Note: Descriptions are shown in the official language in which they were submitted.
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NON-BAKING BINDERS
The invention relates to non-baXing binders based
on pol-vbutadiene oils which oils are liquid at room
temperature and specific hydrocarbons and/or gum oil
(turpentine) and to the use thereof for the consolida-
tion, constructional glueing, coating or impregnation of
building materials, residual materials, waste products
and other materials of any kind.
The use of butadiene oils that are liquid at room
temperature for the production of non-baking resins has
been known in the art for a long time; cf~, for example,
Rompps Chemie-Lexikon, 9th edition, page 32~0 ~Heidel
and Dittmann, Chimia 22 (1968), pp. 213-218~. However,
butadiene oils have hardly found acceptance in the
building sector because they are di~ficult to process.
The liquid polybutadiene oils are known to desiccate
relatively fast when exposed to the oxygen of the air,
so that a storage thereof under a protective gas is
recommended. Also the use of solvents such as white
spirit for adjusting the viscosity of the polybutadiene
oils involves some difficulties, if the product to be
consolidated with the polybutadiene oils is intended to
be dried in the air at conventional ambient temperatures
such as room temperature. Moreover, the commercially
available polybutadiene oils do most readily react with
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water, so that hitherto the building materials to be
bonded had to be employed in a particularly dry,
virtually anhydrous condition.
EP O 211 712 Al describes an organic binder for the
treatment of porous building materials with a solution
of polybutadiene oils that are liquid at room temperatu-
re in aromatic or aliphatic hydrocarbons, and more
specifically xylene, toluene, gasoline F and white
spirit.
Thus, it is one object of the present invention to
provide non-baking (air-drying) binders based on poly-
butadiene oils that are liquid at room temperature,
which binders can be readily handled even in the absence
of a protective gas atmosphere and impart a high com-
pressive strength to the materials to be consolidated.
When materials are to be adhesion-bonded, coated or
impregnated, the main goal is to impart a stron~
cohesion to said materials and/or to protect the surface
from environmental influences as well as to provide a
possibly optimum bond between the materials or primer
for further surface treatments.
It is a further object of the present invention to
recycle residual materials and waste materials such as,
for example, plastics or foam residues for a suitable
re-use.
The above-mentioned objects are attained by means
of non-baking binders based on polybutadiene oils which
oils are liquid at room temperature and aliphatic hydro-
carbons characterized in that they contain aliphatic
hydrocarbons and/or gum oil ~turpentine) which are free
from aromatics.
3 ~
As a result of extensi~e time-consuming tests it
was surprisingly found that the hydrocarbons and/or the
gum oil (turpentine) which are free from aromatics are
capable of imparting a reduced viscosity to commercially
available polybutadiene oils so that for the first time
they are extremely easy to handle. Here, the feature of
an absence of aromatics is of particular significance,
because the conventional contents of aromatics in com-
mercially available aliphatic hydrocarbons such as, for
example, white spirits, render the binder unusable and
are not recommendable for reasons of environment
protection.
It was found that by means o~ the present invention
even materials such as a sand containing more than 2% by
weight o~ water can be bonded, whereas hitherto in prior
art particular preparations had to be made in order to
keep the water contents as low as possible, for example
by a step of thorough glowing. Thus, so far it was
required to employ a sand having an SiO2 content in
excess of 99.5%.
In addition thereto it was found that in the
presence of the aliphatic hydrocarbons and/or the gum
oil (turpentine) which are free from aromatics the
polybutadiene oils can be stored in commercial
containers in the absence of a protective gas atmosphere
for a virtually unlimited time without any change occur-
ring in the properties. However, on the other hand,
upon mixing, spreading, after high-pressure or low-
pressure procedures, immersion, spraying or other
operations with building materials, residual materials,
waste products and other materials of any kind a setting
or drying or baking time is attained which allows a
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problem-free application of the non-baking binders for a
variety of products.
For example, at room temperature or at a slightly
elevated temperature of up to about 50 C or 70 DC there
is achieved a pot life (setting time) of from a few
hours to some days, which pot life may be adjusted such
as to meet the particular requirements. Processing
temperatures of below O ~C, for example down to -50 ~C,
are likewise readily usable. Apart from the temperature
the pot life will of course depend also on the materials
to be consolidated, to be bonded, to be coated or to be
impregnated and on the amount of the non-baking binder
relative to the amounts of the respective materials. An
adjustment of a pre-selected pot life value will be
attainable by simple tests, more particularly by varying
the temperature and the amount of binder in relation to
the respective materials. Furtheron, the ratio of the
amounts of polybutadiene oil and aromatics-free ali-
phatic hydrocarbons and~or turpentine may of course be
varied within a wide range so that, besides the pot
life, the consolidating action of the non-baking binder
can also be varied. Here, high proportions of poly-
butadiene regularly result in strong bonds. An extreme-
ly high setting time may be adjusted by an addition of
water, for example in an amount of up to ~0~ relative to
the binder. The use of up to 99% of water allows to
make the land to grow green.
The term "polybutadiene oils" as used within the
present invention is understood to include both unsub-
stituted and substituted polybutadienes which are
commercially available in many forms from a variety of
suppliers.
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Particularly preferred within t:he scope of the
present invention i5 a polybutadiene oil which comprises
about 72~ of 1,4_cis double bonds, about 27% of
1,4-trans double bonds and about 1% of 1,2-vinyl double
bonds and has a molecular weight of about 1,800, a
density of about 0.91 g/cm3 and a viscosity of 770 mPa-s
(Brookfield) at 20 C. In the product commercially
available under the designation "Polyol(R) 110", the
proportions of the respective double bonds vary around
the values mentioned. Also, the indication of the
molecular weight does not mean that there be present
exclusively one polybutadiene having said molecular
weight, but it denotes an average molecular weight which
may also vary with different batches. The viscosity
value set forth above shows that the polybutadiene oil,
although it is fluid, is already relatively highly
viscous. Nevertheless, such polybutadiene oils still
have a sufficient fluidity even at temperatures down to
-50 ~C.
In a further embodiment, addi~ives known in the art
such as those added to synthetic rubbers may in the same
manner be added to the polybutadiene oils. A survey on
rubber chemicals and additives known in the art is found
in Ullmanns Enzyklopadie der Technischen Chemie, 4th
edition, volume 13, pages 637-671. Thus, in a preferred
embodiment of the present invention the polybutadiene
oils in particular may contain hydrophobing agents,
anti-ageing agents, fatigue-preventing agents, fillers,
pi~ments as well as any of the polymer resins known in
the building sector based on polyurethanes, silicones,
epoxides, acrylates, polyesters, polysulfides as based
on inorganic or organic solvents and also water-based
ones (solutions or emulsions). Suitable amounts of such
agents are known to the artisan, on the one hand, from
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the production of synthetic rubber; on the other hand,
these amounts are determinable by way of simple testing.
The pre-requisite for a use thereof in any case is the
compatibility with the polybutadienes and with the
solvents to be used. Thus, to the binder according to
the invention there may be added, for example, inorganic
and/or organic hydrophobing agents known in the art,
such as organotin compounds, silicones, alkylchloro- and
alkylalkoxysilanes, paraffins, waxes, metal soaps, also
those additionally containing aluminum and/or zirconium
salts, guaternary organic compounds, urea derivatives of
fatty acid-modified melamine resins. The amounts to be
added of such compounds will be governed by the desired
degree of hydrophobization and may be determined, if so
required, by the artisan with simple tests.
In order to accelerate baking, the use of
transition metal compounds, and especially of organo-
metal salts of transition metals is likewise known from
the production of synthetic rubbers. Accordingly, one
preferred embodiment of the present invention consists
of employing polybutadiene oils with desiccants of the
type of polyvalent organometal salts which allow to
adjust a particularly pre-determined setting time.
In a similar manner it may be required or desired
to add wetting agents to the polybutadiene oils in order
to provide an improved adhesion strenyth between the
baked polybutadiene oils and the material to be con-
solidated, to be bonded, to be coated or to be impreg-
nated. Du~ to the ~ se hydrophobic nature of the
polybutadiene oils themselves, non-ionic wetting agents
ha~e shown to be particularly advantageous, among which
nonylphenol ethoxylates are particularly preferred. As
the organometal salts there are preferably used
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compounds containing cobalt, lead, magnesium and/or
manganese, however such low amounts that the environ-
mental compatibilty of the product will not be impaired
and, more specifically, that the water will not be
unduly polluted such as to violate the water-protective
provisions of the pertinent building regulations.
It is true, all known hydrocarbons are basically
suitable to reduce the viscosity of polybutadiene oils.
However, commercial hydrocarbons frequently used as
solvents mostly contain a larger or lesser amount of
aromatics, and particularly of benzene. In contrast
thereto, the invention consists of employing aromatics-
free aliphatic hydrocarbons having evaporation indices
according to DIN 53 170 (evaporation index of diethyl-
ether = 1) in excess of 50, and preferably within the
range of from 100 to 1,000. This causes, upon the
application of the binders, the aromatics-free aliphatic
hydrocarbon or aliphatic hydrocarbon mixture to evapor-
ate in a comparable time while the autoxidation of the
polybutadiene oils proceeds. Thus, within the scope of
the present invention, it is preferred to use mixtures
of isoparaffins having from 8 to 16 carbon atoms, and
especially those having from 11 to 13 carbon atoms, and
contents of aromatic substances of less than 100 ppm,
and especially of less than 50 ppm. That is, the term
"aromatics-free aliphatic hydrocarbons" as used in the
context of the present invention is meant to include
those aliphatic hydrocarbons to be employed - as also
commercially available - which may contain just minor
amounts of benzene, for example in the amount of 100 ppm
or below.
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The term "gum oil" ("turpentine") in the context of
the present invention is understood t;o denote the gum
oil (turpentine) as defined, for example, in Ullmanns
Enzyklopadie der Technischen Chemie, 4th edition, volume
22, pages 553-564, which in the broadest sense includes
natural or synthetic mixtures of mono- or bicyclic mono-
terpenes besides usually small amounts of terpene-oxygen
compounds (e.g. terpene alcohols), sesquiterpenes and
other compounds. Thus, there is further differentiated
between gum turpentine, wood turpentine (steam-distilled
turpentine), sulfate turpentine and destructively
distilled wood turpentine, inclusively turpentine sub-
stitutes, pine oil or orange terpenes.
In a particular embodiment of the present in-
vention, pine oil may be employed as a component of the
non-baking binder. The term "pine oil", according to
Ullmanns Enzyklopadie der Technischen Chemie, 4th
edition, volume 22, pages 561-562, is understood to mean
flammable, colorless to yellow, oily liquids having a
pleasant odour, the main components of which are terpene
alcohols, mainly ~-terpineols, and terpene hydrocarbons.
The composition of synthetic pine oil is distingulshed
from that of natural pine oil, especially by the absence
of borneol, camphor, esters, anethole and ses~uiterpe-
nes. Nevertheless, both synthetic and natural pine oils
are li~ewise usable within the scope of the present
invention.
Thus, according to the invention the binders may
contain both aromatics-free hydrocarbons and turpentine
besides each other. Moreover, a substitution of the
hydrocarbons by the turpentine and vice versa is of
course also possible. The ratio of amounts of these
~ ?,~
components relative to one another i5 usually not
critical within the scope of the present invention, as
both components serve to attain th~ same object, i.e. to
adjust the viscosity and the baking time of the binder.
Moreover, these components are causative for generating
a good resistance even to moist materials and make the
binders according to the invention available to a very
broad range of applications.
Also of certain importance is the total amount of
the aromatics-free aliphatic hydrocarbons and/or tur-
pentine, relative to the amount of the polybutadiene
oils. If the amount of the aromatics-free aliphatic
hydrocarbons and/or turpentine is too low, then the
viscosity of the binder will of course be high, so that
the binder may appear to be not suitable for many
practical applications. On the other hand, a low
viscosity may be desirable for some applications,
especially in the cases of adhesion~bonding or
impregnating of materials, where it is desired that the
binder will penetrate as deeply as possible into the
material. In contrast thereto, when surfaces are to be
coated, a high viscosity may be desirable in order to
cause the binder to immediately adhere to the surface.
The same may be applicable to some particular uses for
glueing or impregnating.
If, on the other hand, the dilution of the poly-
butadiene oils with the aromatics-free aliphatic hydro-
carbons and/or turpentine is too high, then the
consolidating effect provided by the binder will be too
low; this may be compensated by an appropriately select-
ed ratio of the amounts of the matexial to be consolida-
ted and the binder.
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Accordingly, one preferred embodiment of the
present invention consists of binders which contain, in
addition to polybutadiene oils, aromatics-free aliphatic
hydrocarbons in an amount of from 2 to 98% by weight,
and especially from 5 to 60% by weight. Due to the own
odor of the turpentine, the amounts employed thereof are
usually kept lower, so that besides the polybutadiene
oils the turpentine is contained in the binders accord-
ing to the invention in an amount of from 0.5 to 30% by
weight, and especially from 1 to 20% by weight. The
amounts indicated for aromatics-free aliphatic hydro-
carbons and/or turpentine are considered to cover those
cases where either the aromatics-free aliphatic hydro-
carbons or the turpentine, and especially pine oil, are
the only diluent component of the binder as well as the
cases where both the aromatics-free aliphatic hydro-
carbons and the turpentine are contained in the aromatic
binders. The upper limits set forth refer to mixtures
comprising both the aromatics-free aliphatic hydro-
carbons and the turpentine, so that at least 2% by
weight of the polybutadiene oils are present in the
binders.
A further embodiment of the case of the simultan-
eous presence of aromatics-free aliphatic hydrocarbons
and pine oil comprises the presence of from 35 to 89.5%
by weight, and especially 35 to 55% by weight, of
aromatics-free aliphatic hydrocarbons and of from 1 to
15% by weight, and especially 5 to 15% by weight, of
turpentine, relative to the binder. Also here the upper
limits mentioned above are applicable.
Substituted and modified polybutadiene oils are
also known in the state of the art. For example, an
2 ~ .a ~ 3 ~
ester-modifiPd water-miscible polybutadiene oil is sold
under the designation of Polyvest(R) OC 4000. The
commercial product consists of 74% of an ester-modified
polybutadiene oil which has been amine-neutralized and
26% of butyl glycol. It was surprisingly found that
this water-miscible polybutadiene oil can be ~xcellently
dispersed with turpentine. The resulting dispersions
can be readily introduced into the binder compositions
mentioned above. ~pon mixing with a fine moist or dry
quartz sand, for example, there will be obtained a
building material which does not only have an extremely
high compressive strength, but which in addition thereto
exhibits a very high resilience when compared to that of
concrete or cement products, so that the resulting
materials, once comminuted to have the appropriate grain
size, are also suitable for making thin-bed putty.
Accordingly, one preferred embodiment of the
present invention consists of binder which is character-
ized in that from 1/2 to 1/20 of the turpentine has been
replaced by ester-modified amine-neutralized polybuta-
diene oil. Moreover, one further preferred embodiment
of the binders according to the invention is character-
ized in that the ester-modified amine-neutralized poly-
butadiene oil is employed in an amount of from 10 to 30%
by weight of the above-mentioned amount of turpentine.
By way of the use of the binders according to the
invention there may be consolidated, coated or impregna-
ted, in the first place, building materials, residual
materials, waste products and other materials of any
kind. Once the materials have been wetted with the
binder, for example by mixing, immersing, spraying,
spreading, oxidative curing is effected by the action of
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the oxygen of the air, preferably at room temperature,
whereby the material-binder mixture is glued together.
Thus, natural rocks can be durably consolidated, or
contaminated building material, domestic waste or other
materials of various kinds can be encapsulated by the
binders according to the invention.
The ratios of amounts of the materials to be
consolidated, to be bonded, to be coated or to be
impregnated and the binders depend on the particular
requirements of the intended application. If a high
consolidating effect is desired, the amount of binder
will of course have to be high, while a low amount of
binder provides a low consolidating effect, but a high
creeping effect. In one preferred embodiment of the
invention, the binders are employed in an amount of from
0.02 to 30% by weight, relative to the material, for
consolidating, bonding, coating or impregnating building
materials, valuable materials, waste materials and other
materials of all kinds. A particularly preferred
embodiment of the present invention comprises the use of
an amount of from 1.5 to 10% by weight of the binder for
consolidating building materials, residual materials,
waste materials and other materials.
The selection of the materials to be consolidated,
to be bonded, to be coated or to be impregnated is
virtually unlimited. Thus, more particularly, moist or
dry sand, expanded slate, gravel, cement, crushed rock,
wood, mineral fibers, for example fibers of asbestos,
rock wool, glass or glass wool, foam granules, wood
wool, glass wool, rock wool, mica, expanded clay, loam,
clay, melt granules, fibers made of synthetic or natural
products, ceramic fibers, plastics parts, and especially
2 ~ ~q ~) c~ ~';g 'i
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those made of polyethylene, polyurethane, polyvinyl
chloride, polystyrene, the granules or foams made there-
of, minerals, micro-minerals, dusts of all kinds,
carbonates, used-tire granulates, grained waste, sewage
sludge, combustion residues, fly ashes, waste leftovers
from composite members or cement products, slags, glass,
foam glass granules, ceramic parts and wastes can be
consolidated, bonded, coated or impregnated by means of
the binders according to the invention.
Thus, in greater detail, the binders according to
the invention may be used for producing consolidated
areas such as road areas, sidewalk areas, bikeway areas,
tennis courts, car park and garage driveways, courtyard
and backyard paving, pavement pointings, balance and
levelling floors, screeds for floor heating, levelling
screed, molding concrete, thin-bed mortar, thin-bed
putty, joint cement, reversed roofs, water-permeable
drainage rings around trees, pre-fabricated units and
molded parts such as panels, paving, laminated boards,
plant vessels, statues, spacers, drainage panels, filter
plates, stone blanks, natural-rock replicas, natural
rock restorations and in half-timbered building. By
means of the present invention it is possible, to bind
asbestos fibers, for example when present in the form of
spray asbestos of fiber panels, in such a way that an
immediate decontamination or clearing from asbestos by a
removal of the materials will not be required. Impuri
ties and contaminations will usually not interfere, so
that the binders according to the invention can be
directly applied onto the surfaces without any pre-
cleaning. In the same manner the binders according to
the invention can be employed to consolidate plasters or
stones of all kinds. In mining, a use is possible for
binding coal dust.
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2 ~ 7,
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A further possibility of coating surfaces, for
example, consists of using the binder~s according to the
invention as underseal material or protective against
rockfall and gravel in the automotive! sector and as an
adhesive bridge with grease-contain.ing materials and
high-grade steel.
Joint seals, tapes and areas exposed to the action
of noxious materials may be sealed, especially by spray-
ing or spreading, so that the noxious materials will be
prevented from escaping and a disposal and storage
thereof as otherwise obligatory will no longer be
necessary.
For example, the binders according to the invention
may be employed for the consolidation of single-sized or
multi-sized dry sands. The binders, the colors of which
usually range from bright green through dark green,
brown to violet, mostly have a weak specific inherent
odorl that may be superimposed by some amounts of pine
oil.
Once the sands or other materials have been wetted
with the binders according to ~he invention, the process
of oxidative curing by the oxygen of the air proceeds,
~or example at room temperature or an elevated tempera-
ture, and the building material/binder mixture is glued
together to form a body the water-permeability of which
is retained.
Once said body is produced in a negative mold, once
set it may be released therefrom without trouble.
Shaped parts may be directly manufactured in wooden or
other molds. Release agents such as, for example, form
oil usually are not required.
. ~
e
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The binders according to the invention may be
employed, for example, as one-component system for
consolidating sands of various grain sizes. Depending
on the grain size distributions and moisture contents,
input amounts of from 0. 5 to 10% by weight, and
especially from 1. 5 to about 10% by weight, of the
binder, relative to the material to be consolidated, are
preferred. Upon the use of the binder according to the
invention, the color shade of the material to be
consolidated, and especially of the sand, is not
changed. The sand structure and the natural contents of
hollow space in the sand are almost completely retained
even upon a most compact storage.
Thereby, a good water permeability is constituted
of cured binder-sand mixtures. A coloration of the
masses, if so desired or required, is possible by way of
an addition or ~r se known weather-resistant colorant
pigments to the materials to be consolidated, and so is
a previous addition of colorant pigments to the binders.
Curing of the mixtures is effected by an absorption
of oxygen from the air and, hence, is temperature-
dependent. Typical processing times for mixtures of the
binders with various materials of all kinds, for example
sand, amount to 120 minutes at 3 C or 60 minutes at
20 -C. The binder-sand mixtures are preferred to be
produced in mixer devices ~gravity mixers) and have to
be further processed immediately. Smaller amounts may
be readily processed with the use of commercially avail-
able adapters for drilling machines. It is also
possible to prepare the mixes by hand.
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If the binders according to the i.nvention are added
to commercially available cement mixtures, and prefer~
ably trass cement compositions whi.ch, for example,
contain 10 parts by weight of water per 100 parts by
weight of trass cement, then a mass se!tting to be water-
resistant can be obtained. Upon the use of the above-
mentioned modified polybutadiene oil in the binder com-
position there are obtained more or less resilient
molded parts or, in the raw state, also a ready-to-use
mortar, and especially thin-bed mortar, fluid putty or
thin-bed putty, all of which may be employed for the
restoration of concrete. Also possible is the use of
the binders in conventional adhesion promoters or
coating agents. Hereby the materials may be partially
or completely encapsulated.
In addition thereto, it will be possible to use the
binders as additives in all known concrete, screed,
plaster and joint materials. Irrespectively of whether
these materials are of mineral, synthetic or synthetic-
modified origin, the property profile of the materials
employed will not be deteriorated, but will in most
cases be improved by an addition of the binder according
to the invention. If saicl binder is used for the manu-
facture of concrete it may be observed that the tendency
to rusting of the reinforcements because of the higher
surface flexibility is reduced in comparison to that of
the same samples in the absence of said binder.
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2 ~ 3 '~
E X A M P L E
Prisms having the dimensions of 4 x 4 x 16 cm weremade from 100 parts by weight of sand having a moisture
content of about 2 % and 2 parts by weight of a binder
consisting of 41.4 parts by weight of polybutadiene oil
(Univest(R~ S, Huls AG), 10.9 parts by weight of pine
oil (as commercially available, specific weight at
15.5 C within the range of from 0.916 to 0.924; terpene
alcohol content about 70 to 75~); 10.2 parts by weight
of a water-dilutable unsaponifiable amine-neutralized
1,4-cls-polybutadiene oil (74% by weight in butyl
glycol) (Polyvest~R) OC 4000) and 37.5 parts by weight
of aliphatic hydrocarbons (Shellsol(R) T) (relative
molecular weight of 172, an evaporation index according
to DIN 53 170 of 107, an unmeasurable content of aro-
matics of less than 0.01% by weight of benzene and a
boiling range of from 1~2 C to 212 ~C).
The resulting compressive strength was 13.2 N/mm2
after 3 days at 50 DC, 18.5 N/mm after 7 days at 50 C
and at least 30 N/mm2 after 28 days.
The tensile bending strength was determined to be
6.0 N/mm2 after 3 days at 50 ~C. The modulus of
elasticity (Young's modulus) was about 2.9 x 103 N/mm2,
and the tensile strength according to DIN 53 455 was
2.0 N/mm2.
The shear strength was about 1.3 N/mm2 without an
applied load.
The starting sand was a crystal sand of the grain
grade ISO preferred series "G 40", "G 4OT" exhibiting a
grain size distribution within the range of from 0.25
to 1 mm.
