 |
Claims  |
|
|
We claim:
1. A random copolymer for coating or film-forming application consisting
essentially of units of:
1. 1 to 25% of a 1-olefine heat reaction product, made by heating one or
more normally liquid 1-monoolefines having from 6 to 22 carbon atoms per
molecule in the presence of from 0.5 to 10% by weight on the heat-reaction
product of one or more free-radical generating polymerisation initiators,
unitl the product has a non-volatile content, determined at the
mid-distillation point at the 1-monoolefines, or at 250.degree. C,
whichever is lower, of from 1 to 60 parts by weight per 100 parts by
weight of heat-reaction product;
2. 0 to 25% of a monomer selected from the group consisting of acrylamide,
methacrylamide and N-alkylol derivatives thereof, and hydroxyethyl and
hydroxypropyl acrylates and methacrylates and mixtures thereof;
3. 0 to 8% of an ethylenically unsaturated monomer selected from the group
consisting of mono- and di-carboxylic acids, mono-esters of dicarboxylic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic monohydric
alcohols, nitriles of monocarboxylic acids and mixtures thereof;
4. 0 to 60% of a monomer selected from the group consisting of styrene,
vinyl toluene, vinylacetate and mixtures thereof;
5. the balance, to a total of 100%, consisting of one or more
copolymerisable monomers selected from the group consisting of esters of
acrylic and/or methacrylic acids with C.sub.1 to C.sub.10 aliphatic or
cycloaliphatic monohydric alcohols and mixtures thereof;
the percentages of the components 1 to 4 being by weight on the weight of
the copolymer.
2. A copolymer as claimed in claim 1 wherein component (1) is a
heat-reaction product having a non-volatile content of from 8 to 15 parts
by weight per 100 parts by weight heat-reaction product.
3. A copolymer as claimed in claim 1 consisting of:
1. 1 to 25% of a heat-reaction product of 1-decene, made as defined in
claim 1,
2. 5 to 25% of beta-hydroxy propyl methacrylate
3. 0 to 8% of methacrylic acid, and
4. the balance of 2-ethylhexylacrylate and styrene.
4. A random copolymer for coating or filmforming application consisting
essentially of units of:
1. 1 to 25% of a 1-olefine heat-reaction product, made by heating one or
more normally liquid 1-monoolefines, having from 6 to 22 carbon atoms per
molecule, in the presence of from 0.5 to 10% by weight of the heat
reaction product of one or more free-radical generating polymerisation
initiators, until the product has a non-volatile content, determined at
the mid-distillation point of the 1-monoolefines, or at 250.degree. C,
whichever is lower, of from 1 to 60 parts by weight of heat-reaction
product;
2. 0 to 25% of a monomer selected from the group consisting of acrylamide,
methacrylamide and N- alkylol derivatives thereof, and hydroxypropyl
acrylates and methacrylates and mixtures thereof;
3. 0 to 8% of an ethylenically unsaturated monomer selected from the group
consisting of mono- and di-carboxylic acids, mono-esters of di-carboxylic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic momohydric
alcohols, nitriles of monocarboxylic acids and mixtures thereof;
4. 0 to 60% of a monomer selected from the group consisting of styrene,
vinyl toluene, vinyl acetate and mixtures thereof;
5. the balance, to a total of 100%, consisting of one or more
copolymerisable monomers selected from the group consisting of esters of
acrylic and methacrylic acids and di-esters of maleic, fumaric and
itaconic acids, with C.sub.1 to C.sub.10 aliphatic and cycloaliphatic
monohydric alcohols, and mixtures thereof:
the percentages of the components 1 to 4 being by weight on the weight of
the copolymer.
5. A process for the preparation of the copolymer claimed in claim 1 which
process comprises reacting together, in the presence of free-radical
generating polymerisation initiator added gradually during the course of
the reaction:
1. 1 to 25% of a 1-olefine heat reaction product, made by heating one or
more normally liquid 1-monoolefines having from 6 to 22 carbon atoms per
molecule in the presence of from 0.5 to 10% by weight on the heat-reaction
product of one or more free-radical generating polymerisation initiators
until the product has a non-volatile content, determined at the
mid-distillation point of the 1-monoolefine, or at 250.degree. C,
whichever is lower, of from 1 to 60 parts by weight per 100 parts by
weight of heat-reaction product;
2. 0 to 25% of a monomer selected from the group consisting of acrylamide,
methacrylamide and N-alkylol derivatives thereof, and hydroxyethyl and
hydroxypropyl acrylates and methacrylates and mixtures thereof:
3. 0 to 8% of an ethylenically unsaturated monomer selected from the group
consisting of mono- and di-carboxylic acids, mono-esters of dicarboxylic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic monohydric
alcohols, nitriles of monocarboxylic acids and mixtures thereof;
4. 0 to 60% of a monomer selected from the group consisting of styrene,
vinyl toluene, and vinyl acetate and mixtures thereof;
5. the balance, to a total of 100%, consisting of one or more
copolymerisable monomers selected from the group consisting of esters of
acrylic and/or methacrylic acid with C.sub.1 to C.sub.10 aliphatic or
cycloaliphatic monohydric alcohols, and mixtures thereof;
all percentages being by weight based on the combined weight of the
reactants.
6. A process as claimed in claim 5 wherein a chain-transfer agent is
included in the reaction mixture in an amount of from 0.02% to 2.0% by
weight on the combined weight of the reactants.
7. A process for the preparation of the copolymer claimed in claim 4 which
process comprises reaction together, in the presence of free radical
generating polymerisation initiator added gradually during the course of
the reaction,
1. 1 to 25% of a 1-olefine heat-reaction product, made by heating one or
more normally liquid 1-monoolefines, having from 6 to 22 carbon atoms per
molecule, in the presence of from 0.5 to 10.1 by weight on the
heat-reaction product of one or more free-radicals generating
polymerisation initiators, until the product has a non-volatile content,
determined at the mid-distillation point of the 1-monoolefines or at
250.degree. C, whichever is lower, of from 1 to 60 parts of weight per 100
parts by weight of heat-reaction product;
2. 0 to 25% of a monomer selected from the group consisting of acrylamide,
methacrylamide and N-alkylol derivatives thereof, and hydroxyethyl and
hydroxypropyl acrylates and methacrylates and mixtures thereof;
3. 0 to 8% of an ethylenically unsaturated monomer selected from the group
consisting of mono and di-carboxylic acids, mono-esters of di-carboxylic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic monohydric
alcohols, nitriles of monocarboxylic acids and mixtures thereof;
4. 0 to 60% of a monomer selected from the group consisting of styrene,
vinyl toluene, vinyl acetate and mixtures thereof;
5. the balance, ,to a total of 100%, consisting of one or more
copolymerisable monomers selected from the group consisting of esters of
acrylic and methacrylic acids and di-esters of maleic, fumaric and
itaconic acids with C.sub.1 to C.sub.10 aliphatic and cycloaliphatic
monohydric alcohols, and mixtures thereof;
all percentages being a weight based on the combined weight of the
reactants.
8. A process as claimed in claim 7 wherein a chain-transfer agent is
included in the reaction mixture in an amount of from 0.02% to 2.0% by
weight on the combined weight of the reactants. |
|
 |
|
 |
Claims |
|
|
|
Description |
|
|
In the field of surface coatings, such as paints and lacquers, for example,
it is well-known to prepare thermoplastic copolymers containing reactive
hydroxyl groups, optionally containing reactive carboxyl groups also, by
copolymerising beta-hydroxy ethyl or propyl acrylate or methyacrylate with
other ethylenically unsaturated co-monomers and to blend such
thermoplastic copolymers with cross-linking agents such as aminoplasts,
phenoplasts, poly-epoxide resins and poly-iso-cyanate resins to provide
hard and durable crosslinked coatings which are useful in coatings for
example for refrigerators, washing machines and motor cars. It is also
well known to prepare thermosetting copolymers containing for example
reactive amide or substituted amide groups.
One disadvantage of known cross-linked coatings derived from acrylic esters
is that their resistance to certain chemicals, especially alkalis, is
somewhat limited, this arising from the presence of sensitive ester
linkages in the coatings. For this reason, among others, it is known to
incorporate in acrylic copolymers major amounts of styrene, a monomer
characteristically resistant to chemicals, but copolymers which contain
substantial amounts of styrene tend to show brittleness. Another type of
ethylenically unsaturated monomer capable of forming homo-polymers lacking
sensitive ester groups is the class of 1-olefines, by which is meant the
mono-alkyl substitution products of ethylene in which the alkyl carbon
chain is straight or branched.
When however attempts are made to incorporate 1-olefine into acrylic type
copolymers in order to reduce the amount of sensitive ester groups
present, by known methods by heating in the presence of free-radical
generating initiator at atmospheric pressure, unsatisfactory percentage
conversion figures are obtained. For example, an acrylic copolymer of
known type was prepared by heating 16 parts hydroxy propyl methacrylate,
0.6 parts methacrylic acid, 60.4 parts of styrene and 23 parts of 2-ethyl
hexyl acrylate in solution in xylene at 140.degree. C in the presence of 1
percent by weight of peroxide initiator and 99 percent of the monomers
originally present became converted into copolymer. In contrast when the
2-ethyl hexyl acrylate in the above recipe had been replaced by a typical
1-olefine of high purity, namely 1-dodecene and a similar procedure
followed only 80 percent by weight conversion of monomers to copolymer was
obtained. This unsatisfactory result may be attributed to the low
copolymerisability under free-radical generating conditions of 1-olefine
monomers.
By reducing the percentage of 1-olefine monomer present and making various
modifications in the procedure as previously practised in the art it was
possible to attain percentage conversion figures in the range 79.5 to 90.
For a copolymerisation process to be acceptable a percentage conversion
figure of at least 90 or 95 and more usually at least 97 is normally
required, though a gain in yield from a copolymerisation process is useful
at any practicable level.
In order to overcome this difficulty attempts have been made to
copolymerise 1-olefines with other ethylencally unsaturated monomers using
free-radical generating initiator in large amounts much larger than the
catalytic amounts usually employed in copolymerisation reactions.
Percentage conversion figures by such methods however leave much to be
desired. Moreover, apart from the high cost of initiator compounds,
significant amounts of residue from them remaining in the product
adversely affect the properties, such as by reducing chemical resistance.
Surprisingly it has now been found that 1-olefines which have been heated
in the presence of a catalytic amount of free-radical generating
initiator, whereby the amount of volatile material becomes reduced, have
improved copolymerisability with other ethylenically unsaturated compounds
under free-radical generating conditions.
It is known that 1-olefines can be polymerised using ionic catalysts of the
Friedel-Crafts type. However, the resulting polymers contain ionic species
which are difficult and expensive to remove, and which may interfere with
any subsequent free-radical co-polymerisation system involving the
polymers. By contrast, the heat reaction products used in this invention
will normally be substantially free of residues derived from ionic
catalysts. The distinction between free-radical generating polymerisation
iniators and ionic catalysts is well understood in the art of polymerising
ethylenically unsaturated compounds.
The present invention accordingly provides a random copolymer consisting
essentially of units of:
1. 1 to 25% of a 1-olefine heat reaction product, made by heating one or
more normally liquid 1-olefines having from 6 to 22 carbon atoms per
molecule in the presence of from 0.5 to 10% by weight on the heat reaction
product of one or more free-radical generating polymerisation initiators
until the product has a non-volatile content, determined at the
mid-distillation point of the 1-olefine, or at 250.degree. C, whichever is
lower, of from 1 to 60 parts by weight per 100 parts by weight of
heat-reaction product;
2. 0 to 25% of a monomer selected from the group consisting of acrylamide,
methacrylamide and N-alkylol derivatives thereof, and hydroxyethyl and
hydroxypropyl acrylates and methacrylates and mixtures thereof;
3. 0 to 8% of an ethylenically unsaturated monomer selected from the group
consisting of mono- and dicarboxylic acids, mono-esters of dicarboxylic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic monohydric
alcohols, nitriles of monocarboxylic acids and mixtures thereof;
4. 0 to 60% of a monomer selected from the group consisting of styrene,
vinyl toluene, vinylacetate and mixtures thereof;
5. the balance consisting of one or more copolymerisable monomers selected
from the group consisting of esters of acrylic and/or methacrylic acids
with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic monohydric alcohols
and mixtures thereof;
the percentages of the components 1 to 4 being by weight on the weight of
the copolymer.
We have found that the di-esters of maleic and/or fumaric and/or itaconic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic alcohols can be
used to replace the acrylate and methacrylate esters of component (5)
either wholly or in part. Thus the invention includes a random copolymer
consisting essentially units of:
1. 1 to 25% of a 1-olefine heat-reaction product, made by heating one or
more normally liquid 1-olefine, having from 6 to 22 carbon atoms per
molecule, in the presence of from 0.5 to 10% by weight on the
heat-reaction product of one or more free-radical generating
polymerisation initiators, until the product has a non-volatile content,
determined at the mid-distillation point of the 1-olefine, or at
250.degree. C, whichever is lower, of from 1-60 parts by weight per 100
parts by weight of heat-reaction product;
2. 0 to 8% of a monomer selected from the group consisting of acrylamide,
methacrylamide and N-alkylol derivatives thereof, and hydroxyethyl and
hydroxypropyl acrylates and methacrylates and mixtures thereof;
3. 0 to 25% of an ethylenically unsaturated monomer selected from the group
consisting of mono- and di-carboxylic acids, mono-esters of dicarboxylic
acids with C.sub.1 to C.sub.10 aliphatic or cycloaliphatic monohydric
alcohols, nitriles of monocarboxylic acids and mixtures thereof;
4. 0 to 60% of a monomer selected from the group consisting of styrene,
vinyl toluene, vinyl acetate and mixtures thereof;
5. the balance consisting of one or more copolymerisable monomers selected
from the group consisting of esters of acrylic and methacrylic acids, and
diesters of maleic, fumaric and itaconic acids with C.sub.1 to C.sub.10
aliphatic cycloaliphatic monohydric alcohols, and mixtures thereof; the
percentages of the components 1 to 4 being by weight on the weight of the
copolymer.
The present invention also provides a method of making these copolymers by
reacting the components (1) to (5) together in the presence of
free-radical-generating polymerisation initiator added gradually during
the course of the reaction.
The present invention also provides a coating composition comprising a
mixture, in an inert diluent, of a copolymer of the invention and a
cross-linking agent therefor; and articles carrying a cured coating of the
copolymer of the invention cross-linked either by means of reactive groups
copolymerised into the copolymer and/or by means of a cross-linking agent
selected from urea-, melamine-, and phenol-formaldehyde condensates, alkyl
melamines, poly-epoxy compounds and poly-isocyanate condensates.
As used herein the term "1-olefine" is defined to mean normally liquid
1-olefines having from 6 to 22 carbon atoms per molecule. The alkyl
substituent of the 1-olefine may be straight, that is to say `normal`, or
branched and contains between 4 to 5 and 20 carbon atoms and which
therefor 1-olefines from 1-hexane or 1-heptene to 1-docosene are included.
Mixtures of two or more 1-olefines are included within the definition.
As used herein the term "heat-reaction product" is defined to mean the
product obtained by heating one or more 1-olefine, as defined above, in
the presence of from 0.5 to 10% of one or more free-radical generating
polymerisation initiators by weight based on the total of 1-olefine and
initiator, until the non-volatile content determined at the
mid-distillation point of the 1-olefine or at 250.degree. C whichever is
the lower is from 1 to 60 parts by weight of per 100 parts by weight of
the heat-reaction product. The initiator is preferably a peroxide e.g.
di-tertiarybutyl peroxide and di-benzoyl peroxide.
The precise chemical nature of the 1-olefine heat-reaction product is not
known with certainty, but the heat reaction product is believed to consist
of a mixture of unreacted 1-olefine and relatively low molecular weight
polymers of the 1-olefine. We think that the volatile portion of the
heat-reaction product is almost entirely unreacted 1-olefine monomer, and
that the non-volatile component is mostly dimer with smaller quantities of
trimer, tetramer and possibly higher oligomers. The relative proportions
of the various components of the heat-reaction product will clearly depend
upon the non-volatile content.
Suitable ethyleneically unsaturated mono- and dicarboxylic acids are
acrylic, methacrylic, itaconic, maleic and fumaric acids. Maleic anhydride
may be used. Examples of suitable esters are methyl acrylate, butyl
acrylate and 2-ethyl hexyl acrylate.
The copolymers of the present invention may be prepared by solution
co-polymerisation in the presence of free-radical generating initiator,
preferably also in the presence of chain transfer agent. The free-radical
generating initiator, which is used in a catalytic amount, that is to say
from about 0.5 to about 6.0 percent, more usually from about 1.0 to about
3.0 percent by weight of the total reactants, may be di-tertiary butyl
peroxide. The initiator should be added gradually during the course of the
copolymerisation reaction, either by continuous `drip-feed` during part or
all of the reaction time or by incremental additions or by a combination
of such methods.
When required, suitable chain-transfer agents are mercaptans, for example
tertiary dodecyl mercaptan and lauryl mercaptan. The amount added is in
the range 0.02 to 2.0 percent, more usually 0.3 to 1.0 percent by weight
based on the total weight of monomers and is selected with a view to
controlling the average molecular weight of the copolymer to impart an
acceptable workable viscosity to a solution of the compolymer in an
organic solvent at about 50 - 60 percent solid content in 100 parts by
weight of solution. It is well-known in the art that the amount of
chain-transfer agent to be used may be critical.
In a preferred method for making the copolymer the heat-reaction product is
charged into a reaction vessel and heated to the reaction temperature
which normally lies in the range of 80.degree. to 160.degree. C. However,
for systems including vinyl acetate which boils at .about.71.degree. C
reaction temperatures may need to be reduced. The other monomers, having
been mixed together as a separate operation with some inert organic
solvent such as xylene and at least about 0.5 percent of initiator, are
then added gradually as a drip-feed over a period of several hours.
Heating is then continued, preferably with incremental additions of
catalyst at intervals of 1 to 2 hours until a test sample of the reaction
mixture, removed and tested for solid content by known methods, indicates
a value approaching 100% conversion. (Heating times are frequently in the
range of 1 to 24 hours). The reaction mixture is then cooled and further
additions of inert organic solvent made as required.
The proportions and types of the other co-reactants to be selected are
determined by the purpose for which the copolymer is to be used and are
adjusted according to methods known in the art to provide the desired
balance between hardness, flexibility and chemical resistance in the final
coating together with good adhesion.
The copolymers of the present invention are random copolymers, by which is
meant that the various components of the starting reaction mixture (which
are all monomeric except for the heat-reaction product, which contains a
proportion of oligomer) are joined together in the copolymer in a random
order. We believe that the oligomeric part of the heat-reaction product
incorporated into the copolymer does so via a terminal unsaturation, thus
behaving as a 1-olefine monomer with a large pendant group.
The copolymers of the present invention may be either thermoplastic or
thermosetting. Thermosetting copolymers can be made by including
acrylamide or methacrylamide in the monomers used. Thermoplastic
copolymers can be cured using conventional curing agents as is described
below. Even though copolymers containing acrylamide and/or methacrylamide
and/or their N-alkylol derivatives are entirely thermosetting in their own
right it is common practice to include additionally a curing agent in
compositions containing the copolymer to improve the adhesion, hardness
and alkali resistance of the cured film. N-alkylol acryl-amide and
methacrylamide may be used per se as starting materials or generated in
situ in the reaction medium e.g. by reaction of acrylamide or
methacrylamide with butanol/formaldehyde included in the reaction mixture.
Alpha-olefines are prepared by processes which produce as primary products
mixtures of many different olefinic materials including materials gaseous
at ordinary temperature through to solid materials. A given mixture of
1-olefines may be largely separated into individual 1-olefines, or into
close boiling-range fractions containing mixtures of 1-olefines with
similar boiling points, by distillation. Commercial high purity 1-olefines
usually distil over ranges from first distillation temperature to final
distillation temperature which vary from about 10.degree. C for 1-heptene
to about 40.degree. C for 1-heptadecene. Commercially available
close-boiling fractions may distil over a range of from about 50.degree. C
for a C.sub.6 - C.sub.7 fraction to about 90.degree. C for a C.sub.9 -
C.sub.10 fraction and correspondingly wider ranges for high boiling
fractions. Preferably for the present invention the difference between the
first and final distillation temperatures of the alpha-olefine mixture
selected does not exceed about 100.degree. C.
The commercially available mixtures consist mainly of normal 1-olefines but
may contain minor amounts of branched chain 1-olefines and also of
olefines which have an ethylenically unsaturated group within the chain
rather than in the alpha position.
Some alpha-olefines which are suitable for use in this invention are listed
in Table 1, together with an approximate indication of their average first
and last distillation temperature determined by well known methods, and
mid-distillation temperatures derived from them as the arithmetic mean.
Table 1
______________________________________
First Final Mid-
Distillation
Distillation
Distillation
Temp. .degree.C.
Temp. .degree.C.
Temp. .degree.C.
______________________________________
Hexene-1 59 67 63
Heptene-1 90 120 105
Octene-1 118 135 127
Nonene-1 140 160 150
Decene-1 154 195 180
Undecene-1 185 205 195
Dodecene-1 207 245 226
Tridecene-1 225 260 242
Tetradecene-1
243 270 257
Pentadecene-1
260 280 270
Hexadecene-1
270 310 290
Heptadecene-1
300 335 317
Octadecene-1
Beyond scope of normal methods.
______________________________________
The actual mid-distillation temperature varies somewhat between 1-olefines
from one source of supply and another and is to be determined, likewise
the general suitability of a given sample of 1-olefine, by practical
trail. As a general guide the 1-olefine should be substantially free from
substances which might unduly inhibit free-radical polymerisation, such as
sulphur compounds and added oxidation inhibitor. Sulphur compounds
preferably should not exceed a few parts per million and aromatic,
naphthenic, acetylenic and di-olefine compounds should preferably be
absent.
The free-radical-generating initiator should be selected to generate free
radicals at a heating temperature appropriate to the 1-olefines used.
Di-tertiary butyl peroxide for example, is suitable for heating
temperatures in the range of 130.degree. to 200.degree. C. Our preferred
initiators are di-tertiary butyl peroxide and di-cyclohexyl
perdicarbonate.
Other initiators which may be used include organic peroxides,
hydroperoxides and per-acids and esters thereof, for example, tertiary
butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide and di-tertiary
butyl peroxide. Azonitrile initiators, for example, azo-bis-iso-butyro
nitrile may also be used. The initiator is normally used in a catalytic
amount, by which is meant between about 0.5 and about 6 parts, more
usually from 1.4 to 5.6 parts by weight per 100 parts by weight of
1-olefine monomer but the invention also envisages the use of amounts up
to 10 parts by weight of initiator per 100 parts by weight of 1-olefine
monomer in special cases.
In the preferred method of preparing the heat-reaction product, the
1-olefine monomer is charged into a reaction vessel equipped with reflux
condenser, thermometer, stirrer and means for making liquid additions
during the course of the reaction and heated with stirring to a
temperature in the range of 50.degree. C to 250.degree. C, more usually in
the range of 60.degree. C to 200.degree. C, the reaction temperature being
selected having regard to the distillation range and reactivity of the
1-olefines used. When the desired temperature is reached addition of
initiator may be commenced as drip-feed which continues through the course
of the reaction. Alternatively all the initiator may be added to the
reaction vessel at the commencement of the reaction. Organic solvent of a
substantially inert type may be present during the reaction if desired.
The heating time will generally be within the range of 5 minutes to 24
hours. The progress of the reaction is followed by determining the
non-volatile content of small test samples removed for the purpose,
heating being discontinued when the desired value has been reached.
The reaction may be effected in an atmosphere of inert gas if desired.
For 1-olefine starting materials having 6 to 13 carbon atoms in the
molecule the non-volatile contents are determined by heating approximately
1 gram of the reaction mixture for 1 hour at the mid-distillation
temperature of the 1-olefine starting materials as determined by
well-known methods such as described in Specification ASTM D. 1078. For
1-olefine starting materials having 14 to 22 carbon atoms, which tend to
have mid-distillation temperatures which are rather high, non-volatile
contents are determined at 250.degree. C. It is important for
characterisation of the heat-reaction products that the non-volatile
contents be determined at the appropriate temperature. While the reactions
which occur during the heat treatment are not fully understood at least
part of the starting monomeric material becomes converted to relatively
low-molecular weight polymeric material of a type which become vaporised
at relatively low temperatures so that the non-volatile content determined
experimentally is, more than usually in the art, dependent on the
temperature at which the determination is made.
The heat-reaction products used in this invention are stable in the sense
that they retain their advantageous properties for at least 14 days when
stored at ambient temperature.
The level of non-volatile content, and the nature of substantially inert
organic solvent if present, are adapted to the end-use to which the
heat-reaction product is to be put, and in particular, for securing a
satisfactory degree of compatibility with ethylenically unsaturated
compounds with which it is to be subsequently co-polymerised. In general,
the non-volatile content (as defined) will be in the range of 1 to 60,
more usually from 5 to 50 parts by weight per 100 parts of heat-reaction
product. Higher non-volatile contents favour good subsequent percentage
conversion but may promote incompatibility with other ethylenically
unsaturated copolymerisable compounds present in a subsequent copolymer. A
generally preferred range is 7 parts to 40 parts by weight per 100 parts
of heat-reaction product.
In tests with monomeric starting materials it was found that approximately
1 gram quantities became entirely evaporated when heated for 1 hour at the
following temperatures.
Table 2
______________________________________
1-octene 40.degree.C
1-decene 80.degree.C
1-dodecene 120.degree.C
1-octadecene 140.degree.C
______________________________________
It is an advantage of the 1-olefine heat-reaction products used in the
present invention that their presence in the present copolymers has little
tendency to cause brittleness. It is necessary, however, that they are
selected to provide satisfactory compatibility not only with the other
co-monomers when in copolymerised form, but also with any added
cross-linking agent that may be used. Preferably the 1-olefine
heat-reaction product is prepared from 1-olefines with 6 to 14 carbon
atoms per molecule and with a non-volatile content determined at the
mid-distillation temperature of the 1-olefine starting material of 5 to
30, most preferably between 8 and 15 percent by weight. Examples of stable
1-olefine heat-reaction product are as follows:
Product A
1-Decene 95.8
Di-tertiary butyl peroxide
4.2
100.0
The 1-decene was charged into a reaction vessel fitted with stirrer,
thermometer, condenser and means for making addition of liquid during the
course of the reaction, and heated to 165.degree.-170.degree. C. A
drip-feed of initiator was then started and continued for 1-hour.
Characteristics of the 1-decene used were:
Specific gravity 60.degree./60.degree.F
0.744
Normal 1-olefines at least 94.6%
Mono-olefines at least 98.5%
Saturated materials
maximum 1.5%
Distillation range 5% over 164.degree.C
95% over 175.degree.C
Mid-distillation temperature
169 - 170.degree.C
The product was a substantially water-white liquid of viscosity less than
1/2 poise at 25.degree. C and a non-volatile content of 13.4 percent by
weight determined by heating approximately 1 gram for 1 hour at the
mid-distillation temperature.
______________________________________
Product B
1-Decene 96.7
Di-tertiary butyl peroxide
3.3
100.0
______________________________________
The procedure was as described for Product A above except that after
heating for 1 hour the non-volatile content was 9.9 percent when
determined in the same manner.
______________________________________
Product C
1-Decene 97.2
Di-tertiary butyl peroxide
2.8
100.0
______________________________________
The procedure was as described for Product A except that after heating for
1 hour the non-volatile content was 10.8 percent when determined in the
same manner.
______________________________________
Product D
1-Octene 98.6
Tertiary butyl per-benzoate
1.4
100.0
______________________________________
The 1-octene was charged into a reaction vessel as hereinbefore described
and heated to 125.degree. C. A drip feed of initiator was then commenced
and completed after 30 minutes. At this point the non-volatile content
measured at 123.degree. C was 1.5 percent by weight. The characteristics
of the 1-octene used were:
Specific gravity 60.degree./60.degree.F
0.718
Normal 1-olefines at least 95.5%
Mono-olefines at least 98.5%
Saturated compounds
maximum 1.5%
Distillation range 5% over 118.degree.C
95% over 128.degree.C
Mid-distillation temperature
123.degree.C
Products E to I
Heat-reaction products were prepared using 1-octene as used in Example 3
and using the same procedure except that the amount of initiator and the
time of heating were varied. All initiator was added within 2 hours of the
heating temperature being reached.
______________________________________
Time of heating Parts per 100
Percent
of initiator non-volatile
______________________________________
Product E
1 hour 2.8 4.0
F 11/2 " 4.2 6.2
G 2 " 5.6 7.8
H 21/2 " 5.6 8.1
I 4 " 5.6 7.7
______________________________________
Products J - O
Heat-reaction products were prepared in the same manner as in Examples D to
I above except that the 1-octene was replaced by 1-dodecene and
di-tertiary butyl peroxide replaced tertiary butyl perbenzoate. The
temperature of heating was 190.degree.-200.degree. C and volatile contents
were determined at 212.degree.-213.degree. C. The characteristics of the
1-dodecene used were:
Specific gravity 60.degree./60.degree.F
0.762
Normal 1-olefines at least
93.6%
Mono-olefines at least
98.5%
Saturated compounds maximum
1.5%
Distillation range 5% over
205.degree.C
95% over 220.degree.C
Mid-distillation temperature
212-213.degree.C
Time of heating
Parts per 100
Percent
of initiator non-volatile
______________________________________
Product J
30 mins. 1.4 11.1
K 1 hour 2.8 23.1
L 11/2 hours 4.2 32.1
M 2 hours 5.6 39.5
N 21/2 hours 5.6 42.1
O 4 hours 5.6 48.5
______________________________________
Products P - S
Heat-reaction products were prepared in the same manner as described for
Examples J to O above except that 1-dodecene was replaced by 1-octadecene
and non-volatile contents were determined at 250.degree. C. The
characteristics of the 1-octadecene used were:
Specific Gravity 60.degree./60.degree.F
0.792
Normal 1-olefines
at least 88.6%
Mono-olefines at least 98.5%
Saturated compounds
maximum 1.5%
Distillation range:
Beyond range of normal methods
______________________________________
Time of heating
Parts per 100
Percent
of initiator non-volatile
______________________________________
Product P
30 mins. 1.4 17.3
Q 1 hour 2.8 34.6
R 11/2 hours 4.2 45.7
S 2 hours 5.6 55.2
______________________________________
With reference to the figures for non-volatile contents tabulated in the
third column determined at 250.degree. C, it was found that the
1-octadecene starting material became completely evaporated when
approximately 1 gram was heated for 1 hour at 250.degree. C and in fact
also at 140.degree. C, leaving residue nil in both cases.
Product T
______________________________________
1-Decene 99.1
Di-tertiary butyl peroxide
0.9
100.0
______________________________________
1-Decene of the same quality as used in Example 1 was charged into the same
reaction vessel and heated following essentially the same procedure as for
Example 1 at 165.degree.-170.degree. C, heating being continued for 40
minutes. The non-volatile content was 2.4 determined at the
mid-distillation temperature.
Products U to Y
These were on the basis of Example 19 above except that amounts of
initiator and heating times were varied. Nonvolatile contents were
determined at the mid-distillation temperature namely
169.degree.-170.degree. C and also at 150.degree. C, both on the freshly
prepared heat-reaction products and again after storage for 14 days at
ambient temperature.
Results are set out in Table 3. The difference between the figures in the
fifth and sixth columns are within experimental error and indicate
stability as regards non-volatile content for the heat-reaction products
for 14 days.
Table 3
__________________________________________________________________________
Product
Time of
Initiator
Percent non-
Percent non-
Percent non-
heating
Parts per
volatile at
volatile at
volatile at
mins.
100 169-170.degree.C
150.degree.C (initial)
150.degree.C (after
14 days)
__________________________________________________________________________
T 40 0.9 2.4 3.5 4.0
U 80 1.8 8.6 11.3 12.1
V 120 2.8 15.6 19.2 18.9
W 60 2.8 10.8 13.5 12.8
X 90 4.2 17.9 21.4 22.0
Y 120 5.6 30.6 35.0 34.8
__________________________________________________________________________
Product Z
A heat-reaction product was prepared from hexane-1 as follows:
1-Hexene 94.4
Di-cyclohexyl perdicarbonate
5.6
100.0
1-Hexene mixed with di-cyclohexyl perdicarbonate was charged into the same
reaction vessel and heated to 63.degree. C and maintained at
62.degree.-65.degree. C for 1 hour. The non-volatile content was 18.1
determined at the mid-distillation temperature.
The following examples illustrate the preparation of copolymers according
to the invention.
EXAMPLE 1
Part A
1-Decene heat-reaction product
(Product A) 7.19
Part B
Butyl acrylate | | |
