and a 
content of unsaturated carboxylic acids or anhydrides of 5 to 35%, and in 
particular a maleic anhydride content of 5 to 25, preferably up to 20% by 
weight, are suitable for use in paints. Products with a phenol content of 
5 to 30% preferably up to 25% by weight, particularly at least 10% by 
weight and a content of unsaturated carboxylic acids, particularly 
unsaturated dicarboxylic acids or anhydrides, preferably maleic anhydride, 
of at least 5%, preferably 15 to 30% by weight (percentage figures are 
always based on the starting polymer) are particularly suitable as 
printing ink binders. Products with a high phenol content of even above 
30% by weight and a high content of dicarboxylic acid or the anhydride 
thereof or monocarboxylic acids with up to 4 C-atoms, particularly maleic 
anhydride, are suitable as water-soluble paints due to the saponifiable 
groups. 
The products according to the invention both during their formation and as 
a result of subsequent reaction can be modified e.g. with terpene 
compounds such as colophony and/or fatty oils. The addition of these 
substances can take place before, during or after the main reaction. The 
products can also contain at least one unsaturated terpene compound such 
as pinene, dipentene or the like, preferably resinic acids e.g. colophony. 
In addition the phenolic hydroxy group can be esterified (e.g. with acetic 
anhydride) or etherified (e.g. by reacting with an alkylene oxide such as 
epichlorohydrin). It is also possible to react the excess of phenol with 
formaldehyde or harden the resin with hexamethylene tetramine or react it 
with resols. At the free positions of the phenol nucleus it is also 
possible to perform substitution reactions e.g. aryl or alkyl and/or 
aralkyl groups, such as methyl, ethyl, propyl, isononyl and phenylethyl 
groups can be introduced. Styrene or compounds with unsaturated groups 
such as alkenyl groups e.g. the nonenyl group may also be added to the 
phenol nucleus as well as halogen atoms such as chlorine and bromine. 
The products obtained by reacting with formaldehyde or epichlorohydrin are 
generally hardenable e.g. with amines or acid anhydrides. Mixed adducts 
with terpenes, particularly natural resinic acids are very well suited for 
the above applications.

In the following Examples all % are % by weight. Unless otherwise stated 
the viscosity is measured at 20.degree. C in a 50% toluene solution. 
EXAMPLES 
(1) 0.4 g of 100% phenol sulphonic acid are added at 50.degree. C to a 
mixture of 240 g of cis-1.4-polybutadiene oil, 480 g of phenol and 40 g of 
maleic anhydride. The reaction mixture immediately darkens. 
After maintaining the mixture for 1 hour at 90.degree. C, it is 
continuously heated for 3 hours to 180.degree. C and left at this 
temperature for 3 hours. During this time the reaction mixture becomes 
light-coloured. The unreacted phenol is distilled off under heating up to 
220.degree. C. The residual phenol is removed under reduced pressure (60 
mm Hg). 318 parts of a light yellow, tough plastic resin having a 
viscosity of 177 cP and containing about 40 g of bound maleic anhydride 
and 38 g of bound phenol are obtained. After stoving, these products give 
varnish films showing good adhesion and bending strength. 
(2) 0.3 g of 100% phenol sulphonic acid are added at 90.degree. C to a 
mixture comprising 100 g of 1.2-polybutadiene oil, 300 g of phenol and 17 
g of maleic anhydride, whereby the reaction mixture turns dark. It is 
maintained for 1 hour at 90.degree. C, then continuously heated within 2 
hours up to 180.degree. C and left at this temperature for 3 hours. The 
temperature is increased to 220.degree. C in order to distill off the 
excess of phenol. To remove the residual phenol the mixture is heated 
under reduced pressure (60 mm Hg). 138 parts of a yellow, clear, hard 
resin having a melting point of 162.degree. C and a viscosity of 2510 cP, 
containing 17 g of bound maleic anhydride and 21 g of bound phenol, are 
obtained. 
(3) 0.2 g of 100% phenol sulphonic acid are added at 50.degree. C to a 
mixture comprising 120 g of cis-1,4-polybutadiene oil, 240 g cP phenol and 
40 g of maleic anhydride. Heating takes place during 4 hours at 
180.degree. C, whereby the dark coloured reaction mixture becomes lighter. 
The mixture is maintained for 3 hours at this temperature and the 
unreacted phenol is then distilled off at 220.degree. C, first under 
normal pressure and finally under reduced pressure (60 mm). 173 g of a 
clear, yellow brown, comminutable, hard resin having a melting point of 
48.degree. C, containing 40 g of bound maleic anhydride and 13 g of bound 
phenol, are obtained. After neutralization with ammonia or amines, the 
resin is dilutable with water. 
(4) At 90.degree. C 0.15 g of boron trifluoride-phenol are added to a 
mixture comprising 120 g of cis-1,4-polybutadiene oil, 240 g of phenol and 
20 g of maleic anhydride, whereby the mixture becomes slightly 
dark-coloured. It is maintained for 10 minutes at 90.degree. C and then 
continuous heating takes place for 75 minutes at 180.degree. C. While the 
mixture is maintained for 4 hours at this temperature a gentle stream of 
carbon dioxide is passed over. The unreacted phenol is then distilled off 
at 220.degree. C under normal pressure and finally under reduced pressure 
(60 mm). 141 g of yellow, high-viscous resin remain. Products of this kind 
are suitable as adhesive resins for polychloroprene and polyurethane 
adhesives. 
(5) 8 g of maleic anhydride are added at 70.degree. C to 100 g of a liquid 
polyisoprene dissolved in 200 g of phenol. Subsequently 1 g of 100% 
phenol/sulphonic acid is added at 90.degree. C. Under the exothermic 
reaction the reaction mixture becomes dark-coloured. It is kept for 1 hour 
at 120.degree. C, then heated continuously for 3 hours to 180.degree. C, 
maintained at this temperature for a further 3 hours and finally the 
excess of phenol is distilled off at 220.degree. C, under reduced pressure 
towards the end of the distillation. 118 g of a clear, amber-coloured 
resin having a melting point of 83.degree. C and a viscosity of 25 cP are 
obtained. The product contains 8 g of bound maleic anhydride and 10 g of 
bound phenol. 
(6) 250 g of cis-polyisoprene are added to a mixture heated to 160.degree. 
C comprising 300 g of phenol and 5 g of maleic anhydride. Within 5 hours 
2.5 g of concentrated sulphuric acid are added dropwise, whereby the 
polyisoprene is gradually dissolved. Under continuous heating to 
260.degree. C the unreacted phenol is distilled off, under reduced 
pressure (60 mm) towards the end of the distillation. 266 g of cyclized 
rubber modified with maleic acid groups in the form of a clear, light 
yellow resin having a melting point of 130.degree. C and a viscosity of 
3460 cP are obtained. Content of maleic anhydride: 5g, phenol content 11g. 
The products are suitable for the preparation of printing inks. 
(7) 300 g of phenol heated to 160.degree. C are first combined with 1.3 g 
of zinc chloride, then with 15 g of maleic anhydride and finally with 250 
g of cis-polyisoprene. After a short time the reaction mixture becomes 
dark-coloured. After dissolution of the polyisoprene within 4 hours, the 
zinc chloride is precipitated by addition of 2.7 g of soda and separated 
by filtration. The excess of phenol is removed from the filtrate by 
distillation at 220.degree. to 260.degree. C, under reduced pressure (60 
mm) towards the end of the distillation. In a yield of 283 g a cyclized 
rubber modified with maleic groups in the form of an amber-coloured resin 
having a melting point of 148.degree. C and a viscosity of 592 cP is 
obtained which is suitable for printing inks. Content of maleic anhydride 
15 g, phenol content 18 g. 
(8) 400 g of phenol are heated up to 160.degree. C. First 15 g of maleic 
anhydride and then 250 g of an isoprene-styrene copolymer are added 
dropwise within 4 hours. The mixture is maintained for 3 hours at 
180.degree. C and the temperature is subsequently increased to 260.degree. 
C. The excess of phenol is distilled off simultaneously. The residual 
amounts of phenol are removed under reduced pressure. 274 g of a light 
yellow hard resin having a melting point of 175.degree. C and a viscosity 
of 289 cP are obtained. Content of maleic anhydride 15 g, phenol content 9 
g. 
(9) At 90.degree. C 1 g of 100% phenol sulphonic acid is added to a mixture 
comprising 120 g of phenol, 5 g of maleic anhydride and 50 g of a liquid 
copolymer of isoprene and vinyltoluene in a weight ratio of 40:60. The 
mixture darkens immediately under the exothermic reaction. Cooling to 
90.degree. C takes place during 1 hour. The mixture is then heated to 
110.degree. C and maintained for 2 hours at this temperature. Within 5 
hours it is continuously heated up to 180.degree. C and kept for 3 hours 
at this temperature. The excess of phenol is removed by heating to 
220.degree. C and reducing the pressure (60 mm) towards the end of the 
distillation. 61 g of yellow orange, clear resin having a melting point of 
100.degree. C and a viscosity of 101 cP are obtained. Content of maleic 
anhydride 5 g, phenol content 6 g. 
(10) At 90.degree. C g of 100% phenol sulphonic acid is added to a mixture 
comprising 120 g of phenol, 5 g of maleic anhydride and 50 g of a liquid 
popolymer of isoprene, styrene and .alpha.-methylstyrene in a weight ratio 
of 60:20:20. Under the exothermic reaction the mixture turns dark. The 
reaction being completed the mixture is maintained for 1 hour at this 
temperature and for 2 hours at 110.degree. C. In the course of 5 hours 
heating takes place continuously up to 180.degree. C and this temperature 
is maintained for 3 hours. The unreacted phenol is distilled off at 
220.degree. C, finally under reduced pressure (60 mm). 63 parts of an 
orange yellow, clear resin having a melting point of 61.degree. C and a 
viscosity of 35 cP are obtained. Content of maleic anhydride 5 g, phenol 
content 8 g. In the place of the isoprene, styrene, .alpha.-methylstyrene 
copolymer, a copolymer of butadiene, styrene and .alpha.-methylstyrene may 
be used resulting in a product with good properties. 
(11) 0.5 g of 100% phenol sulphonic acid are added at 90.degree. C to a 
mixture comprising 200 g of phenol, 20 g of maleic anhydride and 100 g of 
a copolymer of dicyclopentadiene and styrene in a weight ratio of 70:30. 
Under the strongly exothermic reaction the mixture turns dark. With 90 
minutes it is heated continuously to 180.degree. C and maintained for 3 
hours at this temperature. The reaction mixture becomes essentially 
lighter-coloured. The excess of phenol is distilled off at 220.degree. C, 
finally under reduced pressure (60 mm). A light brown, clear resin having 
a melting point of 104.degree. C and a viscosity of 76 cP with a yield of 
136 g is obtained. The product contains 20 g of bound maleic anhydride and 
16 g of bound phenol. It is suitable as an adhesive resin. 
(12) 1.5 g of 100% phenol and sulphonic acid are added at 90.degree. C to 
a mixture comprising 200 g of phenol, 30 g of maleic anhydride and 100 g 
of a copolymer of 90 g of dicyclopentadiene and 10 g of pinene. The 
reaction mixture turns dark under the strongly exothermic reaction. 
Cooling takes place from 130.degree. C to 110.degree. C where the mixture 
is maintained for 4 hours. In the course of 2 hours it is heated up to 
180.degree. C and kept for 2 hours at this temperature. Subsequently the 
excess of phenol is removed at 220.degree. C, towards the end of the 
distillation under reduced pressure (60 mm). 166 g of a reddish brown 
resin having a melting point of 165.degree. C and a viscosity of 3 340 cP 
are obtained. The product contains 30 g of bound maleic anhydride and 36 g 
of bound phenol, which product is suitable for printing inks. 
(13) 1.5 g of 100% phenol sulphonic acid are added at 90.degree. C to a 
mixture comprising 200 g of phenol, 70 g of maleic anhydride and 100 g of 
a copolymer of 90 g of dicyclopentadiene and 10 g of colophony. An intense 
dark coloration is the result of the strongly exothermic reaction. The 
mixture is maintained for 1 hour at 120.degree. C and subsequent heating 
takes place continuously for 1 hour up to 180.degree. C. After 3 hours at 
180.degree. C the unreacted amount of phenol is distilled off at 
220.degree. C first under normal pressure and towards the end of the 
distillation under reduced pressure (60 mm). 149 g of a clear, brown resin 
having a melting point of 167.degree. C and a viscosity of 1 110 cP are 
obtained. The product contains 20 g of bound maleic anhydride and 29 g of 
bound phenol. It is a suitable resin for printing inks. 
(14) 200 g of a copolymer comprising 30% of pinene and 70% of a hydrocarbon 
fraction of 15% isoprene, 20% piperylene, 25% dicyclopentadiene, 5% 
butadiene and varying amounts of N- and isopentene and cyclopentene, as 
well as is oxylene, are mixed with 100 g of phenol 30 g of maleic 
anhydride and, after heating up to 90.degree. C, 1.5 g of 100% phenol 
sulphonic acid are then added. The temperature reaches 180.degree. C as a 
result of the strongly exothermic reaction, and a dark coloration is 
produced. The mixture is maintained for 3 hours at this temperature and 
the reaction mixture simultaneously becomes lighter coloured. By heating 
up to 260.degree. C the unreacted starting materials are distilled off, 
towards the end of the distillation under reduced pressure (60 mm). 177 g 
of a brown, clear resin having a melting point of 60.degree. C and a 
viscosity of 13 cP are obtained. 
(15) 200 g of a copolymer comprising 10% of pinene and 90% of a hydrocarbon 
fraction of 2.7% of styrene, 5.4% of .alpha.-methylstyrene. 9.2% 
vinyltoluene, 14.6% dicyclopentadiene and 21.4% of indene, and still 
containing aromatic and saturated hydrocarbon, are added to 100g of 
phenol. 30 g of maleic anhydride are added and, after heating up to 
90.degree. C, 1.5 g of 100% phenol sulphonic acid are added. An exothermic 
reaction with simultaneous darkening of the mixture takes place. The 
mixture is maintained for 75 minutes at 120.degree. C, then continuously 
heated for 1 hour up to 180.degree. C, where it is kept during 4 hours and 
subsequently the unreacted starting materials are distilled off at 
260.degree. C, first under normal pressure and then under reduced pressure 
(60 mm). 177 g of a brown, clear resin having a melting point of 
55.degree. C and a viscosity of 13 cP are obtained. 
(16) 2 g of 700% phenol sulphonic acid are added to a mixture of 100 g of 
phenol and 30 g of maleic anhydride. After heating to 80.degree. C 140 g 
of thermally prepolymerized dicyclopentadiene are added within 1 hour. 
Subsequent heating takes place continuously up to 180.degree. C within 4 
hours and the mixture is kept at this temperature. forafurther 4 hours. 
After increasing the temperature to 250.degree. C the residual phenol is 
removed under reduced pressure (60 mm). 226 g of a yellow brown resin 
having a melting point of 100.degree. C and a viscosity of 62 cP are 
obtained. Content of maleic anhydride 35 g, phenol content 56 g. The 
product is suitable as adhesive resin. 
(17) 300 g of polymerized dicyclopentadiene are fused with 140 g of phenol. 
The mixture is heated to 110.degree. C. Subsequently 12 g of 
paraformaldehyde and 45 g of maleic anhydride are added. Heating takes 
place for 2 hours up to 180.degree. C where the mixture is kept for 2 
hours. Within 30 minutes the temperature is increased to 250.degree. C and 
finally the unreacted phenol is distilled off under reduced pressure (60 
mm). 375 g of an amber-coloured resin having a melting point of 
180.degree. C and a viscosity of 460 cP are obtained. Content of maleic 
anhydride 35 g, phenol content 40 g. The product is a particularly 
suitable resin for toluene intaglio inks. 
(18) A mixture comprising 140 g of phenol, 12 g of paraformaldehyde, 45 g 
of maleic anhydride and 70 g of acrylic acid are heated to 145.degree. C. 
Subsequently 300 g of dicyclopentadiene are added dropwise within 3 hours. 
The mixture is then kept under reflux for 5 hours and finally heated up to 
250.degree. C. Residual, unreacted starting materials are removed under 
reduced pressure (60 mm). 339 g of a yellow-brown resin having a melting 
point ranging from 93.degree. to 95.degree. C and a viscosity of 254 cP 
are obtained. Content of maleic anhydride 45 g, phenol content 75. 
(19) 900 g of polycyclopentadiene are dissolved under heat in a mixture 
comprising 143 g of p-tert.-butylphenol and 50 g of xylene. Heating takes 
then place up to 110.degree. C. First 108 g of maleic anhydride and 
subsequently 30 g of paraformaldehyde are added to the mixture, which is 
heated for 3 hours to 180.degree. C and kept there for 30 minutes. Within 
a further hour the mixture is heated to 250.degree. C, whereby slightly 
volatile substances are distilled off. Towards the end of the reaction the 
pressure is reduced (60-80 mm). A yellow brown resin having a melting 
point of 151.degree. C, a viscosity of 156 cP and an acid number of 37 is 
obtained in a yield of 1.112 g (=94%). The molar ratio of phenol to 
formaldehyde is 1:0.95. 
(20) 300 g of polycyclopentadiene and 30 g of colophony are dissolved while 
heating in a mixture comprising 30 g of xylene and 10 g of phenol. At 
120.degree. C 45 g of maleic anhydride and 6 g of paraformaldehyde are 
added. The ratio of phenol to formaldehyde is 1:1.8. During 5 to 6 hours 
the mixture is heated to 250.degree. C. The reaction mixture is still kept 
for a short time under reduced pressure (60 mm). 357 g (=98%) of a yellow 
resin having a melting point of 188.degree. to 194.degree. C and a 
viscosity of 148 cP are obtained. 
(21) 300 g of polycyclopentadiene are dissolved while heating in a mixture 
comprising 30 g of xylene and 5 g of phenol. At 120.degree. C 36 g of 
maleic anhydride, and 30 g of acrylic acid and finally 6 g of 
paraformaldehyde are added. The ratio of phenol to formaldehyde are 1:3.4. 
Continuous heating takes place for 5 hours up to 250.degree. C and the 
mixture is finally heated under pressure for 20 minutes at this 
temperature. 338 g (=90%) of a yellow resin having a melting point of 
220.degree. C and a viscosity of 597 cP are obtained. 
(22) 300 g of polycyclopentadiene are dissolved in 141 g of phenol at a 
temperature ranging from 120.degree. to 130.degree. C. A mixture 
comprising 12 g of phenolformaldehyde (phenol:formaldehyde = 1:0.25) and 
45 g of maleic anhydride is then added. Heating takes place for 2 hours up 
to 180.degree. C and the mixture is maintained for a further hour at this 
temperature. The mixture is then heated to 250.degree. C and the unreacted 
starting materials distilled off under reduced pressure (60 mm). 375 g of 
a yellow brown resin having a melting point of 184.degree. C and a 
viscosity of 497 cP are obtained. 
(23) 1350 g of dicyclopentadiene are polymerized in the presence of 150 g 
of .alpha.-pinene at 230.degree. C under a pressure of 4 atmospheres. A 
semisolid, yellow paste is obtained. 100 g of this product and 47 g of 
phenol are heated to 120.degree. C. Simultaneously 15 g of maleic 
anhydride and 4 g of paraformaldehyde are added. After maintaining the 
mixture for 30 minutes at 120.degree. C heating takes place for 6 hours to 
220.degree. C, the pressure being reduced for the last 30 minutes of the 
reaction. 145 g (=87.5%) of a yellow resin having a melting point of 
76.degree. to 78.degree. C and a viscosity of 70 cP are obtained. 
(24) 600 g of polycyclopentadiene and 30 g of colophony are fused with 60 g 
of phenol. Subsequently 30 g of .alpha.-pinene are added and the mixture 
is heated to 120.degree. C. 72 g of maleic anhydride and then 20 g of 
paraformaldehyde are added and the mixture is kept for 1 hour at 
120.degree. C. It is then heated for 6 to 8 hours at 260.degree. C. After 
removal of the slightly volatile components by distillation 745 g (=92%) 
of an amber-coloured resin having a melting point of 145.degree. C and a 
viscosity of 134 cP are obtained. 
(25) 900 g of polycyclopentadiene and 90 g of colophony are dissolved at 
120.degree. C in a mixture comprising 90 g of phenol and 90 g of styrene. 
Subsequently 108 g of maleic anhydride and 30 g of paraformaldehyde are 
added. After a longer reaction time under reflux the reaction mixture is 
heated for 6 hours to 250.degree. C and then kept for 30 minutes under 
reduced pressure (60 mm). 1192 g (=91.5%) of an amber-colored resin having 
a melting point of 170.degree. -175.degree. C and a viscosity of 144 cP 
are obtained. 
(26) 300 g of polycyclopentadiene and 30 g of cotton seed oil fatty acid 
are liquefied with 5 g of phenol. At 125.degree. C 36 g of maleic 
anhydride are added and subsequently 6 g of paraformaldehyde are 
introduced in small portions. The mixture is heated for 5 hours at 
250.degree. C where it is maintained for 30 minutes under reduced 
pressure. 363 g (=96.5%) of a yellow resin having a melting point of 
170.degree. C and a viscosity of 250 cP are obtained. 
(27) 300 g of dicyclopentadiene polymer are dissolved with heating in a 
mixture comprising 141 g of phenol and 50 g of acrylic acid. At 
120.degree. C 45 g of maleic anhydride and 12 g of paraformaldehyde are 
then added and the mixture is heated for 5 hours at 220.degree. C, thereby 
unreacted phenol is distilled off. Finally the mixture is heated for a 
further 10 minutes under reduced pressure (60 mm). 486 g (.congruent.81%) 
of a resin having a melting point of 180.degree. C and a viscosity of 625 
cP are obtained. 
(28) 300 g of polycyclopentadiene are dissolved in 141 g of phenol and 50 g 
of methyl methacrylate. At 120.degree. C a mixture of 12 g of 
paraformaldehyde and 45 g of maleic anhydride are then added. The mixture 
is heated at 250.degree. C for 6 hours and the excess of phenol is 
distilled off. 350 g of a yellow-brown resin having a melting point of 
192.degree. C and a viscosity of 1250 cP are obtained. 
(29) 300 g of polycyclopentadiene are dissolved under heat in a mixture 
comprising 30 g of xylene and 5 g of phenol. At 120.degree. C first 36 g 
of maleic anhydride and 30 g of acrylic acid and finally 6 g of 
paraformaldehyde are added (ratio of phenol to formaldehyde 1:3.4). 
Subsequently the mixture is continuously heated for 5 hours at 250.degree. 
C and then heated for 20 minutes under reduced pressure. 338 g (=90%) of a 
yellow resin having a melting point of 220.degree. C and a viscosity of 
597 cP are obtained. 
(30) 600 g of polycyclopentadiene and 60 g of colophony are fused in a 
mixture of 60 g of xylene and 20 g of phenol. Then 120 g of acrylic acid 
are added. After heating the mixture to 120.degree. C 72 g of maleic 
anhydride and 6.6 g of paraformaldehyde are introduced. The mixture is now 
heated to 250.degree. C for 6 hours and towards the end of the reaction 
heating is continued under reduced pressure (60 mm). 738 g (=84%) of a 
resin having a melting point of 180.degree. to 185.degree. C and a 
viscosity of 155 cP are obtained. 
(31) 500 g of polycyclopentadiene are dissolved under heat in a mixture 
comprising 25 g of phenol and 50 g of acrylic acid. After maintaining the 
mixture for 1 hour at 100.degree. C it is heated continuously under reflux 
and finally the volatile components are distilled off at 230.degree. C. 
Towards the end of the reaction heating is continued for 15 to 20 minutes 
under reduced pressure (approximately 150 to 200 mm). 513 g (=90%) of a 
yellow-brown resin having a melting point of 110.degree. to 112.degree. C 
and a viscosity of 32 cP are obtained. 
(32) 500 g of a cyclopentadiene polymer are fused in 200 g of phenol and 
the mixture is heated to 100.degree. C. Subsequently 50 g of acrylic acid 
are added and first heated under reflux for 6 hours at 200.degree. C, then 
the excess of phenol is distilled off at 230.degree. C. Finally heating is 
continued under reduced pressure (60 mm). 539 g (=73%) of a light yellow 
resin having a melting point of 115.degree. C and a viscosity of 23 cP are 
obtained. The hydroxyl number is 20 and the acid number 10. 
(33) 500 g of polycyclopentadiene are dissolved under heat in 100 g of 
phenol. At 100.degree. C 50 g of acrylic acid are then added. Subsequently 
4 g of paraformaldehyde are introduced. During 7 hours the temperature is 
increased under reflux to 200.degree. C and then the excess of phenol and 
the volatile components are distilled off at 230.degree. C. Finally 
heating is continued under reduced pressure (60 mm). 539 g (=83%) of a 
yellow-brown resin having a melting point of 110.degree. C and a viscosity 
of 28 cP are obtained. The hydroxyl number is 20, the acid number 12. 
(34) 500 g of a cyclopentadiene polymer are dissolved in 100 g of phenol, 
then at 100.degree. C 60 g of maleic anhydride and 10 g of acrylic acid 
are added. The mixture is heated under reflux for 7 hours at 200.degree. C 
and then volatile components are distilled off at 230.degree. C. Finally 
heating is continued under reduced pressure (60 mm). 564 g (=84%) of a 
light brown resin having a melting point of 126.degree. C and a viscosity 
of 41 cP are obtained. 
(35) 500 g of a cyclopentadiene polymer are dissolved in 100 g of phenol. 
At 100.degree. C 60 g of acrylic acid and 10 g of maleic anhydride are 
added. Subsequently heating takes place under reflux for 7 hours at 
200.degree. C and later volatile components are distilled off at 
230.degree. C. Finally heating is continued under reduced pressure (60 
mm). 547 g (=82%) of a light yellow resin having a melting point of 
122.degree. C and a viscosity of 38 cP are obtained. The hydroxyl number 
is 8 and the acid number 16. 
(36) 900 g of polycyclopentadiene are dissolved in a mixture comprising 90 
g of phenol and 90 g of xylene. At 120.degree. C a mixture of 90 g of 
maleic anhydride and 15 g of adipic acid is then added. Subsequently 30 g 
of paraformaldehyde are introduced. In the course of 5 to 6 hours the 
mixture is then heated to 250.degree. C and towards the end of the 
reaction heating is continued under reduced pressure (100 mm). 1024 g 
(=92%) of a yellow-brown resin having a melting point of 163.degree. C and 
a viscosity of 174 cP are obtained.