Note: Descriptions are shown in the official language in which they were submitted.
~;26'~2~
This invention is concerned with coupling agents for
filled plastics particularly calcium carbonate filled plastics.
In view of the recent shortages of petroleum feed
stocks necessary to manufacture such polymers as polyethylene,
PVC, polypropylene and other polyolefins and the ex~ectancy
that these shortages will continue, there has arisen a need
to incorporate larger volumes of inexpensive filler products
into these polymers. These fillers function as extenders
and reinforcing aids to improve the mechanical properties of
the polymer in which they are incorporated such as tensile
impact strength, ductility and Gardner impact strength. It
is expected that the volume of thermoplastic polymers
requiring fillers will continue to grow at increasing rates
each year.
Coupling agents or adhesion promoters are often
used in filled plastic composites to aid in the incorporation
of filler into the polymer and to form an adhesive bond
between filler and polymer. These coupling agents become
more essential as higher loadings of filler are incorporated
into the plastics. By virtue of such coupling agents,
useful thermoplastic composites containing about 70%
~iller can be processed using conventional extrusion and
injection molding equipment.
Heretofore~ organo-silanes have been the most widely
used coupling agents for filled plastic composites. These
organo-silane coupling agents have demonstrated a high
degree of success in bonding numerous polymer resins filled
with silica, metal silicates or metal oxides. They have not
been as effective, however, in other systems, such as with
~L~Z~7
calci~m carbonate fillers which are used extensively in many
resins. Organo-titanates function to some degree as bonding
agents for calci~m carbonate filled polymers and are therefor
useful as coupling agents.
The present invention, on the other hand, provides
non-titanate, non-silane coupling agents which bond thermo-
plastic polymers to a variety of inorganic mineral fillers.
Thermoplastic resin filler composites containing these agents
exhibit improvements in physical properties, processability
0
and thermal stability. The agents of this invention perform
as well or better than the organo-titanates as coupling agents
for calcium carbonate filled polymers but are distinctly
superior to the titanates in terms of cost.
The coupling agents of this invention comprise mono-,
di-,and tri-, long chain fatty acid esters of Cl to C36
mono and polyhydric alcohols and preferably Cl to C4 mono
and polyhydric alcohols. Preferably, coupling agents from this
class will be selected from the ~roup consisting of the mono-,d -,
and tri-esters of hydroxy fatty acids or acetyl derivatives
thereof.
The present coupling agents are prepared by esterify-
ing the fatty acids with Cl to C36 alcohols and polyols
such as methanol ! propanol, butanol r ethylene glycol, propylene
glycol, pentaerythritol, glycerol, decanol, dodecanol, tetrade-
canol, pentadecanol, hexadecanol, octadecanol, eicosanol, doco-
sanol and tetratriacontanol as well known in the art to form
mono-, di- and tri-esters of fatty acids.
Typical long chain hydroxy fatty acid esters or acetyl
derivatives thereof of this invention are methyl ricinoleate,
methyl acetyl ricinoleate, ethyl acetyl ricinoleate, ethyl
~2~;~Z~
ricinoleate, butyl ricinoleate, butyl acetyl ricinoleate,
glyceryl tri (ricinoleate), glyceryl tri (acetyl ricinoleate)
methyl hydroxy stearate, methyl acetyl stearate, ethyl hydroxy
stearate, ethyl acetyl stearate, butyl hydroxy stearate, butyl
acetyl stearate, glyceryl tri hydroxy ~stearate), and glyceryl
tri (acetyl stearate).
The hydroxy fatty acids or acetyl derivatives thereof
may have saturated or unsaturated fatty acid chains and contain
~8 to 22 carbon atoms, and preferably 18 carbon atoms. Exemplary
compounds are hydroxy stearic acid and ricinoleic acid ti.e.
hydroxy oleic acid) and acetyl derivatives thereof.
The coupling agents of this invention may be repre-
sented by the formula:
IRl
Formula I CH3(CH2)5-CH-cH2 R2 (CH2)7 3
wherein Rl is a hvdroxyl group or acetyl group; R2is
-CH=CH-, or -CH2-CH2-; R3 is a mono, di- or tri- ester
group containing from 1 to 36 carbon atoms.
A preferred compound is an ester of acetyl ricinoleic
acid, i.e. 12-acetyl-9-octadecenoic acid, represented by the
formula wherein 23 represents the ester group:
4-C~-CH
Form~la II: CH3~CH2)5C`H-CH2-CH=cH(cH2)7cOoR3
--4--
Another preferred compound is an ester of acetyl
stearic acid, i.e. 12-acetyl-9-octadecanoic acid, represented
by the formula wherein R3 represents the ester group:
0-C-CH3
Formula III: CH3(CH2)5CH-CH2 CH2 CH2 (C 2)7 3
The preferred hydroxy fatty acid esters and acetyl
derivatives thereof of this invention are lower alkyl mono
ricinoleates and hydroxy stearates wherein the alkyl group
contains from 1 to 36 carbon atoms. While all of the compounds
of this invention act as excellent bonding agents between the
resin and inorganic filler, the methyl acetyl ricinoleate
imparts superior reinforcing properties, such as tensile
impact strength and ductility to the filled resin composites
in which it is incorporated.
The amount of hydroxy fatty acid ester or acetyl
derivative thereof incorporated in the filled thermoplastic
composite can vary over wide ranges. It should however be
employed in amounts of about 0.5 to about 7.5~ by weight of
the filler component, and preferably about 0.5 to about 5%
by weight of the filler component.
It has been found that by virtue of the present
coupling agents, up to 80% by weight, preferably 5~ to 75%
and most preferably 10% to 70~ of inorganic filler can be
incorporated into the resin to form a composite based on the
weight of total composite.
--5--
~26~27
As previously mentioned, the coupling agents of
this invention can be used with a variety of inorganic mineral
fillers including silicas, metal silicates, metal oxides,
hydrated aluminum oxides and antlmony trioxide, the latter
of which are used as flame-retardant additives for polyolefins
and combinations thereof. The thermoplastic resins in which
the coupling agents of this invention may be used to bond
fillers thereto include the polymeric amides, such as nylon and
products of polymerization of organic monomers containing one
or more unsaturated double bonds such as ethylene, propylene,
styrene, acrylobutadiene styrene, methacrylic acid, vinyl
acetate, vinyl chloride and mixtures thereof.
The coupling agents of this invention are particu-
larly useful in calcium carbonate filled thermoplastic resin
composites such as calcium carbonate filled high density poly-
ethylene resins, homopolymer polyprop~lene resins and polyvinyl
chloride resins. The calcium carbonate fillers can be either
coated or uncoated and can vary in particle size distribution
from 0.06 to 6.0 microns. Moreover, resin filler composites
containing the inventive coupling agents can be processed at
temperatures of about 335F. without change in color which
indicates a heat stabilizing effect on the composite.
The long chain fatty acid esters and acetyl deriva-
tives thereof of this invention can be incorporated with the
resin and filler by a variety of conventional methods. For
example, the resin may first be fluxed on a 2 roll calender
at temperatures sufficient to fuse the resin. Next, the
coupler may be blended by mixing with the resin followed by
blending the filler in the resin-coupler mix. In another
26~27
,, .
method, the filler and coupling agent may be blended in a
high speed mixer to coat the coupling agent on the filler.
The coated filler is then milled with the resin on a 2 roll
calender. In still another method, the coupling agent is
first dissolved in toluene followed by slurrying the solu-
tion with filler to again coat the filler. The slurry is
then dried and fluxed with the resin on a 2 roll calender.
The so-formed composite may be compounded and processed by
conventional techniques to fabricate a large variety of self-
supporting or laminar plastic forms.
The bonding action of the hydroxy fatty acid esters or
acetyl derivatives thereof permits the plastics manufacturer to
incorporate increasingly higher levels of low cost inorganic
mineral ~illers without sacrificing certain highly desirable
properties such as impact strength, melt flow and thermal
stability. The fatty acid esters of this invention permit
bonding of fillers other than the silicas, metal silicates
and metal oxides, particularly calcium carbonate. Calcium
carbonate and other non-silicatej non-oxide minerals have
until now, resisted being bonded to organic polymers by means
of conventional coupling agents such as the organo-silanes.
The thermoplastic composite may be compounded and
processed by conventional techniques such as injection molding,
and extrusion. Injection molded calcium carbonate filled
composites prepared using couplers of this invention give
improved reinforcement and melt flow properties relative to
commercial injection molded resin composites filled with a
metal silicate such as talc.
6~
The following examples are given to illustrate the
invention, but are not deemed to be limiting thereof. All
percentages given are based upon weight unless otherwise
indicated.
EXAMPLES 1 to 6
These examples illustrate the effect of the alkyl
acetyl ricinoleate coupling agents of this invention in im-
proving the reinforcing characteristics of high density poly-
ethylene (HDPE) filled with 30% by weight of an uncoated cal-
cium carbonate product having a mean particle size distribu-
tion of 2.5 microns. The coupling agents used ~ere methyl
acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl tri-
(acetyl ricinoleate) and glyceryl tri (acetoxystearate).
A 3% coating of each coupling agent, based on the
filler weig~t was accomplished by premixing 1.8g. of coupler
~ith 60g. of calcium carbonate in a Ronson blender for 1
~inute at 250E. ~he resulting coated calcium carbonate
powdPrs were processed with 140g. of HDPE for 8 minutes using
a 2-roll calender set at 275E. The so-formed stocks were
relnoved and compression molded for 5 minutes at 325~. to
form 40 mil. slabs which were then te ted for tensile impact
strength using a Plastics Ilnpact ~ester (Inodel TM 52004,
Testing Machines, Inc.). The results obtained comprised an
average of six test specimens on each example; 3 cut in a
direction parallel to milling and 3 cut at 90 to the
direction of milling.
As controls, a HDPE sample containing no filler
and coupler, and a sample containing calciuln carbonate fil-
ler and no coupler were tested. A sample containing calcium
~ carbonate filler and an organo titanate coupler, isopropyl
--8--
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triisostearic titanate was also tested. The results are
given in Table 1 below:
As Table 1 shows, a significant improvement in the
reinforcing properties of calcium carbonate occurred when
coated wit'n alkyl acetyl ricinoleates of this invention
(co,npare 2x. 2 with Examples 3,4 and 5). The methyl acetyl
ricinolea~e, glyceryl tri (acetyl ricinoleate) and glyceryl
tri (acetoxystearate) coated calcium carbonate performed as
good or better than thè organo titanate.
EXAMPLES 7 to 17
These examples illustrate that various conventional
cornpounding techniques can be used to incorporate the alkyl
acetyl ricinoleates of this invention in a thermoplastic poly-
meric material to yield a composite having excellent reinforce-
ment properties.
In each example a filled composite containing 30%
calcium carbonate and 70% HDPE was prepared. Exa~21e 8, con-
taining only 30% calcium carbonate without coupler was used
as a control.
Two alkyl acetyl ricinoleates of this invention,
methylacetyl ricinoleate and butyl acetyl ricinoleate were in-
corporated in the composite by different conventional methods
and the resulting milled stocks were compression molded for
5 minutes at 325~. to form 0.040 inch plaques. Specimens
were cut from each plaque and used for tensile impact stren~tn
and ductility tests. An or~ano titanate coupler, isopropyl
triisostearic titanate, was also incorporated into the com-
position for each method employed and ~ested.
-10
6'~
In the first series of examples (8-11) the HDPE was
fluxed on a 2 roll calendar at 275F. and after fusion took
place (2 min.), the coupling agents were added and mixed for 3
minutes. The calcium carbonate filler was slowly added to the
HDPE-coupling agent mixture and the resulting composite mixed
for a total of 10 minutes. A composite containing no coupler
was prepared as a control (Ex. 8).
In Examples 12-14 the calcium carbonate was first com-
bined with the coupling agents in a high speed blender. The so-
0
formed coated fillers were incorporated into the HDPE on a 2
roll calender and milled for 10 minutes.
In Examples 15-17 the coupling agents were first dis-
solved in toluene and this solution was slurried ~ith calcium
carbonate to form a 3% coating over the calciu~ carbonate. The
slurry was dried at 120C. for 45 minutes and t'ne coated
calcium carbonate fluxed with the HDPE for 10 minutes at
275F. on a 2 roll calender.
Table 2 below summarizes the results:
As Table 2 shows, irrespective of the method of coating
the filler and incorporating t'ne coated filler in the resin,
excellent reinforciny properties o the HDPE-filler composite
result. Moreover, methyl acetyl ricinoleate coated fillers
inparted more improved rein~orcing properties to the composite
than the organo titanate coated fillers, except for the method
used in Examples 8-11 in which the ricinoleate was comparable
to the titanate.
EXAMPLES 18 to 30
~ hese examples illustrate the effect on the reinforce-
ment properties o a high density polyethylene resin containing
calcium carbonate filler coated with various amounts of methyl
acetyl ricinoleate.
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12
27
In these examples, methyl acetyl ricinoleate was
blended with calciu~ carbonate having an average particle
size of ~.5 microns in a high speed blender to form calciuln
carbonate coate-~ ~ith from about 0.5 to 7.5~ by weight of
ricinoleate. The coated filler was incorporated with HDPE
using a 2 roll calender to form a 30% calcium carbonate com-
posite. The composites were fluxed for 10 minutes at 275F.,
sheeted off and compression molded to form 0.040 inch plaques
~hicl) were tested for tensile impact strength and ductility.
~ PE sample containing no filler (Ex. 18) and a HDPE sample
containing 30% uncoated calcium carbonate (Ex. 19) ~ere also
tested as controls.
The results are given in ~able 3 below:
As the table shows, improvement in tensile impact
strengtll and ductility over the uncoated filler occurred at
about 1.0% methyl acetyl ricinoleate. Optimum reinforcement
occurred in composites formulated with calcium carbonate
which had a 3.5-4.0% coating of methyl acetyl ricinoleate.
After about 4.0% coating levels, reinforcing properties of
the composite were gradually reduced but still better than
~ith uncoated filler.
EXAMPLES 31 to 4 0
These examples illustrate the improvement of rein-
forcing properties of an HDPE composite containing coated or
uncoated calcium carbonate, by treating the calcium carbonate
with an alkyl acetyl ricinoleate of this invention, methyl
acetyl ricinoleate.
A variety of commercial coated and uncoated calcium
carbonate products having a mean particle size distribution
ranging from 0.06 microns to 6.0 microns were treated with
-13-
6~?.17
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14
methyl acetyl ricinoleate using a high speed blender. The
treated products were fluxed with HDPE for 10 minutes at
275F. on a 2 roll calender to form a composite containing
70~ HDPE and 30% filler. For comparison, a series of coated
and uncoated calcium carbonate fillers were fluxed with HDPE
without prior treatment with a coupler. All stocks were
compression molded 5 minutes at 325F. into .040 inch
plaques and tested for tensile impact properties.
A HDPE sample containing no filler and coupler were
tested as a control.
The results are given in Table 4 below;
As Table 4 shows, in each case, whether the calcium
carbonate filler was coated or uncoated, significant improve-
ment in the reinforcing properties of the HDPE composite was
achieved using treatments of methyl acetyl ricinoleate.
EXAMPLES 41 to 54
These examples show that an alkyl acetyl ricino-
leate of this invention methyl acetyl ricinoleate, can be
used to improve the reinforcement properties of polypropy-
lene homopolymer (PP)/calcium carbonate composite.
Methyl acetyl ricinoleate was used to provide a 3%
coating OVeE a series of uncoated calcium carbonate products
or an additional 3% coating over coated calcium carbonate
products using a high speed blender. For comparisons , the
uncoated and coated calcium carbonate products alone were
also employed for incorporation with PP.
Composites of PP and 30%, 50~ and 70% calcium car-
bonate were prepared by first fluxing the PP for 2 minutes
on a roll calender at 335F. The calcium carbonate
products were subsequently added and the total composite
27
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mixed an additional 8 minutes. The resulting stocks were com-
pression molded for 5 minutes at 350F. to form 0.040 in.
plaques which were then used to determine tensile impact
strength, ductility and Gardner impact strength at 75F.
The results are given in Table 5 below:
As Table 5 shows, at each level of calcium carbonate
in the composite, ~hether or not such carbonate filler was
coated or uncoated, improved tensile impact strength, ductility,
and Gardner impact strength resulted when the fillers were
treated with methyl acetyl ricinoleate according to this
invention.
EXAMPLES 55 to 58
These examples illustrate that methyl acetyl ricinoleate
also acts as a stabilizer additive for thermoplastic resins to pre-
vent discoloration of the filled resin during thermal processing.
In these examples, PP resin composites were prepared
with 30~ calcium carbonate alone, 30% methyl acetyl ricinoleate-
coated calcium carbonate and 30~ isopropyl triisostearic titanate-
coated calcium carbonate. As a control, a PP resin containing
0 no filler or coupling agent was also tested. All samples were
heated to 335F. for 10 minutes and the color observed.
Table 6 below summarizes the results
TABLE 6
_ ~ _____
CaC03
¦EXAMPLEI (2.8 microns)l COUPLER TYPE ICOMPOSITE COLOR
I l___ l10 mlns @335F. I
1 55 I none I None I Clear
'I I I I I
1 56 ! 30 I None I Off-White
I
I 57 1 30 I Methyl Acetyl I Off-White
- I I I Rincinoleate
1 58 1 30 1 Isopropyl Triiso-l Tan-Orange
3 1 1 I stearyl Titanate 1
-18-
~6~27
As Table 6 shows the resin composite containing methyl
acetyl ricinoleate coated calcium carbonate did not undergo any
color change relative to the resin composite containing no
coupling agent.
EXAMPLES 59 to 71
~ . .. .
These examples illustrate that calcium carbonate
treated with 3~ methyl acetyl ricinoleate (MAR) can be
compounded at up to 50~ loading with homopolymer (PP)
resin, and the resulting composite injection molded using
conventional molding techniques.
A series of PP resin composite containing 30%
and 50~ uncoated and coated calcium carbonate were prepared.
Similarly another series of PP resin composites were pre-
pared containing the above amounts of coated and uncoated
calcium carbonate treated with 3% of MAR. PP resin con-
taining no filler or coupler was selected as a control.
For each example, the tensile impact at 75 F.
and Gardner impact (75F. and 0F.) were determined;
melt flow characteristics were determined using procedures
outlined in ASTM D~1238, "Measuring Flow Rate of Thermo-
plastics by Extrusion Plastome~er" with a pressure mass of
2160 grams at 246C.
Comparisons were also made against commercial
injection molded PP resins containing talc as mineral filler
and also against a high impact un~illed copolymer PP resin.
Table 7 summarizes the results:
--19 -
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¢ 0~ O O ~ O (~ O O ~ O 1~ E~
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As the Table shows, the treatment of CaC03 with
methyl acetyl ricinoleate produces injection molded PP/CaC03
composites with improved reinforcement and melt flow proper-
ties over untreated PP/CaC03 composites and over commercial
injection molded PP composite.
EXAMPLES 72 to 74
These examples illustrate the improvement of rein-
forcing properties of polypropylene resins filled with anti-
mony trioxide wherein the antimony trioxide is treated with
methyl acetyl ricinoleate as a coupling agent.
Antimony trioxide functions as both a flame retar-
dant and a filler because of the relatively large amounts
often required to flame retard polypropylene compositions.
Such antimony oxide often results in a loss in physical pro-
perties of polyolefin composites.
In these examples, antimony oxide having a mean
particle size distribution of about 1.5 microns was coated
with 3% of methyl acetyl ricinoleate based on the antimony
trioxide weight. The MAR treated antimony tiroxide was
compounded with PP to provide a 16.7% loading on a 2 roll
calender, compression molded and tested for tensile impact
strength.
As controls, a PP resin containing no antimony
trioxide and coupler and a PP resin/Sb203 composite
containing 16.7~ Sb203 alone was also tested. The re-
sults are given in Table 8 below:
~ .
21-
6~;~7
TABLE 8
~ MAR % I TENSILE I --I
I EX. I Sb203 1 ~based on I IMPACT ST~. I DUCTILITY
Sb203wt? I(ft-lbs/in ) I (millisecs)_l
1 72 1 0 1 0 1 133 1 1.2
- I 73 1 16.7 1 o I go l 0.9
1 74 1 16.7 1 3 1 121 1 1.5
~L ............. _ . I .. _ I _ ................. I
As Table 8 shows, MAR treated antimony trioxide/PP
composite gave significant improvements on tensile impact
strength and ductility over untreated antimony trioxide com-
posite.
EXAMPL S 75 to 77
These examples illustrate the improvement in re-
inforcing properties of polypropylene resin filled with
aluminum trihydrate (ATH) wherein the ATH is treated with
methyl acetyl ricinoleate as a coupling agent.
Aluminum trihydrate is useful as both a flame/smoke
retardant and filler in many thermoplas~ic applications.
In these examples, ATH having a mean particle size
of about 1 micron was coated with 3% of methyl acetyl ricino-
leate based on the ATH weight. The MAR treated ATH was com~
pounded with PP to form a 25% loading using a 2-roll calender,
compression molded and examined for tensile impact strength.
As controls, a PP resin without ATH and coupler and
a PP resin/ATH composites containing 25~ ATH alone was also
tested. The results are given in Table ~.
-22-
6~Z7
TABLE 9
MAR `~ I TENSILE
I EX. I ATH ~ I (based on I IMPACT STE~. I
ATH wt.) _ I(ft-lbs/in
1 75 1 6 1 0 1 106
1 76 1 25 1 0 1 35
1 77 1 25 1 3 1 80
I _ _ !
Table 9 shows that tlAR treated PP/ATH composites
develop significant improvements in tensile impact strength
over the untreated ATH composites.
EXAMPLES 78 to 81
These examples illustrate the improvement in reinforcing pro-
perties of polypropylene filled with the amounts of calcium carbonat
(uncoated or coated) having a mean particle size distritubion of
- 2.5 microns according to the procedure of Examples l to 6. The
coupling agents used were docosylhydroxystearate whérein the
alcohol is a by~product mixture containing C20 - C28 linear
primary alcohols containing about 60% C22; and tetratriacontyl
ricinoleate wherein the alcohol is a by-product mixture containing
.~ 20 ~5% C34 saturated primary alcohol and remainder being non-reactlve
material being 500 molecular weight normal paraffin.
As Table lO shows, a significant improvement in reinforcing
properties of calcium carbonate occurred when coated with the
compositions of this invention.
The invention being thus described, it will be obvious
that the same may be varied in many ways, such variations are not
to be regarded as a departure from che spirit and scope of the
invention, and all such modifications are intended to be included
within the scope o the following claims.
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