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Description  |
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This invention relates to improved plasticizers, blends of plasticizers
with different polymers, and process for preparing the plasticizers and
the blends.
Balmer et al, U.S. Pat. No. 3,224,996, disclose copolymers of an acrylate
with either propylene or ethylene as plasticizers for vinyl polymers;
these plasticizers have good performance properties, but tend to be
inefficient in plasticizing and softening, and the resins plasticized with
these plasticizers flux too slowly during processing. Furthermore, the
plasticizer/resin blends generally are not sufficiently clear and do not
possess sufficient tear strength for many applications. Another
disadvantage of the Balmer et al. plasticizers is the high pressure,
usually about 1000 to 10,00 psig., required for their preparation.
Coaker et al, U.S. Pat. Nos. 3,809,667 and 3,923,720 disclose liquid
copolymers of two different alkyl acrylate monomers useful as flow
improvers for a variety of polymeric substrates. They do not disclose or
suggest the utility of substantially less costly polymers containing
significant amount of copolymerized olefin for the purposes of such flow
reduction, nor are their polymers suitable for the plasticization of
poly(vinyl chloride).
Leister et al., U.S. Pat. No. 3,968,148, disclose oligomeric terpolymers of
1-alkenes and certain esters of unsaturated acids in a number-average
molecular weight range similar to applicants'. It will be perceived by
examination of their patent that their work was solely directed to oil
additive applications, and that no suggestion was made that these polymers
would be useful for the uses herein disclosed.
It is an object of the present invention to produce plasticizer polymers
having high efficiency in plasticization and softening, and shorter flux
times.
A further object is to prepare plasticizers at low pressures.
A still further object of the invention is to prepare plasticized
compositions having improved electrical insulating properties which are
retained after exposure to water.
Another object is to produce plasticized vinyl chloride compositions having
good fogging resistance and hydrocarbon resistance.
Another object is to provide modified polypropylene compositions having
improved flow without significant loss in other physical properties.
These objects, and others which will become apparent from the following
disclosure, are achieved by the present invention which comprises a blend
of about 1 to 600 parts by weight of a plasticizer which is the free
radical polymerization product of (A) one or more olefins having 6 to 18
carbon atoms, and (B) one or more C.sub.1 to C.sub.6 esters or diesters of
monoethylenically unsaturated mono- or di-carboxylic acids, the molar
ratio of (A) to (B) being about 0.1/1 to 1.5/1, with about 100 parts of a
different polymer.
The olefins having 6 to 18 carbon atoms are monoethylenically unsaturated
hydrocarbons and can be linear, branched or cyclic. Oligomers of ethylene,
propylene, butylene, isobutylene, pentene, hexene, and the like, having
the specified carbon atoms, or linear alpha-olefins, such as octene-1,
decene-1 and the like, are the preferred olefin sources. The suitable
olefins are preferably liquids at room temperatures. Mixtures of olefins
are suitable.
The C.sub.1 to C.sub.6 esters or diester of monoethylenically unsaturated
mono- and di-carboxylic acids are vinyl esters such as alkyl acrylates,
monounsaturated diesters such as dialkyl maleate or fumarate and the like.
"C.sub.1 to C.sub.6 esters or diesters" is meant to include esters derived
from alcohols having one to six carbon atoms, i.e., the C.sub.1 to C.sub.6
refers to the alcohol-derived moiety. For example, methyl acrylate, ethyl
acrylate, methyl thioacrylate, ethyl thioacrylate, methyl thioacrylate,
methyl di-thio-acrylate, diethyl methyl maleate, diethyl maleate, dimethyl
fumarate, diethyl fumarate, 2-chloro-ethyl acrylate, 2-methoxyethyl
acrylate, 2-ethoxy ethyl acrylate, vinyl acrylate, allyl acrylate, propyl
acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl
acrylate, sec-butyl acrylate, n-amyl acrylate, isopropyl thio acrylate,
phenyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate and phenyl thio
acrylate etc. Methacrylates such as methyl methacrylate and 2-ethyl hexyl
methacrylate are also suitable. Mixtures of one or more of these esters
and diesters are suitable.
The preferred esters are C.sub.1 to C.sub.6 alkyl acrylates and mixtures
thereof. One particularly preferred mixture is of ethyl acrylate with
butyl acrylate.
The polymerization product of (A) and (B) further includes polymerized
units of (C) monovinylidene monomers which are chosen from the group which
are polymerized or copolymerized by free radical initiation and can
include acrylonitrile, methacrylonitrile, fumaronitrile, acrylic acid,
methacrylic acid, maleic anhydride, itaconic acid, acrylamide,
methacrylamide, N-alkylacrylamide, N,N-dialkyl acrylamide, 2-hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, vinyl acetate, vinyl 2-ethylhexoate,
styrene, vinyl toluene, chlorostyrene, vinyl chloride, and vinylidene
chloride.
The ratio of the olefin (A) to the ester of diester (B) in the monomer
mixture can be widely varied. Usually a molar excess of olefin is used,
generally in a molar ratio of about 0.5/1 to about 10/1, preferably about
0.5/1 to 4.5/1 and most preferably about 1/1 to 2.5/1. In the plasticizer
polymer, the molar ratio of olefin to ester or diester is generally about
0.1/1 to 1.5/1 and preferably at least about 0.2/1. For plasticization or
flow improvement of olefin-based polymers such as modified polypropylene,
it is preferred that the molar ratio be about 0.4/1 to about 0.85/1.
The ratio of monomer (C) to the olefin (A) and ester or diester (B) can
also be widely varied. In some cases, no monomer (C) is required to
achieve the desired properties, in others, up to 0.25/1 (expressed as
(C)/[ (A)+ (B)] may be required.
The plasticizers are prepared by polymerizing the monomer mixture at a
temperature of about 120.degree. to 250.degree. C., preferably about
180.degree. to 235.degree. C., at low pressures (one of the advantages to
the process aspect of the invention) on the order of about 2 to 15
atmospheres, preferably about 3 to 10 atmosphere, in the presence of free
radical polymerization catalyst at a preferred concentration of about 0.1
to 10%, more preferably 0.5 to 2.5%, by weight based on acrylate. When the
more reactive alpha-olefins are employed less vigorous reaction conditions
may be utilized, including atmospheric pressure conditions.
Suitable catalysts as initiators include organic compounds having peroxide
bonds in general, for example, diallyl peroxide, ketone peroxide, aldehyde
peroxide, ether peroxide, hydroperoxide, dihydrocarbyl peroxide, peracid
ester, percarbonate and percarbamate. Representative examples of the
organic peroxide include benzoyl peroxide, lauroyl peroxide, caprylyl
peroxide, 2,4-dichlorobenzoyl peroxide, 4-nitrobenzoyl peroxide, 4-methoxy
benzoyl peroxide, 4-chloro benzoyl peroxide, acetyl peroxide, stearolyl
peroxide, phthaloyl peroxide, methyl ethyl ketone peroxide, cyclohexanone
peroxide, t-butyl hydroperoxide, p-methane hydroperoxide, diisopropyl
benzene hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl
peroxide, t-butyl cumyl peroxide, t-butyl perbenzoate, t-butyl
perisobutyrate, t-butyl peracetate, t-butyl peroxypivalate, phenyl
percarbamate, diisopropyl percarbonate and t-butyl perisopropylcarbonate.
Preferred are cumen hydroperoxide, di-t-butyl peroxide, t-butyl
peracetate, and t-butyl hydroperoxide.
The plasticizer can be prepared by either a batch, semi-continuous, or
continuous process at high yields, and with resulting molecular weight of
about 500 to 6000 (number average); for plasticization of poly(vinyl
chloride), a range of 700 to 1300 is preferred, whereas for flow
improvement of polypropylene a range of 2500 to 4500 is preferred.
The plasticizer polymer is blended with a different polymer to provide
flexible and semi-flexible articles. The blending is easily accomplished
due to the easily handleable viscosity of the plasticizers usually in the
range of about 10 to 60 poises. Suitable blending techniques include for
example, dry blending or dispersion mixing, compounding on a heated
two-roll mill, extrusion, calendering, casting, injection molding, and
coating of a substrate.
The plasticizer polymer can be used as the sole plasticizer or can be used
in combination with other plasticizers. The concentration of plasticizer
in the blends is typically 1 to 90% by weight, more preferably about 5 to
50% by weight.
The different polymer is preferably a polymer or copolymer of vinyl
chloride, usually PVC itself, but can also be polypropylene, polyethylene,
polyvinylacetate, acrylic polymers, cellulosics, polyamides, polysulfides,
polyurethanes, urethanes, polyvinylbutyral, polyvinylbutyral,
polyvinylbutyralpolyvinylalcohol copolymers, synthetic rubbers, such as
butadiene-acrylonitrile, butadiene-styrene, or chloroprene polymers, and
various rigid thermosets, i.e., polyester resins, phenolic resins, urea
formaldehyde resins, or melamine resins. The different polymer may be a
blend of several polymers, such as polypropylene blended with and/or
grafted to an ethylene/propylene rubbery substrate.
The blends can, and typically do, contain other additives such as
stabilizers, fillers, pigments, foaming agents, or other conventional
additives.
The blends of the invention have a very wide range of utilities. One very
suitable use for the blends is for electrical insulating materials due to
the superior electrical insulative properties which are retained even
after exposure to water. The property of fogging resistance makes the
blends very suitable for automotive interior applications. "Fogging" is
the collection of condensed plasticizer vapors on interior glass surfaces
of automobiles.
Another advantageous property deriving from the use of the plasticizers of
the invention is higher clarity and tear strength versus the closest
previous plasticizer; also "plasticizing efficiency", i.e., rate of
fluxing, etc., is improved.
Another advantageous property deriving from the use of the polymers of this
invention is the improved flow of modified polypropylene without sacrifice
in other physical properties. It is known that certain impact-modified
polypropylenes and also certain thermoplastic elastomers based on blends
or grafts of polypropylene with ethylene/propylene elastomeric substrates
exhibit undesirably poor flow in extruded and especially injection molding
operations, which cannot be readily corrected by increase in processing
temperature. The problem is most acute in regions of low shear, such as in
the total filling of mold cavities. Polymers of the present invention at
relatively low use levels allow improved flow without a sacrifice in the
needed use properties of stiffness, elongation set, etc.
The following examples are presented to illustrate a few embodiments of the
invention, but we do not intend the invention to be limited to the
illustrated embodiments. All parts and percentages are by weight unless
otherwise indicated.
______________________________________
--M.sub.n = Number Average Molecular Weight
P.sub.3 = Propylene trimer
EA = Ethyl acrylate
BA = Butyl acrylate
VSC = Varnish Scale Color Test which is
a standardized test
T135,000, .degree.C.
= Temperature at which a modulus of
135,000 psi is achieved
ATREOL No. 9
= A type of mineral oil
EHA = Ethyl hexyl acrylate
AN = Acrylonitrile
PPA = Polypropylene adipate
DOP = Dioctyl phthalate
2-HEA = Hydroxyethyl acrylate
DIB = Diisobutylene
ULT = Ultimate elongation
______________________________________
EXAMPLE 1
To a 2-1, stirred Parr autoclave was added 126 parts propylene trimer (1.0
mole); the reactor was sealed and sparged with nitrogen and heated to
190.degree. C. where the pressure was 40 psig. The gradual addition of 100
parts (1.0 mole) of ethyl acrylate, containing 1.2 parts (1% on wt. of
acrylate) or cumene hydroperoxide (CHP) was begun at constant rate. The
acrylate/CHP addition was completed over a period of 4 hours, at the end
of which time the temperature was 200.degree. C. and pressure 75 psig. The
reactor was heated an additional 1.0 hr., at 190.+-.5.degree. C. and then
cooled. The product was stripped of unreacted monomers (propylene trimer
and ethyl acrylate) at a pot temperature of 50.degree.-100.degree. C./10-5
mm Hg and from lower mol. wt. volatiles at a pot temperature of
210.degree. C. at 0.1 to 5 mm Hg. The product is undistilled bottoms
materials, which needs no further purification. Yield 105 parts.
EXAMPLE 2
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 280
Ethyl acrylate 120
Cumene hydroperoxide 2.8
______________________________________
Process: That of Example 1. Product yield 120 parts.
EXAMPLE 3
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 315
Ethyl acrylate 100
Cumene hydroperoxide 3.15
______________________________________
Process: That of Example 1, except at a reactor temperature of 250.degree.
C. and 175 psig pressure. Product yield 118 parts.
EXAMPLE 4
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 560
Ethyl acrylate 120
n-butyl acrylate 120
Cumene hydroperoxide 1.2
______________________________________
Process: That of Example 1, except at a reactor temperature of 220.degree.
C. and 115 psig pressure. Product yield 260 parts.
EXAMPLE 5
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 560
Ethyl acrylate 160
2-ethylhexyl acrylate 80
Cumene hydroperoxide 5.6
______________________________________
Process: That of Example 1. Product yield 265 parts.
EXAMPLE 6
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 280
Ethyl acrylate 140
n-Butyl acrylate 140
Cumene hydroperoxide 2.8
______________________________________
Process: That of Example 1, except polymerization temperature of
220.degree. C. at 115 psig pressure. Product yield 220 parts.
EXAMPLE 7
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 280
Ethyl acrylate 140
n-Butyl acrylate 98
2-ethylhexyl acrylate 42
Cumene hydroperoxide 2.8
______________________________________
Process: That of Example 1, except polymerization temperature of
220.degree. C. at 115 psig pressure. Product yield 250 parts.
EXAMPLE 8
______________________________________
Charge: Parts:
______________________________________
Propylene tetramer (a mixture
of C.sub.12 olefins) (P.sub.4)
504
Ethyl acrylate 85.5
n-Butyl acrylate 85.5
Cumene hydroperoxide 1.71
______________________________________
Process: That of Example 1, except polymerization temperature was
210.degree. C. and pressure 65 psig. Product yield 160 parts.
The plasticizing properties of the above plasticizers (Examples 1-8) to 67
phr in PVC and with 1.7 parts Ba/Cd laurate stabilizer are listed in Table
I. The details of the test methods used are described in Rohm and Haas
Publication MR-80.
EXAMPLE 9
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 350
n-Butyl acrylate 160
Acrylonitrile 8
Cumene hydroperoxide 3.5
______________________________________
Process: That of Example 1, product yield 170 parts.
EXAMPLE 10
As a comparison, conventional polyester plasticizers, poly-(propylene
adipate) (PPA) of molecular weight (M.sub.n) of about 900 and 4000, and
conventional monomeric plasticizer, dioctyl phthalate (DOP), are
incorporated in the same PVC formulation and compared in Table I to the
plasticizers of Examples 1-9. The plasticizers of the instant invention
can be made with varying degrees of plasticizing efficiency, low
temperature flexibility, extraction resistance, and migration resistance.
The preferred composition (Example 4) has adequate plasticizing efficiency
and low temperature flexibility to be commercially acceptable, and has
superior resistance to extraction by oils and hydrocarbons and migration
into materials such as foam rubber when compared to polyesters of similar
mol. wt. and when compared to common monomeric plasticizers. In addition,
the composition of Example 4 is dramatically superior to the common
monomeric plasticizer for resistance to loss via volatility and extraction
by soapy water.
TABLE I
__________________________________________________________________________
Plasticizer
No. of Example
1 2 3 4 6 7 8 PPA PPA DOP
__________________________________________________________________________
--M.sub.n 1150 880 890 780 907 1260 1000 900 4000 390
Olefin P.sub.3
P.sub.3
P.sub.3
P.sub.3
P.sub.3
P.sub.4
P.sub.3
Olefin Wt.-% 15 25 30 25 15 25 20
Acrylate EA EA EA EA/BA
EA/BA
EA/BA
BA/AN
1/1 1/1 1/1
G-H Viscosity ZY+ W+ W T W+ Y- T K Z12 A
VCS Color 2 1 2 2 2 2 2 1 5 1
Shore A Hardness, 10 sec.
88 83 80 79 86 86 84 72 87 68
T135,000, .degree.C.
+12.5
+5 -3 -5.5 -2.0 -6.5 -8 -17 -6 -35
Volatility. 24 hr. 90.degree.
C. % (ACOG/14X)
2.0 3.6 2.1 1.2 1.7 4.8 1.8 1.3 0.6 6.2
1% Ivory Flakes Extr'n.,
24 hr./90.degree. C., %
7.0 7.2 10.5 3.6 6.3 9.7 2.2 4.5 8.3 6.9
n-Hexane Extr'n.,
2 hr./.degree. C., %
0.3 1.9 6.8 10.6 7.8 17.1 20 12 0.2 27.7
Atreol No. 9 Extr'n.,
10 days/RT,% 0.1 0.1 0.4 2.0 7.3 0.1 9.0
Migr'n. into Foam Rubber
7 days/60.degree. C., 1/4 psi,%
1.6 3.3 3.4 3.2 6.4 0 14.4
__________________________________________________________________________
EXAMPLE 11
Critical tests for the amount of volatile material in a compound are the
automotive fogging tests. The Fisher Body Division of General Motors Corp.
Test No. 46-3, revised 2/67, and conducted at 175.degree. F., is utilized
for the present tests. The performance of the composition of Example 4 is
shown in Table II.
TABLE II
______________________________________
FISHER BODY TEST NO. 46-3, TEMP. 175.degree. F.
Plasticizer* Deposit On Glass
______________________________________
Material From Example 4 (Table I)
None
DOP Gross
Glass Plate Control None
______________________________________
*Formulation:
100 PVC
67 Plasticizer
1.7 Ba/Cd Stabilizer
______________________________________
EXAMPLE 12
Insulation for electrical wires and insulation for electrical wires and
insulating tapes are frequently required to maintain a high degree of
resistivity after immersion in or exposure to water. Plasticizers of the
instant invention (Examples 3 and 4) are equivalent in performance to DOP
(and industry standard) and superior to conventional polyester
plasticizers for maintaining volume resistivity after immersion in water,
as illustrated in Table III. All are evaluated in the following
formulation:
100 Parts PVC;
55 Parts Plasticizer;
10 Parts Dibasic lead phthalate;
5 Parts No. 33 clay;
0.5 Parts Paraffin wax;
0.5% by weight bisphenol A based on the plasticizer content.
TABLE III
______________________________________
Example
Example PPA
3 4 DOP -- M.sub.n = 1000
______________________________________
Volume Resistivity
ohm-cms .times. 10.sup.-12
90.degree. C. Dry
1.0 1.5 0.4 0.6
After Immersion
in Water at 75.degree. C. For
1 Day 2.6 1.6 1.2 0.07
1 Week 3.8 0.6 0.9 0.04
1 Month 0.5 0.9 1.2 0.01
______________________________________
EXAMPLE 13
In Table IV, a side-by-side comparison is presented between the
plasticizers prepared in accordance with U.S. Pat. No. 3,224,996 versus
those of the present invention. Plasticizers of similar composition
(olefin to acrylate ratio, wt.-%) and mol. wt. have been selected for
comparison. The advantages of the plasticizers of the present invention
over prior art plasticizers are in compatibility (flux times, clarity, and
color slab, stress-whitening resistance and tear strength), efficiency,
and low temperature flexibility (Tf). The preferred composition, F, has
the best overall application properties.
EXAMPLE 14
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 252
Ethyl acrylate 57
n-Butyl acrylate 57
Cumene hydroperoxide 3.5
______________________________________
Process: That of Example 1, except polymerization temperature of
200.degree. C. at 115 psig pressure. The product is lower mol. wt.
material, separated via distillation at 200.degree.-230.degree. C./0.1 to
5 mm Hg from undistilled higher mol. wt. bottoms material after the
removal of unreacted monomers. Product yield 70 parts.
TABLE IV
__________________________________________________________________________
Plasticizer A B* C D E* F G H
__________________________________________________________________________
P.sub.3 /EA
P/EA Data Rept'd
Data Rept'd
E/EA P.sub.3 /EA
P.sub.3 /EA
P.sub.3 /EA
in Ex. 11 of
in Ex. 12 of /BA /BA
U.S. 3,224,996
U.S. 3,224,996
P/EA P/MA
Ratio of components,
wt.-% (.+-.5%)
30/70 30/70 30/70 30/70 30/70 25/37.5
25/50/
25/75
/37.5 25
M.sub.n 890 908 772 684 1190 780 800 880
Plasticizer in PVC,
wt.-% 40 40 40 40 40 40 40 40
Tear Strength
V. Good
Good(-)
Not Rept'd
Not Rept'd
Poor V. Good
V. Good
V. Good
Clarity of Slab
Good Poor Not Rept'd
Not Rept'd
Poor Good Good Good
Color of Slab
Lt.Yellow
Dk.Tan
Not Rept'd
Not Rept'd
Straw Pale Straw
Pale
Straw
Flux Time, min.
3/4-1 1-11/2
Not Rept'd
Not Rept'd
2 (+) 1-11/2
1- 13/4
1-11/2
Degree of Stress-
Whitening None Slight
Not Rept'd
Not Rept'd
Slight
None None None
(+) (+)
Shore A Hardness
80 89 88 87 86 79 82 83
T135,000, .degree. C. (low
temp. flexibility,
lower being better)
-3 +6 -5.5 +4 -2.0 -5.5 -1.5 +5
Volatility, 24 hr./90.degree. C.,
% (ACC6/14X) 2.1 2.8 2.9 3.4 0.8 1.2 1.6 3.6
1% Ivory Flakes Extr'n.,
24hr./90.degree. C., %
10.5 5.3 5.0 11.7 1.3 3.6 3.9 7.2
n-Hexane Extr'n.,
2hr./.degree. C., %
6.8 5.0 31.8 16.5 8.6 10.6 6.9 1.9
__________________________________________________________________________
Note:
P.sub.3 = propylene trimer, a mixture of C.sub.9 olefins
P = propylene monomer
E = ethylene
EA = ethyl acrylate
BA = butyl acrylate
MA = methyl acrylate
* = plasticizers B and E were prepared according to U.S. 3,224,996.
EXAMPLE 15
______________________________________
Charge: Parts:
______________________________________
Propylene trimer 350
n-Butyl acrylate 163
2-Hydroxyethyl acrylate 14
Cumene hydroperoxide 3.5
______________________________________
Process: That of Example 1, except polymerization temperature of
235.degree. at 135 psig pressure. The product is obtained after stripping
the unreacted monomers (propylene trimer, n-butyl acrylate and
2-hydroxyethyl acrylate). Product yield: 185 parts.
EXAMPLE 16
______________________________________
Charge: Parts:
______________________________________
Di-isobutylene 310
n-Butyl acrylate 163
2-hydroxyethyl acrylate 14
Cumene hydroperoxide 3.5
______________________________________
Process: That of Example 1, except polymerization temperature of
215.degree. C. at 150 psig pressure. The product was obtained after
stripping the unreacted monomers. Product yield 195 parts.
The polymers of Examples 14-16 were evaluated as a plasticizer for
poly(vinyl butyral) (PVB) resin. The evaluation data are described in
Table V. The plasticizing properties of Examples 14-16 have been compared
with commercially used plasticizer triethylene glycol di-2-ethylbutyrate
(Table V). The plasticized PVB resins are especially useful as the
interlayers in laminated safety glass in architectural and vehicle
applications. The techniques for evaluating the plasticizer properties
described in Table V are well known to those who are skilled in the art.
TABLE V*
__________________________________________________________________________
Plasticizer at 45 phr Triethylene Glycol
No. of Example 14 15 16 di-2-ethylbutyrate
__________________________________________________________________________
M-n 500 700 800 --
Olefin P.sub.3
P.sub.3
DIB --
Olefin wt.-% 40 25 30 --
Acrylate EA/BA
BA/2-HEA
BA/2-HEA
--
= 1/1
= 11.5/1
= 11.5/1
G-H Viscosity G K M --
VCS Color 1 2 2 1
Compatibility C C C C
Low Temperature -18 -8 -5 -38
Fluxibility, 135,000, .degree.C.
Brittle Point, .degree.C.
-35 -38 -20 -66
Volatility, 4 hrs/150.degree. F.
0.90 0.60 0.75 0.5
in air % loss
High Humidity Spew, 4.degree. C./7 Days
Slight
Def. Def.+ Def.+
Water Immersion 100.degree. F./10 mins.
0.3 0.45 0.35 0.7
% absorbed
% Plasticizer extracted
1.10 0.90 0.7 0.9
Tensile Strength, psi
3850 3000 3200 3000
100% Modulus, psi
1320 850 1100 230
% Ult. Elongation
305 285 290 235
Clarity of Film Excellent
Good Fair Excellent
__________________________________________________________________________
PVB resin ("Butacite") was obtained from E.I. duPont Co. Application
evaluation was carried out on 30 mil pressed sheet utilizing the procedur
known to the art.
EXAMPLE 17
The preparation technique of Example 1 was employed to prepare a polymer
suitable for plasticization of PVC based on an .alpha.-olefin. To the
reactor were charged
110 Parts (1.3 moles) hexene - 1
700 Parts toluene to the reactor was heated to 210.degree. C. and to it was
fed over four hours
334 Parts (3.74 moles) ethyl acrylate
195 Parts toluene
8.4 Parts cumene hydroperoxide
the reactor was heated an additional one-half hour at 210.degree. C.,
cooled, vented, and the toluene, unreacted monomers and low volatiles
stripped as in Example 1.
EXAMPLE 18
The polymer of Example 17 was compared against a conventional polyester
plasticizer in the manner taught in Example 10. At 67 phr, the following
properties were found, demonstrating utility of the subject polymer as a
plasticizer in PVC:
______________________________________
Conventional
Example 17
Polyester
______________________________________
Volatility, % 1.4% 0.7
Soap extraction, %
7.9% 5.2
Hexane extraction, %
5.5% 1.0
Shore A * Hardness
91/87 82/79
T.sub.135,000, .degree.C.
-3 -15
______________________________________
EXAMPLE 19
To a reactor similar to that described in Example 1 was charged 660 parts
(4.7) moles of decene-1. The reactor was swept with nitrogen for 10
minutes, sealed and heated to and maintained at 135.degree. C. The
pressure within the reactor throughout the run varied from 10-20 psig.
(0.7-1.4 kg./cm..sup.2 gauge). Over a period of three hours was fed 400 g.
(4 moles) of ethyl acrylate and 13.2 parts of t-butyl perbenzoate. The
reactor was held for one hour further and then stripped at 150.degree.
C./0.5 mm. pressure to yield 442 g. of polymeric nondistilled product,
analyzing as 48% olefin/52% acrylate by weight, number average molecular
weight by gel permeation chromotography (M.sub.n - GPC) 3860.
EXAMPLE 20
In a manner similar to that used in Example 19 were prepared the following
polymers:
______________________________________
COMPOSITION
POLYMER Olefin, wt. %
Acrylate, wt. %
.sup.--M.sub.n -GPC
______________________________________
20-A Hexene-1, 37 Ethyl 31.5 1430
Butyl 31.5
20-B Octene-1, 39 Ethyl, 61 4230
20-C Dodecene-1, 50
sec.-Butyl, 50
4330
20-D C.sub.11 --C.sub.14 mix, 62
Ethyl, 38 4330
______________________________________
EXAMPLE 21
On a two-roll mill operating at speeds of 26 rpm (front roll) and 20 rpm
(back roll) were milled for four minutes at 350.degree. C. blends of the
polymeric additive of Example 19 and several polypropylene samples. Flow
data were determined by ASTM-D-1238, condition L and are shown in the
following Table:
______________________________________
Flow.sup.1 (g./10,in.)
Oligomer Modified
(Weight Percent)
Unmodified 2 3 4 5
______________________________________
Profax.sup.2 6523
4.3 -- -- -- 11.0
Profax 8623/Profax
7.3 10.5 -- -- 25
6323 (1:1)
Profax 7523 5.7 7.8 8.0 8.9 --
Exxon.sup.3 805Mc
6.4 8.5 9.2 10.5 13
______________________________________
.sup.1 ASTM D1238 condition L (g./10 min.); a higher value shows improved
flow
.sup.2 Hercules Inc.
.sup.3 Exxon Chemicals
EXAMPLE 22
Blends of the additive of Example 19 with several commercial modified
polypropylenes were prepared by mixing in a Henschel mixer, extending to
form pellets, and injection molding. The properties are shown in Table VI;
it should be noted that impact strength, heat distortion temperature and
tensile strength are only slightly changed, while flow continues to be
improved.
EXAMPLE 23
The polymeric additives (10 parts) of Examples 19 and 20 were milled for 5
minutes at 350.degree. F. with 100 parts of Uniroyal's thermoplastic
elastomer TPR-1900, believed to be a graft or blend of polypropylene with
an ethylene-propylene rubber similar to materials taught in Fischer U.S.
Pat. No. 3,862,106. Flow properties were measured at several shear rates
on a Siegloff-McKelvay thermometer at 400.degree. F.
______________________________________
MELT VISCOSITY, Poise at 400.degree. F.
SHEAR RATE.sup.-1
ADDITIVE sec
SAMPLE 10 phr 10 40 200
______________________________________
TPR-1900 -- 45700 18800 6400
TPR-1900 Ex. 19 14300 5900 2600
TPR-1900 Ex. 20-A 12500 -- --
TPR-1900 Ex. 20-B 12300 -- --
TPR-1900 Ex. 20-C 22000 -- --
TPR-1900 Ex. 20-D 14300 -- --
______________________________________
TABLE VI
__________________________________________________________________________
PHYSICAL PROPERTIES OF MODIFIED AND UNMODIFIED POLYPROPYLENE
IZOD IMPACT.sup.2 (ft.-lb.)
Elonga-
Tensile
Tensile
Gardner
Melt.sup.1 Flow
Notched
Notched
Unnotched
DTUFL.sup.3
(.degree.C.)
tion Stress
Modulus
Impact
(g/10 min.)
23.degree. C.
-18.degree. C.
-18.degree. C.
66 psi
264 psi
(%) (psi)
(psi)
(in.-lb.,
__________________________________________________________________________
RT)
pp-8623/pp-6323
7.2 1.1 .+-. .1
0.3 .+-. .1
8.0 .+-. 2.3
112 58 8.9 3800
175,500
118 .+-. 8
(1:1).sup.4
pp-8623/pp-6323/
10.0 1.1 .+-. .2
0.2 .+-. .1
8.8 .+-. 1.6
110 55 9.9 3600
163,500
108 .+-. 7
oligomer (2%)
pp-7523.sup.4
4.6 1.6 .+-. .1
0.3 .+-. .1
4.8 .+-. 1.1
108 60 12.1 4000
183,800
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