close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3090773

код для вставки
May 21, 1963
E. L. HILLIER
3,090,763
DRY BLENDING VINYL RESIN
Filed Jan. 25, 1960
INVENTOR
EDWARD L. H/L L IE1‘?
av
Zia‘
ATTORNEY
United States Patent O?ice
3,090,763
Patented May 21, 1983
2
1
3,090,763
DRY BLENDING VlNYL RESIN
Edward L. Hillier, Cuyahoga Falls, Ohio, nssignor to The
United States Stoneware Company, Tallmadge, Ohio, a
corporation of Ohio
Filed Jan. 25, 1960, Ser. No. 4,406
4 Claims. (Cl. 260-23)
This invention relates to an improved process of using
a powdered additive with a plasticized vinyl resin to pro
duce a iree~?owing powder, known as a dry blend.
Dry blends have been on the market for some time.
Only certain types of vinyl resins and certain plasticizers
have been usable in their production. When a powder
ing additive (described in detail hereinafter) is added to 15
a damp, particulate mass of any extrusion grade of plas
ticized pearl-type vinyl resin (as hereinafter explained),
the resin-plasticizer blend becomes free ?owing. A blend
Di-Z-ethylbutyi phthalate
Bis(diethylene glycol monoethyl cthe:)phthalate
Di-n-hexyl phthalate
Di-Z-ethylhexyl phthalate
Diiso-octyl phthalate
Di-lsethylhexyl hexahydrophthalatc
Trien~butyl phosphate
Tributoxyethyl phosphate
Cresyl diphenyl phosphate
Z-ethylhexyl diphenyl phosphate
Tricresyl phosphate
Di-n-hexyl adipate
Di-butyl-Z-ethoxyethyl adipate
Di-Z-ethylhexyl adipate
Diiso-octyl adipate
Octyl decyl adipate
Butyl phthallyl butyl glyeollate
Ethyl phthallyl ethyl glycollate
is free ?owing if it has a flow rate of at least 5 cc. per
second by equipment described in ASTM D-392-38 (ap
20
parent density test). The rate of flow as there described
is referred to herein, and particularly in Table V, as the
Polygiycol di-2-ethylhexanoate
"dry blend flow.”
The powdering additive may be any one or more very
finely divided solid materials of a large class which com
Di-n-butyl sebacate
Di~2-ethylhexyl sebacate
Di-2‘ethylhexyl azelate
Methoxyethyl acetyl ricinoleate
25
prises both organic and inorganic compounds. These
Polyesters of dibasic acids and diols (known as dif
ferent grades of Paraplex and manufactured by Rohm
& Haas Co.)
Chlorinated paraiiin
will be described hereinafter.
There have been various disadvantages or limitations
Epoxidized soya oil
Tetra-n-butyl thio disuccinate
inherent in the prior methods of producing free-?owing
blends, primarily because it has been possible to use only 30 l3is(dimethyl benzyl)ether
certain resins and certain plasticizers in producing them.
Any of these and any other plasticizer can be used in
In the process of this invention, any pearl-type resin and
carrying out the invention.
The plasticizer is mixed with the resin after the resin
any plasticizer can be used.
Furthermore, the dry blends of the prior art have not
been too satisfactory. The extrudates obtained from
them have often been porous, of high “?sh eye" content
and rough surfaced, due to inadequate densi?cation of
the resin-plasticizer mass in the extruder.
has been heated, or while heat is being transferred to the
resin to assist solvation. The plasticizer may be heated
before being added to the resin. After plasticizing and
preferably after cooling, the powdering additive is added
This can be
overcome by increasing the length of the extruder work
ing chamber or by using a higher internal working pres
to the plasticized resin, and this is all done in the same
40
sure. Such remedies increase the cost per unit output.
According to this invention such difficulties are over
come. The resin-plasticizer product treated with the
powdering additive has a higher bulk density than that
of the prior art materials. It approaches the theoretical
which is the speci?c gravity of the product. The increase
in bulk density of the dry blends obtained by the process
of this invention will be illustrated by examples, in what
follows.
The vinyl resins used in carrying out the invention in
clude both homopolyrners of vinyl chloride and copoly
organic powdering additives are no more than one-tenth
percent soluble in either hot or cold water. The organic
powdering additives are generally less than about 5 per
cent soluble in the plasticizer being utilized in the blend.
Although the powdering additive is not mixed with the
plasticizer, if organic it is of such a nature that upon
dispersing 5 parts (by weight) of the additive in 100 parts
of the plasticizer employed, there is no evidence of set
tiing, the additive being ?ne enough to form a homo
geneous, stable, opaque dispersion in the plasticiaer.
The following table lists many materials of very dif
mers of vinyl chloride and any one of the many mono~
Such monomers include, for ex
ample, vinyl acetate, vinylidcne chloride, diethyl maleate,
etc. The term "polymer" is used herein to include homo
polymers and copolymers of vinyl chloride.
Many liquid plasticizers have been used with vinyl
resins. The following are listed merely as illustrative: ‘
Dimethyl phthalate
Diethyl phthalate
Dimethoxy ethyl phthalate
Dibutyl phthalate
Butyl cyclohexyl phthalate
Butyl benzyl phthalate
Dibutoxy ethyl phthalate
The term “powdering additives" is used herein to refer
to solids as de?ned in this paragraph. Whether organic
or inorganic, the powdering additive is so ?nely divided
that it passes through a ISO-mesh screen. if of an in
organic composition, the powdcring additives are amor
phous as distinguished from crystalline, and this distinc
tion can be determined visually or microscopically. in
mers with which vinyl chloride has been copolymerized
to produce a resin.
vessel as a part of one continuous operation.
erent chemical compositions which were eli'ective as pow
60
dering additives, and others that were not satisfactory in
the concentrations used. The different powdering addi
tives were tested in this formula:
Parts by weight
Marvinol VII-24 __________________________ __ 100.0
05 Butyl phthallyl butyl glycollate ______________ __
75.0
Tin stabilizer _____________________________ _Ultramarine blue __________________________ -_
1.0
0.l
3,000,763
3
4
The first column gives the water solubility for inorganic
additives and the plasticizer dispersibility of organic addi
MATERIA LS TESTED, ETC.-—Conti nucd
tives as S0]. (soluble or dispersible), Ins. (insoluble or
non-dispcrsible), Sl. Sol. (slightly soluble or dispersible),
Organlcs
V. Si. 501. (very slightly soluble, dispersible) and Disp.
(stable, opaque dispersion). The second column indi
Plaatlclzer
dlsperalblllty
Conden
tratlun
used
(per
Em
elency
catcs the concentration in which the material was em
ployed in percentage, based on the weight of the vinyl
polymer. The next column indicates whether or not the
added material was effective as a powdering additive, 10
Alumlnum stearute
the various materials in the concentrations used being
rated as E (excellent), G (good), F (fair), I’ (poor)
Cadmium stnuru
Load stcorato..
and B (bad).
Oulelum sloarato
l'inrlum nteurnw.
arm-
COLO R8
Those rated F, G or B have ?ow rates in
excess of 5 cc. per second.
s.
The list is not intended to
I‘htholdcysnlno
Phtholdcynnlne
be complete.
eon ................ ._
lue ................. _.
Dlphcnyl thloearbnzono ______________ ..
Ornsol red ('IZCI dye) .................. ..
O~eresol phthuleln .................... ..
MATERIALS TESTED AS POWDERING ADDITIVES
Concen
tratlnn
Wntor
]norganlcs
soluhlllty
used
nnsms
20
Em
Bakelite VYNV~2 .................... ._
PVC, Eseambla 2260..
l’VO, Dow 100-4 ____ ..
alone;
(PW'
cent
25 Saran A..
Epon i000...
Ethyl oellulo
I‘llovlc A0 ................ ..
MISCELLANEOUS
Ȥs.- newr-magsi
Hydroqulnono ....................... -.
allic aeld._--_
gliydror
bonzoleu-cld:
-Oxynap Lholc acid.
35
0 onurle acid ..... ._
Dlphanyl carbonate. .. ..._
II droxylamlne hydrochloride.
0 uooso _________________ ._
lioramcthylenetetramtne
Beta naphthol
Ultrox ZrBl0|.....
Urea ........ ..
oxmu
Cellto
Oroun
grnnulate
50 Sugar,
Guitar powdered
Bios) - -
Glycol lite-notes...
nnnd. .
65
According to this invention the plasticizer is added to
the resin as it is being agitated ‘by movement of the vessel
containing the resin, and heat is supplied to cause absorp
tion of the plasticizer in the resin. Then as a part of llhO
same operation, the resin is preferably cooled, as by con
tact with a gas which is cooler than the resin. The resin
should be cooled to a temperature above room tempera
ture and below about 250" F. The powdering additive
is then added, still as a part of the same operation.
Stabilizers, coloring materials, etc. can be incorporated
with the resin or plasticizer, or both, in any usual man
ner. Dry compounding ingredients may be mixed into
Graphite .... ........ ............... ....
Copper
In! ........ ._
24
B
wdcr........
.
lus.
,
24
]!
Rhombulullun. .... ..
.
inn.
.
24
B
lnl.
.i
24
lnl.
__i
8
F~G
In8....._._..
4
E
Iron powder ......... ..
.
Aluminum powden.
.
Lnmphloc
................ ... ....... ..
B
70 the resin before adding the plasticizer.
Dry pigments
may be mixed as a powder with the ?nely divided resin
without being dissolved therein. Liquids may be added
to the plasticizer, and ?nely divided solid compounding
75 ingredients may be suspended in the plasticizer before it
3,090,763
6
is mixed with the resin.
The Dow Chemical Co;
Dow l00-4—_Type 1
Usually liquid compounding
ingredients will be added to the plasticizer to insure uni
form distribution throughout the resin. A ?nely divided
Dow lll-4--Type l
compounding ingredient other than the powdering addi
Escambia Chemical Corporation:
Escambia USS-Type l—low molecular weight
Escambia l200—Ty=pe 1
tive may the mixed with the free-?owing resin after the
powdering additive has been added to it, or such a com
pounding ingredient may be mixed with the powdering
additive before it is mixed with the resin.
The pearl-type vinyl resins that can be used in carry 10
ing out this invention, include the ?rst three of the fol
lowing four types of resins all of which are referred to
herein as extrusion grades to distinguish them from Type
No. 4 which includes resins all of which are soluble is
The
(about 20 percent) at room temperature in active sol
vents such as methyl ethyl ketone and are used as solution
resins in paint and lacquer formulations. These types
of resins do not include emulsionpolymerized, dispersion<
grade paste resins.
20
Escambia 1225—Type 1 '
Escambia
Escambia
Escambia
Escambia
1250—-Type
HOD-Type
2225—Type
2250--Type
l
2
2
2
Firestone Tire & Rubber Company:
Exon 915-'l‘ype 1
Exon 925—-Tyipe l.
Exon 666—Type l—low molecular weight
Exon 402—-Type l—low molecular weight
Type No. 1.—~This type of resin is available as large
agglomerates that are relatively porous. The polymer is
made by the suspension or pearl process. Thirty to 100
The Goodyear Tire & Rubber Company:
Pliovic S-50—Type l—low molecular weight
Pliovic K-90——Type l
percent of the agglomerates is retained on an 80- to 100 25
mesh screen. Seventy percent of an average material is
retained on an SO-mesh screen. The bulk density of such
agglomerates runs ‘from 0.450 to 0.500 gram per oc.
The B. F. Goodrich Company:
Goon 101 EP-Type l
Geon 118-Type 3
Microscopic examination shows these resin agglomerates 30
Geon l01-—Type l
to be spherical, dull, white and smooth. This type of
Geon 101 EPF 2l-—Type l
resin has been used in producing dry blends, as disclosed
Geon 202-Copolymer of vinyl chloride and vinyli
in the prior art.
dene chloride
Type No. 2.—This type of resin, also made by the
35
pearl or suspension method, has most of the general
characteristics of the former type.
Union Carbide Corporation: VYNW-é-Type 3—~Co
polymer of vinyl chloride and vinyl acetate
The particles are ex
tremely large and differ from Type No. 1 in that (1)
the agglomerates are retained 100 percent on an 80—rnesh
screen, and (2) their ‘bulk density is higher, ranging up 40 General Tire & Rubber Company:
Vygen l0S—-Type l
to 0.550 gram per oc. They have a high capacity for
Vygen
l20-Type l
absorption of plasticizer and the plasticized resin can be
Vygen l6l—-Type 3
truly free ?owing. This type of resin has been used in
the production of dry blends, according to the prior art. 45
Naugatuck Chemical Company:
Type No. 3.—This type of resin is known as a. cold
Marvinol VR-24-—Type l
blend resin and is made by the pearl or suspension
Marvinol VR-33-‘Upe 3
method. The agglomerates are small and they absorb
Marvinol MX~240l--Type l—low molecular weight
large amounts of plasticizer. The bulk density is in the
50
Marvinol VR--26~Type l—low molecular weight
range of 0.3 to 0.35 gram per cc. These resins are usu
ally mixed cold, i.e. plasticizer is added without heating.
Monsanto Chemical Company: Opalon 300 FlvL-Type 1
When plasticized they are not free-?owing.
Type No. 4.—This type is limited to the solution-grade
resins. On microscopic examination they are dense, 55 Diamond Alkali Company:
Diamond PVC—450-—Type 1
glassy particles rather than spongy, dull particles. They
Diamond DX—35—Type l—low molecular weight
are of such small particle size that no less than 20 per
Diamond DX-30-Type l—low molecular weight
cent will pass through a l20-mesh screen. They include
Diamond 500—-Type 1
(I) copolymers of vinyl chloride with at least about 10 BO
to 15 percent of vinyl acetate or vinylidene chloride and
Rubber Corporation of America:
Insular 155~—Ty-pe l—low molecular weight
Insular 200—Typc l
(2) homopolymers of vinyl chloride of low molecular
weight and an intrinsic viscosity of no more than about
0.80. They can be made by different processes and when
made by the pearl or suspension type process, and only 65
J. P. Frank Chemical Co.:
when so made, may be utilized in carrying out this inven
tion.
Presto 315—40—Type l
Presto 325-40-Type l
Reference will be made herein to various commercial
Presto 402—4tl—Type l—low molecular weight
resins and they will be identified by their trade names. 70
Those that are listed immediately below are all made by
Thompson Chemical Company: Trulon 520~Type l—
low molecular vweight
the pearl or suspension process and are identi?ed under
the name of the manufacturer of each. Each of the fol
lowing is a polyvinyl chloride homopolymer unless other
wise identi?ed.
75
The following tables give properties of various resins.
3,000,703
TABLE I
General Prapernes of Varrous Vmyi Resms
Dimer‘
Rosin
nlon
1111mm»
Bulk
density
Burlncc
M011, sq.
1.22
1.21
1.17
1.17
1.10
1. 1a
1120
1020
104
v low
044
.440
.4011
.001
.4110
.400
40.1
4.43
142
174
1111
123
100
1721
0103
0110
.0174
0177+
0120
0104
212
212
212
212
212
212
0
P
G
o
0
G
XXIX
1.03
1.02
1.02
zux
1. 01
374
417
401
03.1
410
.072
.483
4014
203
488
400
402
1.00
v. low
0123
0103
0102
0120
01.10
0100
.0177+
212
212
212
212
212
212
212
O
0
P
P
P
P
0
lty
Dow 100-4 _______________ _.
Own 101 ................ ._
Rammbla 1200 ___________ ..
Eacmnblu 22110 ........... ..
Vyxun 120 ............... ..
0011100 11001-‘M .......... ..
Dry blend characteristics
intrinsic
vlseos-
otor
Particle
11110, cm.
cmJg.
Tgnllapq
Ml:
Flow
007
100
12:1
340
171
14s
102
10.1
100
0
xxu
1.020
043
2104
0000
212
P
nu
. 4.13
004
0:111
00117
212
P
xxxx
011
.200
.204
4011
007
1211
110
.0100
.0103
212
212
011
011
0.1
.88
v. low
407
114
.400
.1104
.040
1.143
4112
404
041
11711
21a
211
100
.0177+
.0102
.0103
.0100
.0100
100
100
100
100
0
0
G
P
P
P
P
83
.
047
17s
.0103
170
P
.004
B72
2100
017
(H6
0111
01:1
480
100
1:10
110
210
.0140
0120
.0141
.0004
170
100
212
100
P
P
P
P
1.00
.
xxxx
xxxx
xxx:
1117171
1111
100
.711
1477
.000
538
.041
200
2:14
.0000
0070
212
100
P
P
..
.72
.020
.1124
233
.0082
100
P
.71
.071
.088
1711
.0007
170
P
Diamond DX-iltl ........ ..
xxxx
1.138
. 606
120
.0188
170
P
Morvinoi LAX-2401.
Pllovio B-w .... __
Marvinol V1t-20.
The 1ntr1ns1c vlscosity was determined accordmg to
No powdermg addltive was used 10 makmg these deter
ASFM D—l243~58T. The dispersion parameter de?nes
the spread of the particle size by a single number instead
minations.
of a curve; the smaller the number, the more uniform 45
the particle size. The bulk density of the resin is given
in grams per cubic centimeter as determined by ASTM
D—39Z—3B.
TABLE II
These values vary somewhat from batch to
.
bmh. The dry_b1wd ?ow is de?ned as G (good) or
.
.
P (poor). The recorded dry-blend characteristics are 60
Funon Temperature and Mel! Flow of
Dr
y Blends
based on prior art.
Table 11 given data on blends of the following formula:
Resin
tongwriiim. iiieiiofliit"
°
. Koilcr
hot bench
65
P a!- (s b y
' ht
welg
.
Resin
___________________________________ __
'61:] 0t11,b1l-1z1er_b_l___________________________ __
-
tramnrine
B.
0 arv
aloilaiovlitMll
________ n
n0
—‘ ......... _.
'_
104
m]
g‘.
102
P.
.
1011
E.
-
:a
{E
~
100 13‘.
-
"2
1.0
3.0
.
B.
.
0.1
.
190
Exnn 011s ................. ..
ue ___________ .__
.
107
.
MnrvinolVR-Z? ___________ _.
Titanium dioxide __________________________ --
.
Dow 100-4 ................................. ._
Goon l0] _________________ ._
75.0 60 15132553? MX-ml -------- --
100.0
Butyl phthallyl butyl glycollate .............. __
(air oven)
Eow 11112-41‘. """"""""" "
m“
V
nigiin
._
_
iii 8'.
.
.
.
180
188
1112
Blamong
anion 15%41;.
.
162
E.
170
E.
Vyg0n105._..
.
178
O.
Vygcn 101 ____ __
.
182
O.
$38: 1%?
'
i3: gin
Diamond PVC-2
Diamond 4150...
65 Diamond 0011
'
The purpose is to show the wide range of fusion ternperatures and the melt ?ows of the resins to which the
F~
.
21
vYNW-d...:: ........................... Q
102
13.
B.
P.
E. '
invention pertains. The melt ?ow was a visual observa- 70
tion 0f the ease with which the blend melted and spread
out at 430' F. in an air oven.
The following letter: are used to compare the melt ?ow
characteristics: E, Excellent; (3, Good; F, Fair; P, Poor;
B, Bad.
_
‘
.
75
Cenain of the resins to which the invention is appli-
;
3,000,703
cable were examined microscopically and the results of
the examination are recorded in the following table:
TABLE III
10
The accompanying drawing illustrates quite schemati
cally equipment that can be used.
The vessel 5 is cy
Observnlions of Microscopic Examination
of Varied Vinyl Resins
Relative 31m
Resln
Clarity
Shape
Largest
Comments
of resin
particle
Average
Nnrvlnol
ODltlOl] 300V FM
11-24.
00% large
Borne r0
‘shaped.
D o.
00% small.
Do.
All small.
Mnrvtnol
Vii-25 _ _ . _ ..
90 % blizl
Some rod shaped 60% large.
Diamond DXAKS .... ._
Diamond
All small.
DX-liO . . . . ..
Vygun lit-‘i.
l'liovlc K
VNYW-tl.
Not round .
Conguium, all particles are loose
Marvlnol V
ogglomeratos.
Here the sizes are given on an arbitrary scale, the object
lindrical. The mouth 6 is shown as open, but in practice
may be closed, and the vessel will be provided with a
being merely to record relative sizes.
30
vent for the air or other gas. Preferably the gas is in
The following table compares the volume shrinkage
troduced at one end of the vessel and vented from the
during fusion of various resins to which the invention
other end. There is a bull ring 9 at the lower end of the
is applicable; the resins being formulated as above but
vessel, driven by the gear 10, driven in turn by the motor
without any titanium dioxide.
11. The top end of the vessel is supported by idler 12.
TABLE IV
The plasticizer is supplied by the pipe and spray nozzle
Comparison of Volume Shrinkage During Fusion
15. Air, or other gas (hot or cold) is shown as being
supplied through the conduit 17, although the air is pref
With Bulk Density of Blend
Percent
Rcsln
shrinkage
420° F., 12
min
Bulk don
slty, gJcc.
erably introduced through appropriate means located at
the bottom of the vessel.
The resin is added to the vessel in the form of a pow
der or agglomerates. The vessel is not ?lled more than
about one-third full, so that as it is rotated on its tilted
axis the contents are tumbled and thoroughly mixed.
The resin is preheated or heated by hot air supplied
through conduit 17. Hot air is supplied to the vessel
during the salvation of the 'plasticizer, whether the resin
has been preheated or not. The speed of solvation will
depend upon the amount of plasticizer added and the
temperature of the resin, and the temperature may be
50 any temperature above 60“ F. up to the maximum tem
perature above which degradation commences.
After the addition of the plasticizer is completed, tum—
bling is continued until solvation is complete. Then
cold air is blown into the vessel while tumbling if the
Gcon IOIEI'F-Z’L
Morvlnol MX-‘M'JL.
Insular 155 ...... __
ow
IOIH . . . . ..
Opulon 30(JFM..
temperature is above about 250° F., and its contents are
cooled to a temperature approaching room temperature,
for example, a temperature between about 60° and about
250' F. Then, preferably without interrupting the tum
bling action, the powdering additive is added. It may
be added all at once. For example, inside of one minute,
Escomhla H
Eseitmbla i200.
5 pounds of powdering additive may be added to 100
pounds of resin-plasticizer mixture in a 150- to ZOO-gal
lon vessel tilted at an angle of 15 to 30 degrees and ro
at 20 to 60 revolutions per minute.
The percent shrinkage was determined by volume change 65 tated
The following examples are illustrative. The drum
determined by water displacements. The bulk density
and its contents are most efficiently heated or cooled
of the blend is given in grams per cc. as determined by
by blowing air or outer gas through the drum, such gas
ASTM D-392-38.
being at a temperature su?lciently higher or lower than
The mixing of the resin and plasticizer, ‘and then the
the drum contents to produce the desired temperature
powdering additive, is carried out in a vessel in which 70 change. Each of the products had a ?ow rate of over
there is no agitator. The resin, etc. are tumbled and
5 cc. per second (ASTM D-392—38) and they are there
mixed together by moving the vessel. Thus the vessel may
fore described as tree ?owing.
be shaken, but preferably its contents are tumbled by
EXAMPLE 1
rotating it on a tilted axis. The vessel may be generally
One hundred parts (by weight) of Marvinol VR-24
cylindrical, but vessels of other shapes may be used.
75
11
3,000,703
12
was mixed for ten minutes in a heated drum tumbler at
170° F. to bring it to this temperature.
minutes, and the mixing was continued for another 20
To this was
minutes at about 170° F. About 3.5 percent of ti
tanium dioxide was then added, all at once, as a powder
ing additive and in each case the mixture immediately
became a free-flowing dry blend. Data on this treat
added 70 parts of di-2~el.hylhexyl phthalate which had
previously been heated to 170° F. The piasticizer was
added over a period of 10 minutes. The resultant mix
was tumbled for 20 minutes to permit solvation of the
plasticizcr in the resin, and thrn cooled for 10 minutes to
room temperature.
ment of the different resins is included in the following
table:
TABLE V
The resultant batch was a damp,
sticky, somewhat granular mixture which possessed no
free-flowing ability. To this there was added, all at
once, as a powdering additive, 6 parts of Geon 121 (a,
Avar-
which is an extremely small particle-size, dispersion grade
resin). The particles or agglomeratcs of the mixture im
To this was added 70 parts of tri-2-cthy1hexyl phosphate
preheated to 212° F. The blend was tumbled at 170° F.
for 20 minutes and then cooled to room temperature.
The resulting mixture was soft, flul‘fy, coherent, and had
no tendency to free flow. Six parts of ?nely divided ti
tanium dioxide was added, all at once.
The resulting
mixture was free ?owing and powdery.
Eh AMPLE 3
One hundred parts (by weight) of Marvinol VR-24
was tumbled in a heated drum at 190' F. for 10 minutes.
To this was added, during ten minutes, 70 parts of
Paraplex 6-53, 8. high molecular-weight ester polyester
additive
poratlng
powdurtng
5171!,
Dry
Dry
lJry
Dry
cm.
blcnrl
flow
bland
bulk
blend
flow
blend
hulk
120 cc.
|;./cc.
120 cc.
glee.
506.] density, see./ dcllsll)’.
Geon 121 is an emulsion polymer and a dispersion
grade of vinyl resin not suited for preparation of dry
blends.
was mixed in a. heated drum at 170° F. for 10 minutes,
additive
tlcio
tremely free-?owing and powdery.
EXAMPLE 2
Alter Incor
age pur
l'tesin
mediately disintegrated into a product which was ex
One hundred parts (by weight) of Marvinol VR-24
Dolora tnc0r~
porattng
powdcrlng
high moleculapweight polyvinyl-chloride homopolymer
I‘cnri~typ0 resins of rela
llvcl lilgh molecular
20
welt: it:
.0153
20
.311
7. 5
. 5-’10
con _______ _,
.0172
WP‘
. 310
12.0
.5218
Fscn1nblnl250..
Dow 1004 _____________ ..
.0174
22
.348
7.0
.610
. 0177+
12
_.
. 0122
24
.375
0. 0
.5150
Opnlon 300 FM . _ _ _ _ _ . ..
l‘isenmhin 2250..
.0134
16
.330
7. 0
. 630
V H1011 120 ____ __
.422
6. 0
. 500
Pearl-typo resins 01 medium
molecular weight:
Dow 111-4 ............. ._
.0103
[1.0
.500
Exon 915 ..... __
.0100
15. 0
. 550
.0100
0.0
.585
0136
10.0
.520
_
Escambln 1225.__..
Diamond PVC-450 ____ -_
Pearl-typo resins 01 low mo
lccular weight:
.0103
5.0
Vygen 105 ____ ._
.0103
20.0
. 470
Diamond DX—35..
Diamond DX—30._
Escnrnbin 1200 ........ __
.0119
.0138
12.0
20. 0
. 060
. 6T0
.0082
15. 0
l’llovic B—50__
Marvlnul VB
can 202 ..... ..
.641
.542
.0090
14.0
. 540
.0125
14.0
.560
plasticizer manufactured by Rohm & Haas Co. and hav 35
The dry blend densities were determined as described in
ing a gravity of 1.08. The plasticizer had been pre
ASTM D-392-38. The particle size was measured by
heated to 212° F. The resultant mixture was tumbled at
US. Standard screen sizes. To determine the "dry
190’ F. for 20 minutes and then cooled to room tem
perature. The resultant mixture was damp, spongy and 40 blend flow," as there de?ned, a funnel was used as de
scribed in ASTM D—392~3B and the time required for
heavy. To this mixture was added 6 parts of Pliovic A0
120 cc. of powder to How through an ori?ce of 16 inch
(a eopolymer of polyvinylchloride and diethyl maleate
was measured. The letters "WF‘ mean that the powder
manufactured by The Goodyear Tire 8: Rubber Co.,
which is a dispersion grade resin which is ground to a
very ?ne particle size when manufactured). The in—
corporation of this resin as a powdering additive con
verted the mixture to a free ?owing and powdery product.
The blend of this example is illustrative of the more
di?icult materials from which to prepare a dry blend,
has a ?ow rate of less than 5 cc. per second and wouldn't
flow sui?ciently fast for commercial use. Each of the
resins treated is a polyvinyl chloride homopolymer except
Geon 202 which is a copolymer of vinyl chloride and
vinylidene chloride manufactured by The B. F. Goodrich
Company. The table shows the effect of the powdering
additive on the flowing properties of the different prod
due to the high viscosity and low solubility of Paraplex 50
ucts, comparing the ability to ?ow before and after being
6-53. It is useful for electrical insulation, gaskets, etc.,
treated with the powdering additive. For certain of the
and is non-migrating, i.e. it will not soften painted sur-,
resins the bulk density is given both before and after
faces or other forms of plastics with which it is brought
adding the powdering additive because improvement in
into contact.
bulk density has been found to be a particularly good
515 indication that a dry blend is obtained.
One hundred parts of Marvinol VR-24 was mixed at
The examples are illustrative. Variations may be
190' P. for 10 minutes. To this was added 70 parts of
made in the procedure. For instance, the temperature at
di-2-ethylhexyl adipate (Adipol ZEH) which had been
which the process is carried out will depend upon the
previously heated to 212' F. The plasticizer was added
during a period of 10 minutes. The resultant mixture 60 melting point of the resin, etc. The powdering additive
can be added all at once, or in increments or continu
was tumbled at 190° F. for 20 minutes and then cooled
ously-preferably during a brief period to economize
to room temperature. The resultant mixture was ?utfy
time. Different types of tumbling equipment can be
and coherent with no free-flowing tendencies. To this
used, etc.
was added, all at once, 6 parts of a ?nely divided pre
cipitated calcium carbonate (Super Multifex). After 05 The invention is covered in the claims which follow.
What I claim is:
mixing for 10 minutes this blend was free-?owing and
powdery.
l. The process of converting into powder with a flow
EXAMPLE 4
Other experiments were carried out in the same
rate in excess of 5 cc. per second, a blend of a resin pow<
der or aggregate and su?icient plasticizer to give a damp,
equipment using different resins, and adding 75 parts of
butyl phthallyl butyl glycollate per 100 parts of the 70 particulate mass with a blend ?ow rate substantially less
than 5 cc. per second, which resin is selected from the
resin. The resin was ?rst tumbled in the vessel for 10
class consisting of pearl-type, extrusion-grade polymers of
minutes to bring it to a temperature of 170-210‘ F.
vinyl chloride, utilizing in the process a powdered addi~
For lower molecular weight resins 170’ F. is satisfactory;
tive selected from the class consisting of organic and in
for higher molecular weight resins 210' F. is recom
mended. Tho plasticlzer was added over a period of 10 75 organic solids so ?nely divided as to pass through a 150
mesh screen, said inorganic additives being amorphous as
3,090,763
14
13
opposed to crystalline, and being no more than one‘tenth
of one percent soluble in water, and said organic addi
tives being less than substantially 5 percent soluble in
tives being less than substantially 5 percent soluble in the
plasticizer at room temperature, 5 parts of which organic
additives when dispersed in 100 parts of said plasticizer
ganic additives when dispersed in 100 parts of said plas
the plasticizer at room temperature, 5 parts of which or
ticizer form suspensions which are stable and remain
opaque on standing, said mixing of said additive into the
plasticized resin being continued until the mixture is crn
forrn suspensions which are stable and remain opaque on
verted into a ?nely divided powder with a ?ow rate in
standing; which process comprises mixing said additive
and the plnsticized resin and continuing the mixing until
excess of 5 cc. per second.
3. The process of claim 2 in which all of the steps
the mixture is converted into a ?nely divided powder with
a ?ow rate in excess of 5 cc. per second.
10 of the process are carried out within one vessel and heat
rate in excess of 5 cc. per second, a btend of plasticizer
is supplied from heated gas within the vessel and the
contents of the vessel are cooled by transfer of heat to
and a resin selected from the class consisting of pearl
a gas within the vessel.
type, extrusion-grade polymers of vinyi chloride, which
process comprises solvating plasticizer into the resin with
ditive is a polyvinyl chloride homopolymer prepared by
2. The process of converting into powder with a ?ow
heat in an amount sufficient to result in a damp, particu
late blend which has a flow rate substantially less than
5 cc. per second, and then cooling the plasticized resin
and with the resin temperature between room tempera
ture and 250° F., mixing with it a powdering additive 20
selected from the class consisting of organic and inor
ganic solids so ?nely divided as to pass through a 150
mesh screen, said inorganic additives being amorphous as
opposed to crystalline, and being no more than one-tenth
of one percent soluble in water, and said organic addi 25
4. The process of claim 1 in which the powdering ad
emulsion polymerization.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,056,796
2,835,620
Macht et al. ____________ __ Oct. 6, 1936
Bartlett ______________ __ May 20, 1958
2,958,669
Hoffman _____________ __ Nov. 1, 1960
OTHER REFERENCES
Chemical Engineering, June 1954, pages 210-217.
Документ
Категория
Без категории
Просмотров
0
Размер файла
814 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа