Note: Descriptions are shown in the official language in which they were submitted.
9~ t;~
This invention relates to new and improved filled
polyester compositions containing specified organo-titanate
esters. More specifically, the instant invention relates to
polyester compositions having improved physical properties
obtained by linking the filler to the polyester chain.
It is known that certain organic titanate esters
may be used to treat the surfaces of inorganic fillers to
enhance their compatibility with polymeric material. Such
applications are shown in U.S. Patents 3,660,134 (Morris
and Oliver) and 3,697,474 (Morris, Oliver and Prescott),
issued to the Freeport Sulphur Company on May 2, 1972 and
October 10, 1972, respectively. These filled polymeric
materials are well known and find application in fibers,
sheet material and shaped solid articles. The aforesaid
patents specifically relate to organic derivatives of ortho-
titanic acid containing at least two hydrolyzable groups.
In accordance with the instant invention, it
has been found that treating inorganic fillers with selected
classes of organic titanate esters imparts even greater
advantages than that obtained by following the teachings
of the aforesaid patents. This effect is particularly
outstanding when the polymeric material is a polyester.
The first class of the organo-titanate salts
which may be used in accordance with the practice of
the instant invention may be represented by the formula:
(I) (RO)zTi(A)X(B)y
wherein R is a monovalent alkyl, alkenyl, alkynyl or aralkyl
group having from 1 to about 30 carbon atoms or a sub-
stituted derivative thereof. The R group may be saturated
or unsaturated, linear or branched, and may have from 1 to 6
substitutions including halogen, amino, epoxy, cyano, ether,
thioether, carbonyl, aromatic nitro or acetal. In a particular
;'~
l~ssa)~
molecule, all of the R groups may be the same or different,
so long as they fall within the above class. It is preferred
that the R group be alkyl having 1 to 6 carbon atoms and be
all the same.
The monovalent group (A) may be thioaryloxy,
sulfonyl, sulfinyl, diester pyrophosphate and diester
phosphate. The thioaryloxy group may be a substituted or
unsubstituted thiophenoxy or thionaphthyloxy group containing
up to about 60 carbon atoms. It may be substituted by alkyl,
alkenyl, aryl, aralkyl, alkaryl, halo, amino, epoxy, ether,
thioether, ester, cyano, carbonyl, or aromatic nitro groups.
Preferably no more than three substituents per aromatic
ring are present. The thioaryloxy groups wherein the aryl
is phenyl or naphthyl are preferred.
The sulfonyl, sulfinyl, diestex pyrophosphate and
diester phosphate ligand, respectively, are represented
by the following formulas:
-OSO2R", -OSOR", (R"O)2P(O)OP(O)(OH)o~ and
(R"O)2P(OJO-
wherein R" may be the same as R' as defined below. Where Ais a sulfonyl or a sulfinyl group, it is preferred that R"
be phenyl, a substituted phenyl or an aralkyl group having
from 5 to 24 carbon atoms in the alkyl chain. Where A is a
phosphate group, it is preferred that the R" group have
from 6 to 24 carbon atoms, and where A is a pyrophosphate
group, it is preferred that the R" group be alkyl having up
to 12 carbon atoms.
The monovalent group (B) may be acyloxy (OCOR') or
aryloxy (OAr). R' may be hydrogen or a monovalent organic
group having from 1 to about 100 carbon atoms; particularly,
an alkyl, alkenyl, aryl, aralkyl or alkaryl group. The
aryl in R' and (OAr) groups may be substituted or unsub-
stituted phenyl or naphthyl groups, preferably containing
- 2 -
1~9 ~ ~ ~t~
up to 60 carbon atoms. Additionally, the R' group may be
substituted with halo, amino, epoxy, ether, thioether,
ester, cyano, carboxyl and/or aromatic nitro substituents.
Generally up to about six substituents may occur per R'
group. The R' group may contain intermediate hetero atoms
such as sulfur or nitrogen in the main or pendant substituents.
R' is preferably a long chain group having 18 carbon atoms.
Most desirably, all R's are the same. In formula (I)
the sum of x, y and z must be 4; x and z may be 1, 2 or 3;
and y may be 0, 1 or 2. Preferred are those compounds where
z is 1.
The second class of organic titanate salts which
may be used in the practice of the present invention may be
represented by the following formula:
(II) (~RO~Ti(OAr)p(OCOR')q
where R, R' and (OAr~ are as defined above and p and q may
each be 1, 2 or 3, but p+q must equal 3.
Of the above classes of compounds, preferred are
those where R' contains functional groups, that is, olefinic
or acetylenic unsaturation, or amino or hydroxyl groups. Most
; preferred are such compounds wherein the R' group is poly-
functional. From the standpoint of efficiency, it is most
desirable that such functional groups have less than 8
carbon atoms. Where desired, one of the R' groups may have
a long chain group in order to lower the viscosity of the
filled polyester.
The aforesaid classes of organic titanate salts
have distinct advantages over the ortho-titanium organic
derivatives having at least two hydrolyzable groups as -
described in the aforesaid Freeport Sulphur Company patents.
For example, with the organic titanate esters shown in
Formula II, those most closely related to the aforesaid
, .,
1~99~5
prior patents, where there is only one hydrolyzable group,
the rheology of the filled polymer is improved. In the
case of the phosphorus-containing compounds of Formula I,
the polymeric materials are stabilized with regard to
ultra-violet light and have enhanced flame retardance.
The sulfur-containing compounds of Formula I show improved
thermal stability and greater flex modulus as compared to the
carbon compounds.
In the case of the preferred class of compounds,
namely, those containing functional groups, the mechanical
properties are far better than those obtained heretofore.
Stress, tensile strength, flexibility, shear resistance,
adhesion in surface coating applications, resistance to
chemical attack and the other advantages of cross-linking
are obtained. In all instances, the filler becomes more
tightly incorporated in the polymeric structure. This bond
results in a structure which is more readily able to transfer
energy and therefore results in a stronger material.
The improved composition of the invention
consists of a polyester material containing a filler which
has been treated with one or more of the aforesaid organic
titanate salts. Where the titanate is nonfunctional, the
filler and the polyester are bound together by Vanderwahl's
forces. On the other hand, where functional groups are present,
the reaction product of the filler and the organic titanate
salt is grafted to the polyester resin. ~here multi-
functionality is present, the compositions will in fact be
cross-linked.
A broad range of polyester resins may be used
in the composition and processes of this invention. In
preparing the polyester, a mixture of one or more glycols
and one or more alpha, beta ethylenically unsaturated
1~9~S
polycarboxylic acids may be employed.
By way of non-limiting example, it may be mentioned
that polyesters can be prepared from such acids as maleic,
fumaric, aconitic, mesaconic, citraconic, ethylmaleic,
pyrocinchoninic, veronic, or itaconic acid (with or without
other acids) and such glycols as ethylene, diethylene, tri-
ethylene, polyethylene, 1,3-propylene, 1,2-propylene, di-
propylene (1,3 or 1,2), butylene or styrene glycol.
The copolymerizable ethylenically unsaturated
monomers suitable for mixing with the foregoing unsaturated
polyesters are also well known and are described in full
detail in the patents previously referred to. Canadian
Patent No. 703,001, issued February 2, 1965, contains a
particularly extensive disclosure of such monomers. This
patent shows representative monomers any and all of which
may be mixed with the polyester for use in this invention.
The preparation of the polyester itself involves
heating, usually at a temperature of 280 to 480F. for
a period of from 4 to 24 hours, a mixture of one or more
glycols and one or more alpha, beta-ethylenically unsaturated
polycarboxylic acids. Usually a dicarboxylic acid (or
its corresponding anhydride~ is used. For purposes of
the invention, the resulting self-condensation esterification
product has, as indicated, an acid number of from lO to lO0.
Such a polyester is sometimes called an "alkyd" and
although it is commonly referred to as "resinous," it may
be either a viscous liquid or a solid in the uncured state.
In conventional practice polyesters are mixed with copolymer-
izable ethylenically unsaturated monomers ~e.g., styrene,
vinyl toluene, methyl methacrylate, vinyl acetate, diallyl
phthalate, triallyl cyanurate), frequently in amounts of from
5% to 80% by weight of the mixture of polyester and monomer,
1~9eJ~S
and then cured to a solid, insoluble, infusible, cross-
linked state with the aid of conventional catalyst systems.
The composition is characterized by the ability
to be cured to a solid, infusible, insoluble, cross-linked
state, under the influence of the polymerization catalyst
and/or "promoters" usually used for this purpose, notably
peroxidic materials, such as benzoyl peroxide, hydroperoxides
such as tertiary butyl hydroperoxide, ketone peroxides such
as methyl ethyl ketone peroxide, with or without such
catalytic materials as cobalt, manganese and the like, as
well as such promoters as N-methylaniline or the like
(U.S. Patent 2,449,299, Hurdis, September 14, 1948), diethyl
aniline or the like (Hurdis, 2,480,928, September 6, 1949),
or various other conventional catalyst mixtures. The catalyst
may be used in conventional amounts, usually from 0.2 to 3%
by weight of the polyester-copolymerizable monomer mixture,
although larger amounts such as 4 or 5% can also be used.
Cobalt or the like is usually used in the form of sufficient
soluble cobalt salt (e.g., cobalt acetate, octoate, oxide or
hydroxide, chloride or nitrate~ to supply for example from
0.001 to 0.2%, or more of cobalt ion. The promoters are
frequently used in amounts of from 0.001 to 1%, or up to 2%
or more, by weight, based on the weight of polyester plus
copolymerizable monomer. Depending upon the amount and kind
of catalyst and promoting materials, the composition can be
cured readily at essentially room temperature (e.g., frequently
60F. to 80F.), or, if desired, at elevated temperatures
(of the order of, e.g., 120 to 350F. for a period of
from 5 minutes to 4 hours or more) particularly during
the final stages of the cure.
A wide variety of ligands, subject to the limita-
tions heretofore expressed, may be used in the practice
~i9~S
of this invention. The most suitable depends upon the
filler-polyester system and to a lesser degree upon the
curative and/or extender systems employed.
Examples of specific R ligands are: methyl,
propyl, cyclopropyl, cyclohexyl, tetraethyloctadecyl,
2,4-dichlorobenzyl, 1-(3-bromo-4-nitro-7-acetylnaphthyl)-
ethyl, 2-cyano-furyl, 3-thiomethyl-2-ethoxy-1-propyl and
methallyl.
Examples of A ligands useful in the practice of
this invention include 11-thiopropyl-12-phenyloctadecyl-
sulfonyl, 2-nitrophenylsulfinyl, di(2-omega-chlorooctyl)phenyl
phosphato, diisonicotinyl pyrophosphato, 2-nitro-3-iodo-
4-fluorothiophenoxy, 2-methallylphenoxy, phenylsulfinyl,
4-amino-2-bromo-7-naphthylsulfonyl, diphenyl pyrophosphato,
diethylhexyl pyrophosphato, di-sec-hexylphenyl phosphato,
dilauryl phosphato, methylsulfonyl, laurylsulphonyl and
3-methoxynaphthalene sulfinyl. Examples of aryloxy groups
are 2,4-dinitro-6-octyl-7-C2-bromo-3-ethoxyphenyl~-1-
naphthoyl and 3-cyano-4-methoxy-6-benzoylphenoxy.
Examples of the R' groups are numerous. These
include straight chain, branched chain and cyclic alkyl
groups such as hexyl, heptyl, octyl, decyl, dodecyl, tetra-
decyl, pentadecyl, hexadecyl, octadecyl, nonadecyl,
eicosyl, docosyl, tetracosyl, cyclohexyl, cycloheptyl,
and cyclooctyl. Alkenyl groups include hexenyl, octenyl
and dodecenyl.
Halo-substituted groups include bromohexyl,
chlorooctadecyl, iodotetradecyl and chlorooctahexenyl.
One or more halogen atoms may be present, as for example
in difluorohexyl or tetrabromooctyl. Ester-substituted
aryl and alkyl groups include 4-carboxyethylcapryl and
3-carboxymethyltoluyl. Amino-substituted groups include
"~,
113~9~
aminocaproyl, aminostearyl, aminohexyl, aminolauryl and
diaminooctyl.
In addition to the foregoing aliphatic groups,
groups containing hetero-atoms, such as oxygen, sulfur
or nitrogen, in the chain may also be used. Examples of
these radicals are ethers of the alkoxyalkyl type, including
methoxyhexyl and ethoxydecyl. Alkylthioalkyl groups include
methylthiododecyl groups. Primary, secondary and tertiary
amines may also serve as the terminal portion of the
hydrophobic group. These include diisopropylamino, methyl-
aminohexyl, and aminodecyl.
The aryl groups include the phenyl and naphthyl
groups and substituted derivatives. Substituted alkyl
derivatives include toluyl, xylyl, pseudocumyl, mesityl,
isodurenyl, durenyl, pentamethylphenyl, ethylphenyl, n-
propylphenyl, cumyl, 1,3,5-triethylphenyl, styryl, allyl-
phenyl, diphenylmethyl, triphenylmethyl, tetraphenylmethyl,
1,3,5-triphenylphenyl. Nitro- and halo-substituted may be
exemplified by chloronitrophenyl, chlorodinitrophenyl,
dinitrotoluol, and trinitroxylyl.
Amine-substituted components include methylamino-
toluyl, trimethylaminophenyl, diethylaminophenyl, amino-
methylphenyl, diaminophenyl, ethoxyaminophenyl, chloro-
aminophenyl, bromoaminophenyl and phenylaminophenyl. Halo-
substituted aryl groups include fluoro-, chloro-, bromo-,
iodophenyl, chlorotoluyl, bromotoluyl, methoxybromophenyl,
- dimethylaminobromophenyl, trichlorophenyl, bromochlorophenyl,
and bromoiodophenyl.
Groups derived from aromatic carboxylic acids
are also useful. These include methylcarboxylphenyl, di-
methylaminocarboxyltoluyl, laurylcarboxyltoluyl, nitro-
carboxyltoluyl, and aminocarboxylphenyl. Groups derived
S
from substituted alkyl esters and amides of benzoic acid may
also be used. These include aminocarboxylphenyl and methoxy-
carboxyphenyl.
Titanates wherein R' is an epoxy group include
tall oil epoxides (a mixture of 6 to 22 carbon alkyl groups)
containing an average of one epoxy group per molecule and
glycidol ethers of lauryl or stearyl alcohol.
Substituted naphthyl groups include nitro-
naphthyl, chloronaphthyl, aminonaphthyl and carboxynaphthyl
groups.
Illustrative of the compounds useful in the
instant invention are:
3 7 ( 02c6H4cl2H25~2(oso2c6H4NH2~ C3H O)Ti-
[P()(OC H17~2]3; (i-C3H70~Ti(Oc6H4C(cH3)2c6 5 3
(i C H O)Ti[OP(O)(oC12H25)]3; (i C3H7 ) 70 141 3
6 12 ) ( C6H4NH2)3; (nC4H9o)2Ti[opo(oc6H4c8Hl7)2]2;
[CH30(CH2)20]Ti(OCOC6H4Cl)[OP(O~(OH)OP(O)(OCH3)2]2;
(i-C3H7)(nC12H25)Ti(S2C6 5)2
(C H CH2)Ti(CC70H141)3; (i C3H7 ) 2 2
H (OC H4)12CH2C6H4N2]3; (CH3o)Ti(ococ72Hl4l)2 2
( ( 2)4)Ti[Cc(c22H43)3]2(ccHc2H5);
(nC16H310)Ti[OcOc6H4cH20cH2c6H3(c36H73)2]2( 70 141
(i-C3H70)Ti[OCOC(CH3)=CH2)3; (i-C3H70)Ti(OCOCH2NH2)3;
(C6HllO)Ti(OCOCH20CH3)2(0COCHClCH3); (CH30)Ti(OCOCC13)3;
(C2H50)Ti(OCOCHBrCH2Cl)(OCOC6H5)(0COCH2NH2);
(i-C3H70)Ti(oCoC2H5)(ococH2cN)[ococH2N(cH3)2];
(CH3)2CHOTi[OCO(CH2)14CH(CH3)2]2 3 2
(CH3)2CHOTi[OCO(CH2~14CH(CH3~2][0COC~CH31=CH2~2;
(CH3~2CHOTi[OCO /_ \ C02(CH2)nCH3]3, where n is greater
~
than 8 and less than 15;
[(CH3)2CHOTi[OcO(cH2)l4cH(cH3)2]2o ]2 34 68
(CH3)2CHOTi[OcO(cH2)l6cH3]3; ( 3 2 ~ 2]3;
3 2 [ ( 2)5NH2]3; (CH3)2CHOTi[OCocH2cH2NH2]3; and
(CH3)2CHOTi[OCO(CH2)pCH~CH(CI-I2)qCH3]3, where the sum of
p + q is more than 6 and less than 18.
The amount of the titanate reacted is at least
0.01 part, preferably from 0.1 to 5 parts, and most preferably
between 0.2 and 2 parts, per 100 parts of inorganic solid.
The optimum proportions required are a function of the in-
organic solid and the alkoxy titanium salt selected, and thedegree of the comminution, i.e., the effective surface area,
of the inorganic solid. The reaction of the titanate takes
place on the surface of the inorganic filler. The RO group
splits off and an organic hydrophobic surface layer is formed
on the inorganic solid. The unmodified inorganic solid is
difficult to disperse in an organic medium because of its
hydrophilic surface. The organo-titanium compound may be
incorporated into an organic medium (low molecular weight
liquids or higher molecular weight polymeric solids) with
the inorganic solid. Alternatively, the organo-titanate may
be first reacted with the inorganic solid in the absence of an
organic medium and thereafter admixed with the latter.
By means of the present invention, the dispersion
of inorganic materials in polyester polymers is improved
and achieves (1) improved rheology or higher loading of
the dispersate in the organic medium; (2) higher degrees
of reinforcement by the use of fillers, thereby resulting in
improved physical properties in the filled polymer; (3) more
complete utilization of chemical reactivity, thereby reducing
the quantity of inorganic reactive solids required; (4) more
efficient use of pigments and opacifiers; (5) higher inorganic-
to-organic ratios in a dispersion; and (6) shorter mixing
- 10 -
1`~3~ S
times to achieve dispersion.
Also, according to the invention herein, the
reaction with the RO groups on the organo-titanates may be
carried out neat or in an organic medium to form a liquid,
solid or paste-like solid dispersion which can be used in the
compounding of the final polymeric system. Such dispersions
are very stable, i.e., having little tendency to settle,
separate, or harden on storage to a non-dispersible state.
The present invention results in the formation
of reinforced polyesters which have a lower melt viscosity,
improved physical properties, and better pigmenting character-
istics than the prior art materials.
The inorganic materials may be particulate or
fibrous and of varied shape or size, so long as the surfaces
are reactive with the hydrolyzable group of the organo-
titanium compound. Examples of inorganic reinforcing materials
include metals, clay, carbon black, calcium carbonate, barium
sulfate, silica, mica, glass and asbestos. Reactive inorganic
materials include the metal oxides of zinc, magnesium, lead,
and calcium and aluminum, and iron fil~ngs and turnings.
Examples of inorganic pigments include titanium dioxide,
iron oxides, zinc chromate, ultramarine blue. As a practical
matter, the particle size of the inorganic materials should
not be greater than 1 mm, preferably from 0.1 micron to 500
micron .
It is imperative that the alkoxy titanium salt
be properly admixed with the inorganic material to permit
the surface of the latter to react sufficiently. The
optimum amount of the alkoxy titanium salt to be used is
dependent on the effect to be achieved, the available
surface area of and the bonded water in the inorganic material.
Reaction is facilitated by admixing under the
proper conditions. Optimum results depend on the properties
of the alkoxy titanium salt, namely, whether it is a liquid
or solid, and its decomposition and flash points. The
particle size, the geometry of the particles, the specific
gravity, the chemical composition, among other things, must
be considered. Additionally, the treated inorganic material
must be thoroughly admixed with the polymeric medium. The
appropriate mixing conditions depend on the type of polymer,
whether it is thermoplastic or thermosetting, its chemical
structure, etc., as will be readily understood by those
skilled in the art.
Where the inorganic material is pretreated with
the organic titanate, it may be admixed in any convenient
type of intensive mixer, such as a Henschel or Hobart mixer
or a Waring blender. Even hand mixing may be employed.
The optimum time and temperature are determined to obtain
substantial reaction between the inorganic material and
the organ~c titanate. Mixing is performed under conditions
at which the organic titanate is in the liquid phase, at
temperatures below the decomposition temperature. While it is
desirable that the bulk of the hydrolyzable groups be reacted
in this step, this is not essential where the materials are
later admixed with a polymer, since the substantial completion
of the reaction may take place in this latter mixing step.
Polymer processing, e.g., high shear mixing, is
generally performed at a temperature well above the second
order transition temperature of the polymer, desirably at a
temperature where the polymers will have a low melt viscosity.
Temperatures for mixing the polyester resins with
the treated filler are well known in the art. Casting resin
types are best processed at room temperatures but tempera-
tures up to 100C. may be used. Thermoplastic polyesters are
generally processed from 200 to 325C. A variety of mixing
- 12 -
,
.
1`~9~
equipment may be used, e.g., two-roll mills, Banbury mixers,
double concentric screws, counter or co-rotating twin screws
and ZSK type of Werner and Pfaulder and Busse mixers.
When the organic titanate and the inorganic
materials are dry-blended, thorough mixing and/or reaction
is not readily achieved and the reaction may be substantially
completed when the treated filler is admixed with the polymer.
In this latter step, the organic titanate may also react with
the polymeric material if one or more of the Rl groups is
reactive with the polymer.
The amount of filler used depends on the particular
polymeric material, the filler and the property requirements
of the finished products. Broadly, from 10 to 500 parts of
filler may be used based on 100 parts of polymer, preferably
from 20 to 250. The optimum amount may be readily determined
by one skilled in the art.
To illustrate further the invention, attention
is directed to the following examples. In certain of these
examples, the number of ligands per molecule is expressed
by a mixed number. In such cases, it should be understood
that the structural formula represents a blend of compounds
and the mixed number is the average number of such ligands in
the blend.
The organic titanate esters of the invention may
be readily prepared by reacting the tetraalkyl titanate with
the appropriate organic acid. Examples of such preparations
follow.
Example A: Preparation of Organo'-Titanate Este'rs
One mole of tetraisopropyl titanate is admitted
to a vessel equipped with an agitator, an internal heating
and cooling means, a vapor condenser, a distillate trap and
liquid-solid feed input means. Agitation is commenced with
the tetraisopropyl titanate at room temperature. Liquid
- 13 -
1~9~S
isosteric acid is metered into the vessel at a controlled
rate so that the exothermic reaction is maintained below about
350F. until 3.19 moles of the acid are added. The iso-
propanol is removed from the reaction product by distillation
at 150C. at 50 mm Hg to remove potentially objectionable
volatiles.
The organic titanate thus produced has an
average of 3.19 moles of isostearate per molecule. The ester
structure is determined by ascertaining the isopropanol
liberated from the reaction and the residual isostearic acid.
It is found that about from 3.1 to 3.3 moles of ;sopropanol
are recovered in the typical run. Substantially no unreacted
isostearic acid is detected. The physical properties of the
ester are:
Specific Gravity at 74F. 0.944
Flash Point (COC), F 3.5
Viscosity, LV, at 74F., cps 120
Pour Point, F. Below -5
Decomposition Point, F. Above 400
Gardner Color 15 Max
Appearance Reddish
Oily Liquid
Example B: Preparation of (i-C3H70)0 7Ti(OCOC~CH3)=CH2)3 3
One mole of tetraisopropyl titanate is added
to a vessel such as described in Example A, and stirring
commenced. Liquid methacrylic acid is added at a controlled
rate so that the exothermic reaction is maintained below about
180C. until 3.50 moles of the acid are added. Isopropanol
is removed from the reaction product by distillation at
150C. at 50 mm Hg to remove volatiles.
The organic titanate thus produced has an average
of 3.3 moles of methacrylate per molecule. The product
- 14 -
1~39C~S
structure is determined by ascertaining the ispropanol
liberated from the reaction and the residual methacrylic
acid. From 3.1 to 3.3 moles of isopropanol are recovered.
About 0.2 mole methacrylic acid plus isopropyl methacrylate
are detected. The physical properties of the product are:
Specific Gravity at 24C. 0.92
Flash Point (COC), C 120
Pour Point, C. About 130
Decomposition Point, C. Above 200
Appearance Tan Solid
The following examples illustrate the practice
of the instant invention:
Example 1
This example teaches the use of compounds of
this invention, viz., (A) (CH3O)Ti~OCOCH=CH2)3, ~B~
3 7 ( 3) CH2]3, (C) (i-c3H7O)2Ti~oso2cH2cH2cocH=cH
and (D) (BrCH2CH2O)Ti[ OP(O)(OCH2CH=CH2~3 as flex
property modifiers for polyester resin.
Formulations were prepared containing 100 parts
of a cobalt activated polyester resin (GR 643, a trade-
mark of W. R. Grace Co.), 1 part of methyl ethyl ketone
peroxide, 60 parts of high surface area calcium carbonate,
and 0.3 part of alkoxy titanium salt, as indicated in
the Table below.
Samples measuring 1~2" x 5" x 1/8" thick were
cast and cured at ambient temperature for 30 minutes.
The castings were tested and the results shown in Table A
below.
- 15 -
9~5
Table A
Alkoxy Flex Flexural
Titanium Salt Modulus psi Strength psi
None 1.5 x 10 4 x 10
A 3.5 x 10 7 x 10
B 4.0 x 10 10 x 103
C 2.0 x 106 6 x 103
D 1.0 x 10 8 x 103
The above data establish clearly the improved
flexural properties obtained by the use of the organo-
titanates of the invention.
Example II
This example shows the effect of isopropyl
dimethacryl isostearoyl titanate (E~ and isopropyl triiso-
stearyl titanate (F) on the properties of a mineral-filled
polyester employing a variety of fillers. The polyester
employed was the same as that described in Example I. The
titanate compound was premixed with the filler in a Waring
blender. Thereafter, the treated filler was added to the
polyester, mixed and then cured with methylethyl ketone
peroxide at 22C. Table B shows the effect of the titanate
treatment on the physical properties of the cured polyester
tested at ambient temperature.
- 16 -
~ 1~b9~ 5
Z
~.~
H\
Q co o
a~ oco ~ co oo
O
N ~)
H 41 O O O O O O
.C
~n
~0
S~
~ X u~
~1 er 1~ ~ ~ 1` ~ o o In
U~
O
X :X ~ O a~
~ o ~er O ~ UlCO 0
¢i Q ~ I O ~ ~ 1 0
m a)
~ ~:
E~ 'E-~ m n Ln u~ L)~
~C ~P ~I ~ ~ o O
o a) ~ a) a
o ~ o~ o ~ o~ ~
Z ~ Z _ Z_ _
d~
a~
~rl _ ~ ~ _
e ~ o a) a~
~ ~: N ,q N N
--I O-rl h ~
O U~O tQ
O O h h
~ ,e, ,1 e .,, ~ .,,
s~ ~ u ~ e, ~
~/ ~ O ~ ~1 0 (1
14 ~ --Q, u~
17-20
1~99q~S
The above data clearly sho~ the impr~vem2nt
obtained by treating the filler with the isopropyl
dimethacryl isostear~yl titanate (E). Depending on the
particular filler employed and the filler loading,
improvement is shown in the Izod Impact Strength, the
flexural strength, and the flex modulus of the cured
compositions. In the case of the unsaturated titanate,
namely, the isopropyl trl~sostearoyl titanate (F), the
flex modulus was decreased. This shows the superiority
of the unsaturated titanates with regard to the properties
tested.
Example III
This example shows the effect of titanate coupling
agents on the viscosity of a dispersion of calcium carbonate
(particle size 5 microns) in a low molecular weight
polyester plasticizer (Paraplex G33, trademark of Rohm &
Haas Co. for polyethylene adipate, mol. wt. ca. 1000).
One part by weight of each titanate indicated below was
added to separate samples containing 30 parts by weight
of the plasticizer and 70 parts by weight of the filler.
Mixing was done with the aid of a Waring blender. The
following results were obtained:
*Trade Mark
,Af--~
lr3~ S
. h u~ 1~ o
V ~
o ~ ~ ~ ~ o
CU CU ~
~U ~ ,. '
+~
~o ~ o o o
,1
~ o~ O
X ~ ,~
~:
.,1
Cq .
o m ~ o o ~
~a
~1 N N c~ o 1~
\
~ ~1
C~ ,1
S~
a) ~ ~ o o u~
~L ~ ,i 0~ ~ O
1:~ ~ J r-
~>
~ ~ ~:
E~
~1,_
O
NU~
O
h O,s:
o ~P~
h h
~1 ~ C)
~ +~a) c)
U~ ~ ~ o
O O
~q
.,~
rl ~
h h
0 +~
~ ~1
E~
:~ 0~ O' 0
X h 5-- h
O
~. ~ O O O
,1 o tn to u~
¢~j H H H
l.S~.
l.r~9~S
The above data show that a full range of
viscosity control can be achieved. Increased
viscosity is particularly important as it i~proves
the thixotropic properties of the dispersion. This
is useful in applications such as painting and
prlnting. The phosphate formulation's comparatively
low viscosity facilitates mixing while giving high
viscosity use~ul in later applications. Viscosity
tests were also ~ade on polyester compositions
containing the following titanates. The number in
parenthesis after the compound is the viscosity
determined: isopropyl dimethacryl isostearyl (18.0);
isopropyl dimethacryl isostearoyl (25.5); isopropyl
di(dodecylbenzenesulfonyl) p-aminobenzene sulfonyl
(21.5), and isopropyl tri(dioctylpyrophosphato) (8.7).
The pyrophosphate is unique in its ability to decrease
viscosity: an effect of importance in reducing energy
requirements for mixing.
Example IV
The effect of isopropyl tridodecylbenzenesul~onyl
titanate on the viscosity of a calcium carbonate (5 micron
particle size) dispersion in a 500 molecular ~reight
(polyethylene glycol adipate) polyester was determined.
The dispersion contains 33 wt. ~ of calcium carbonate,
5 part of the titanate was added and tnoroughly mi,~ed
in the polyester. The initial Broo~field viscosity at
25 C. was 1625 centipoise for the control and 1600
centipoise after aging for 2I~ hours at 150 ~. On the
r -
. ,
99~4~
other hand, the viscosity of the treated material
was initially 2900 centipoise and 4700 after aging.
This increase in viscosity is advantageous be~ause it
allows the formulation to be blended at low viscosity
and, upon aging, give a higher viscosity useful in many
applications
Example V
The effect of isopropyl trimethacryl titanate (G),
isopropyl tri(dioctylphosphato)titanate (H), isopropyl
triacryl titanate (I) and isopropyl didodecylbenzene
sulfonyl, 4-aminobenzene-sulfonyl titanate (J) on the
flexural strength of 50% Wollastonite P-l (trademark of
Interpace Corporation of a naturally occurring calcium-
mag~e~lum-aluminum silicate fiber) filled polyester
resin is demonstrated in this example. (The polyester was
that described in Example I.) One weight percent of
each titanate was premixed with the filler by dry blending
in a Waring blender. The treated filler was then
thoroughly blended with the polyester. The resulting
dispersion was cured at room temperature. The following
results were obtained:
Table D
Alkoxy Titanium Salt Flexural Strength, psi
None 14,000
(G) 21,500
(H) 18,200
(I) 24,400
J ) 16 ~ 3 00
~ 24 ~
~9~S
The above data show the increased flexural
strength of the filler polyes-ter treated according to
the invention. The olefinically unsaturated titanates
gave the best result.
Example VI
Two unsaturated triglyceride alkyl polyester
surface coatings were prepared and laminated on fiberboard
substrates. The formulations and curing conditions were
as follows:
Coating
Components, pts._by wt. A B
Polyester 85 85
Melamine 15 15
Titanium dioxide (Rutile) 95 95
Toluene sulfonic acid catalytic amount
Volatile organic solvent 40 20
Isopropyl dioctylphosphato
titanate - 1.1
Cure time, min. 15 15
Cure temperature, C.191 135
The cured coatings were tested for pencil
hardness. The titanate modified coating, B, had a
hardness of H while the unmodifled coating was
substantially softer, B hardness.
After 100 hours of a 5~ salt spray at room
temperature, the coating of the invention had less than
1/8" of creepage at the scribe, while coating A had a
creepage of 1/4". This shows superior dimensional
- 25 -
1~399~
stability. ~'urthermore, the reverse impact strength
was qunlitatively superior.
In coating B, because of improved flow, only
one-half the solvent was required, This reduces the
energy required to drive off solvent and to cure ann
the cost of the coating.
- 26 -
