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Патент USA US3096307

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United States Patent O?ice
Hem, ,jj'itiil
1
2
350%,297
ARTIFICIAL BGARD AI‘ID PROCESS FOR
vention is made by condensing a hydrocarbon oil with an
aldehyde in the P16861166 Of an acid catalyst. The hydro
pREpARING SAME
carbon oil is a ‘fraction containing substantial amounts
Melvin E. ?eterlrin, Brookhaven, and Stewart S. Kurtz,
of aromatic hydrocarbons. The ‘boiling range of the oil
Jrn, Merion Station, Pa., assignors to Sun Oil Com- 5 is from about ‘200° F. to 650° 'F. Sources of the oil in
Pany, Philadelphia, Pa., a corporation of New Jersey
elude recycle streams from catalytic and thermal crack
NO Drawing File? Mm‘- 15, 1961, Sef- NO- 95,790
ing, fractions separated by distillation and solvent ex
6 Cla‘ms' (CL260-9)
traction ‘and blended aromatic stocks. It is desirable
This invention relates to improvements in ‘arti?cial
that the oil contain ‘from 210-100% aromatic hydro
boards bonded by heat and pressure from a ?ller and a 10 carbons, preferably from 25-50% aromatics.
thermoplastic hydrocarbon resin.
Paraformalde‘hyde is the preferred condensing agent
In the past resins have been prepared from aromatic
although formaldehyde, formalin, and other carbonyl
petroleum fractions and formaldehyde in the presence of
compounds can be used.
an acid catalyst. When these resins ‘are combined with
Suitable condensation catalysts include formic acid,
cellulose or lignocellulose ?llers under heat and pressure, 15 sulfuric acid, metal chlorides and hydrogen halides such
the resulting molded shapes lack suf?cient strength in
as HR Fcrmic acid is preferred because of the high
comparison with commercial materials such as Masonite.
The object of this invention is to provide a superior
arti?cial board having a petroleum resin binder. A par-
quality resin produced when it is used as catalyst.
The reaction conditions employed in producing the
resin depend upon the catalyst and other factors. Gen
ticular object ofthe invention is to provide ahigh strength 20 er?lly speaking, temPeIamIeS 0f 80 t0 200° C» Pressures
hardboard having a sawdust and/ or shredded paper ?ller.
of atmospheric to 300 psig and oil~aldehyde molar
We have found that additional strength is achieved by
ratios of l.0:l.0 to 20:10 are suitable. The catalyst
the addition of hexamethylenetetramine to the resin and
can be present in amounts ranging from 25 to 100% by
?ller prior to the molding operation.
volume based on the aromatic oil feed.
Hexamethylenetetramine has been used previously as 25
Following condensation, the lower boiling fraction
a hardening agent for thermosetting resins and with cerhaving a vapor temperature endpoint of vfrom 800 to
tain other resins as disclosed in US. Patent No. 2,418,950° F. at atmospheric pressure is distilled olf. Vacuum
293. With petroleum resins, however, the addition of
distillation of 5 mm. to a vapor temperature endpoint of
hexamethylenetetramine had no signi?cant re?ect-as
from about 480° F. to 610° F. is preferable.
will be seen from the examples appearing later in the dis- 30
The resulting resin will have an initial boiling point of
closure. We have discovered that when hexamethylenefrom SOD-950° ‘F. and a ring and ball softening point
tetramine is added in small amounts to mixtures of petoof ‘SO-150° C.
leum resins and a cellulose or lignocellulose-?ller prior
Table 1, below, shows the resins resulting from con
to hot pressing, the resulting arti?cial board. product is
densation in the presence of a formic acid catalyst at the
stronger.
.
35 conditions indicated.
The hydrocarbon resin component of the present in7
In all cases the reaction mixture
was agitated with a motor driven stirrer.
TABLE -I
Comparison of Runs at Various Temperatures and
Pressures
RUNS 0N PRESSURE REACTOR »
Products
Reaction
Run
No.
Chg.
Stk.a
Soft
Terran" Pressure,
Time,
p.s.i.g.
hrs
10-3
12-3
12-3
100
140
140
Atrn.
80-110
80-128
6
0
1
3
10-7
140
80-120
10-7
160
100-185
10-7
180
80-135
Intermediate resin
B.R.,
Ringand Appear-
° F.d
Ml.
ball,
864-925
824-864
39
822-894
864-47 7
651-864
814-044
737-044
0
Final resin
ance I
78
________ __
61
67
57
49
2
Total,
>650° C.
B.R., Ringand Appear
Grams
enthalpis: O FI
° F.
>700
b . ,
ance l
________ __
RUNS IN GLASS REACTOR AT ATMOSPHERIC PRESSURE v
8 ____ -9 ____ __
10-3
10-7
1 102
1 102
Atm.
Atm.
11
650-814
31
814-930
64
5 C
23
>930
10
651-694
56
094-931
59
5 C
36
>930
-
118
106
6 E
6 E
65
102
Z E30ceiul.
oildin rtealctor brought to temperature, then solution of (II-I20 in CHOOH (20 g./125 ml.=0.l6 g./m_i. acid) added from blowcase.
ic aci on a yst.
11 Regular run in glass reactor; 3,000 mi. oil, 725 m1. acid, 120 g. paraiormaldehyde (0.16 gJml. acid). Data shown are % actual-to provide com
parison with pressure reactor runs.
d Boiling points are “equivalent atomospheric" ?gures converted from vacuum distillation data.
8 See the following table:
mdM
Charge
Type
N1,N
d4?"
Gel aro
matics
Percent
0A
Percent
UN
Per
cent
01>
10-3 ____ __ Cat. gas oll____
1. 4875
0. 8644
31. 9
23
22
55
12- _________ __(lo ______ __
10-7 _________ __do ______ __
1. 4987
1. 4991
0. 8791
0.8753
48. 2
41. 8
28
30
20
16
52
54
1 1, liquid; 2, viscous liquid; 3, soft plastic; 4, intermediate plastic; 5, hard plastic; 6, brittle. A, water white clear; B, light yellow clear; 0, yellow
cleamél?deep yellow clear; E, brown; F, dark brown; G, black.
1
e mi.
3,09 6 ,297
3
The products in Table I above are divided into soft,
intermediate and ?nal resins. The ?nal resins are used
in making the arti?cial board of the invention. The
?nal resins are obtained by Vacuum distillation and rep
resent about 10-15 % by volume of the total resin prod
uct. The table shows that the use of elevated tempera
tures and pressures (runs 1-7) speeds up the reaction
considerably over low temperature operation at atmos
pheric pressure (runs 8 and 9).
42
ing from 0.1 to 6% by weight, preferably from 1.0 to
4.5% by weight.
The hardboard of the present invention may be made
by any of the many methods employed in molding opera
tions of this type. Broadly speaking, the mixture to be
molded is mixed to provide good distribution of the in
gredients. The resin is usually ground to a ?ne powder
prior to the mixing step. The mixture is then placed in
the mold and heated while pressure is applied. Tempera
The ?nal resins are solid at room temperature and 10 tures in the range of 250—450° F. and pressures of 200
to 10,000 p.s.i. are suitable. A continuous process can
have a ring and ball softening point of from about 90
be used if desired.
The following examples in Table II show the eifect
Other petroleum resins than those shown above can
of changing various components and conditions in mak
be used as the resin component of the arti?cial board of
the present invention.
15 ing hardboard. The mold was the standard 2" x 6" x ?/16"
size used for making test blanks.
The resin is employed in amounts ranging from 5 to
150° C.
TABLE ‘11
Variable Study of Petroleum Resins in Wallboard Type
Formztiarion
Weight
_
Per-
Variable
Per-
Per-
cent of cent of cent of
Wood
resin 1
Mold
Mold
Mold
of
time
temp.
pressure
chg.
hexa
28° C.
80° C.
modu- Bend
Variable
lus of
(g.)
.001”
Weight Loss
modu
(g.)
lus of
ruiJ-
rup
ture
ture
Series 1
Temp.-mo1d ______ __
40
8
2
10
(2)
10, 000
50
Series 2
250° F _________________ _.
Time _____________ _.
40
8
Resin _____________ __
40
Hexa ______________ __
40
6
Weight chg. to
40
s
2
(2)
2
(a)
(1)
325
10,000
50
10
325
10,000
50
10
325
10,000
8 46
10
325
10,000
(1)
, 600
2, 640
2 mm... .
3, 600
313
7.1
______ __
5min____
3,500
310
7.9
______ __
10 min__.-_
20 min--.
4,140
2, 820
285
218
7. 6
9.0
8 g-_
.
Size of wood dust-.Resin melt point__-_
40
6
6
2
2
10
10
325
325
10, 000
10, 000
50
50
213
3,000
2, 820
1, 650
255
250
260
2g
3,370
275
,310
300
1. 5
1. 0
0.5 g---
2, 690
2, 760
2, 400
____ ..
7.1
6.1
11. 3
3. 9
6.0
275
252
265
5. 8
5. 6
5. 6
5. 3
30 g_ __
<940 ____ __
30-28- 4= 1. 6
40 g50 g-
1,820
3,480
258
203
40—36.4= 3. 6
50—41.7= 8.3
60-48
60 g_ __ _
40
3,100
6g
4g
2g
0 g.____
2
mold.
2, 703
300° F_-.-
350°_ F__-_
.
5,170
183
Coarse medium (avg)
?ne.
2, 950
2, 880
250
260
#217 100° C ____________ _.
3, 530
3,000
280
150
6. 1
5. 8
6.2
#209 92° C ____ _#200A 84° C- _
__
#219 80° C _____________ __
2, 900
2, 880
3, 000
191
240
255
6. 3
6. 7
6. 1
#20013 100° G..__
,420
193
= 2
6.0
6.3
1 Resin #219, Ring & Ball M.P. 80° C.
2 Variable: see column at right for numbers.
3 Plus hexa.
The table shows that without hexamethylenetetramine
the modulus of rupture (28° C.) was 2,310. This value
may be wood, paper, straw, corn stalks, bagasse, nut 60 increased to 3,370 with the addition of 2.0 gms. of hexa
methylenetetramine. This was an unexpected develop
shells, and other ?bers from naturally occurring and
ment in View of the following data which shows that
man~made sources. A particularly suitable material is
hexamethylenetetramine has no effect on the resin alone.
sawdust. The latter has not been popular for making
‘Eight grams of petroleum resin similar to those dis
hardboard because the ?bers are too short. Commercial
closed in Table I were mixed with two grams of hexa
hardboards contain ?llers made by special treatment of
wood. We have found that sawdust is well suited as an
methylenetetramine and heated to 325° F. at 800 p.s.i.g.
extender for petroleum resin when it is used in con
for 10 minutes. The same treatment was given to the
junction with hexamethylenetetramine. We have also
resin alone. Ring and ball softening points of the two
found that paper ?ber such as shredded newsprint alone
samples were obtained.‘ The resin containing hexameth
or in conjunction with sawdust provides a high strength 70 ylenetetrarnine had a softening point of 94° C. and the
hardboard.
plain resin had a softening point of 92° C. which indi
The sawdust may be coarse, medium, ?ne, or mixed.
cates that the hexamethylenetetr-amine has little or no
The ?ller is present in amounts ranging from 50 to
eifect on the petroleum resin.
95% by weight, preferably from 70 to 85% by weight,
Table III shows the e?ect of mixing various amounts
based on the total mixture.
Hexamethylenetetramine is present ‘in amounts rang- 75 of sawdust and paper with the resin and hexamethylene
30% by weight, preferably from 15 to 25% by weight.
The ?ller material employed in making arti?cial board
3,096,297
5
tetramine.
6
With 20 weight percent sawdust and 80%
from 75.0 to 95.0 wt. percent of a cellulosic ?ller and
paper, a modulus of rupture of over 6000 was achieved.
from 0.1 to 6.0 wt. percent hexamethylenetetramine.
2. An arti?cial board according to claim 1 in which
TABLE III
the cellulosic ?ller is sawdust.
E?ect of Varying Wood to Paper Fiber Content of
3. An arti?cial board according to ‘claim 1 in which
5
Pressed Hardboard
the cellulosic ?ller is ground paper.
4. An arti?cial board according to claim 1 in Which
Grams Grams Grams Grams
Wood/
Mod. of rup
wood
paper
resin
hexa
paper
ture at 28° 0.
40
40
40
36
32
24
16
0
0
0
4
s
16
24
0
0
8
s
8
8
s
0
2
2
2
2
2
2
100/0
100/0
100/0
90/10
80/20
60/40
40/60
8
4
0
0
0
32
36
s
s
2
2
20/80
10/90
6,850; 1 7, 400
7,650
40
40
40
s
0
0
2
2
0
0/100
0/100
0/100
6,200
2, 000
1,850
powder ?bre
"17.,
750
1,000
3,100
4, 000
5,300
5,350
5,550 15
troleum resin prepared by condensing a hydrocarbon
fraction boiling in‘ the nange of ‘from about 200° F. to
about 650° F. containing aromatic hydrocarbons with
formaldehyde in the presence of an acid catalyst, at a
temperature in the range of 80—200° C. and a pressure
in the range of atmospheric to 300 p.s.i.\g., and separating
the said resin.
6. The arti?cial board produced by the process of
1 Repeat run.
Various modi?cations of the invention such as blending
of resins, the employment of ?reproo?ng agents and the
formation of the arti?cial board into ?oor tiles and the
like will be apparent from the foregoing description to 25
those skilled in the art.
We claim:
11. An arti?cial board consisting essentially of a heated
and compressed mixture of from 5.0 to 30.0 wt. percent
of petroleum resin prepared by the condensation of an 30
‘aldehyde and a hydrocarbon fraction containing aro
matic hydrocarbons boiling in the range of from about
200° F. to about 650° F. in the presence of an acid cata
lyst, at condensation conditions suitable {for the particular
aldehyde, hydrocarbon fraction and catalyst employed,
the cellulosic ?ller is a mixture of ground paper and
sawdust.
5. A process for making arti?cial board which com
prises heating and pressing a mixture of from about 0.1
to about 6.0 Wt. percent hexamethylenetetramine and
from about 75.0 to about 95.0 wt. percent of a cellulosic
?ller with from about 5.0 to about 30.0 wt. percent pe
35
claim 5.
>
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,054,243
Cowdery ____________ __ Sept. 15, 1936
2,397,398
2,418,293
Badertscher et al ______ __ Mar. 26, 1946
Farber _______________ __ Apr. 1, 1947
OTHER REFERENCES
Ellis: “Chemistry of Synthetic Resins,” volume 1, pub
lished ‘by Reinhold Publishing Company, ‘1935, page 695.
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