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7T " Patentedgsept; 24, 1946
WATFRiSPPW' vit}:slivon"s commons; ' "
» Milken-Morgan; Columbus; 01316; assignortog" "
v .1 A’'tporation
iii-mm-r nonmana
o'or‘I h,‘
- v -
a ., Serial No; 581,328" 7
ieiawH (arisen
' or-vi‘rcomposition "HBO: rather than ?ance ,j ' an
This iapplication , is aé continuation in part 10f‘.
chemical ,iniormation indicates ‘that-‘3 boric 1 acid
vmy,,|.p1'_)licati_on Serial No.‘ 508,956‘ ?led November » ‘ H330: ‘is-really a hydrzztegof, the acid
4,21943 which is a continuationfin part o?my' ap—‘i ' is mbemekedupon as HBOfé-HzO.
plication Serial No; 380,816, ?led February 21;‘{194 l;v ~ ' . ‘in: carrying outv the invention 11min one
Stable resinousproducts that are water soluble 1 men ‘or borica'cid with an aik'yl ammo tempering.“
and‘at- the~.-same time
heap and readily‘available; -
coatings,= back-?lling and-many other-types vof:
_ 1 i
v;.'I'heynrlixtureaisthen heated above lOO’C; up to a, Q
‘In the textile industry fabric constructions have
‘ maximumot; approximately. 200° C.‘ I ilndin gen-_
in the past been sized‘by the application of starch, _
alkyl~_’ahiinol; ami'negof the followingv geneTaL v
‘ binders, plasticizers,ascompositions‘ior uae‘in'
sworn in’ the paper and'textileindustries.
"whichysp‘eci?cally is‘ either ' a'mliamines'or ‘ an
have considerable ~,uses in i the V artsjasiadhesives, ~
gelatinpand water, soluble , gumvcomppsitions for
the purpose" of . applying '. coatings which: cement;
eral that ,ztemperatures'oi' around ~1301-to 150°C;
arersu?lci'ent?tor thereaction ‘andrthe heating is
down the extraneous ?berson the surface ‘oi’fthef 115. vcarrievli' out‘ until more than one mol o water-‘has >
yarns ociabricand thereby-give a greater smooth-1 been‘iost, - It‘is apparent that one mol get water ,
_' ‘ness and uniformity ‘of appearance; Injthecase‘ iwmibe lost. by the dehydration of the boric acid. '
oi’ warp sizing,’ it is particularly essentialthat a; 351303,’; own to themetaborate form, HBO: and
good'surfacfeiillrn bevprepared in order tq have»; _ any I?il‘ther water molecules lost‘ must represent
"20 ‘reaction
acceptable-conditions for-weaving“ ‘Propern bind-_
ing oi the starch
' breakingjoi the yarns and subsequentstormingv 01f
necessary vtov
the'loom's, ~~In suchvcompositions there is also
between the iacidand the ‘ammo_;°°m_
-In the above general "iormula for arninol'v'com-v
",~pounds,, which are satisfactory iorfuse 'in'g‘this' -
subsequently used'iatty‘type softeners along with , 7 invention, x- - l'nay ‘ represent either '- simple;
hygroscopic agents which are added to'in'crease '25 branched alkyi chains or groups? containing not 1
v 7' the amount of moisture retainedin the starch e. over ?ve,_,carbons;=-in which one or more hydroxyl '
~' or amino groups appear. I! may also stand for"
dull!!! Processing. 7
In U.‘ 8. Patent‘:T195331 menace, July" 15, 3
1932, v water .soluble resinous ' ‘products 3 have ":been'
made;by reaction of glycols orxpolyhydric'alco-r
hols, .such as; ethylene ‘glycol, diethylene ‘glycol;
are small integers, within vary
‘inQi'roni 2'to v6 and peirom 0_to;6;. Y is either '
' etc, byreactlng- these with boric-‘acid. "While such!
products are water soluble, they have ‘found only‘ I i hydroxyl(ol-ll-oramihoiiNHz),,1 I
In the. general formula R stands‘ for-'eitherhye
‘ ~~ limited usesdue to‘their unstabilit’yl'in ‘particular.’
‘ and water. solutions‘ soon1~aiter preparation ‘be; “' 35’drojgeho'r1any group oithe type described by x. I, - . I
come cloudy and- turbid .;due to‘ boric: acid ‘rapidly . - Suitable?amino icompoundsieforcondensation
hydroiyzing and splitting‘ outoijthe -compoundZ-'_
~ pletl'ely destroyed, thereby
I "aveiiound that-stable waterf-soluble/resins
_ with boricfacidgto‘secure water ‘solublelreslnst are ’
i ' as renews: "monoethanolamine, ‘diethanolamine; 1
'mono- anddiisppropanolarnine,ethylenediamine; I ‘
40‘diethylene latriaminmqdipropylene triamine, tri-f.
ethylene‘ tetramine', tetraethylene__. penta'min'e,
may beprepared which may be keptior- a long-5“; _ heptaethylene
,octamine-v 'hexaprppylene hepta
mine; , fhexamethylene ‘
time in water solution 'wlthouthydrolysis by re-‘ '1 ethyl-‘>1,
3 propanediol, 2-amino--2,-;methyl'-1-pro-v
acting borlc, acid with compoundsicharacterized
propanedioi, vtril Q
by containing- an amino group. Borlc acid is an 45"p?nol;*7Z-aminO-Z-methyI-mL
amino methane,'2r-arninoé21rnethyleh‘
inorganic acid,_ and while ltsior'mula is generally»
butan‘ol; ,‘2-amino-l-pentanol and vhydroxy ethyl
- poly'basic'acidgiven as HaBOayit
not considered
heating .it to
asa > ' I ethylene diamine."
Y The complexv polyamino ‘compounds; such as
low temperatures, it; easily. gives ‘up :onemclecule » ~
50 heptaethylene' octamlne. ‘hexapropylene hepta- » in v
of water, and} thereafter-- reacts according to the
andother similarlong chaincompounds,
generalii’ormulafor metaboric acid (H302). Its,‘ ‘A vmine
may be‘ easily ‘synthesized by jreaction of alkyl
reaction in" aqueous solutions have been frequently
' ' ‘shown byph'ysical chemical measurementsto in-.
dlhalides and organic amines panther-‘known
‘ :‘ methodsoi sy'nthesis._ v15y proper selection of the '
dicate the i0rmula,,HBOa rather than H3303.v u aikyl di-halides and'amino‘compounds, various‘
vThe organic
toi?boric acid’ indicate an 1 acid ~
structures may be built up to obtain the desired
characteristics of the ?nal boric acid condensate.
The detailed practice of the invention is illus
trated. by the following examples wherein the
The water solution can be kept without any ap
parent evidence of change. The resin is easily
softened on heating
and is permanently thermo
' plastic.
Example 1.-62 parts 01 boric acid (1 mol) were
Rayon yarns when sized in a vbath containing
parts are given by weight:
‘a solution of 4% gelatin and 1% of the above
mixed with 61 parts (1 mol) of monoethanola
resin were satisfactorily sized for weaving oper
mine and gradually heated until water was col
lected in the sidearm tube. Heating was'con
tinued until 155° C. at which point 1% mols of ‘10' Example 5.—-89 parts of 2~amino-2-methyl-1
propanol -(1 mol) were mixed with 62 parts of
water were split out and the residue in the ?ask
'boric ,acid (1 .mol) and, gradually heated until
cooled down. This yielded a water-soluble, vis
waterv was collected in the sidearm tube. Heat
cous resin which was hard, glassy, practically col
orless or slightly yellow, transpa'rent,_ and non-' \ ing was continued until 130° C. at which point
hygroscopic in nature. The resin is readily sol- 15 11/2 mols of water were split out and the residue
in the ?ask cooled down. This yielded a water
uble in water and from such aqueous solutions'the‘
resin can be again-secured by drying down, thus
soluble, amber, viscous ‘resin which was hard,
indicating that the product is stable and does not I transparent, and slightly hygroscopic in nature.
hydrolyze. The water solutions can be kept with
The resin is readily soluble in water ‘and. from
.out any apparent evidence of change. _The resin 20 such aqueous solutions the resin can be again
secured by drying down, thus indicating that‘
is easily softened‘ on heating and is permanently
the product is stable and-does not hydrolyze.
The water solutions "can be kept’withou‘t any ap-;'
A cotton warp wound on a beam in the usual
-' .
parent evidence of‘change'.v The resin‘is easily
manner was run through a size which was pre
pared by boiling ,30# of potato starch, 7%# of 25 plastic.‘
softened by heating
and is permanently thermo
1 '
fatty g1ycerides,'21/2#'soda ash in 100 gallons of
water to which was added 2%# of the above wa
In sizingthreads ‘and twines, a composition
ter soluble resin. The yarns when'dried showed.
a smooth hard‘ surface, did not fray'during the
weaving and permitted operation of the looms 30
at high efficiency.
Example 2.—62 parts of boric acid: (1 mol). ‘
‘ were mixed with 116 parts (1 mol) of hexameth- "
ylene diamine (1,6 hexanediamine) and emu-
prepared by boilinglin 100 gallons of'water, 50#
of tapiocavdextrin, 10#- 01' talc and 10# of the
above resingave a hard smooth surface, but ?ex
ible, which. characteristic is desired‘ for sewing
threads, twines'etc.
‘Example 6.~—318 parts ‘of heptaethylene octa
'mine' (1 mol) were mixed ‘with 82 partsof boric
ally heated until the water was collected in'the 35 acid (1 mol) and heatedto 135-140‘ C., at which
sidearm tube.
Heating was continued until 140°‘ '
point 2 mols of water were split out and ‘the
C. at which point 2 mols of water‘were split out
and the residue in the ?ask cooled down. This
residue in the ?ask cooled down.
yielded a water-soluble, viscous resin which was ~
and hygroscopic in nature‘; The resin is readily.
hard, slightly yellow, transparent and non~hy
soluble in water and such aqueous solutions can
groscopic in nature. The resin is readily soluble 4' 0 be kept without any evidence‘ of: hydolysis after _
long periods of time.
1 ~
> a
‘ Example 7..—-To 485‘ parts (1 mol) of apoly
alkyl amino, condensate having the following for
Example 3.—.-60 parts of ethylene diamine (1
‘ mol) were mixed with 62 vparts of boric acid (1
mol) and gradually heated until water was col
‘were added 62 parts (1 mol) of boric acid. neat
lected in the sidearm tube. 1 Heating was 0on7
.was applied until 140". C; wasreached, at which
tinued until 130°._C. at which point 2 mols of wa
point 2 mols of water were‘split ‘out and the
ter-were split out and the residue in the ?ask 50 boric acidlconden'sate in the ?ask cooled down.
cooled down. This yielded a water-soluble, vis
The resinous productobtained was easily water-7
cous resin which was hard, glassy, ‘practically ‘col--v
soluble. r6110 “transparent andv s11¢h?yhy8ro_
orless or slightly yellow, transparent, and non-g
hygroscopic in nature. The resinyis readily sol
Example 8.-,—To'~ 131 parts (1 mol) "ofdipro.
uble in water and from such aqueous solutions 55 pylene triamine were added 62 parts of boric'acid '
the resin can beagain secured by drying down,
(1 ‘mol) and the- temperature‘
thus indicating that the product‘ is stable and ,
until 'the water was collected in the sidearm tube. '
gradually raised '
does not hydrolyze. The water solutions can be , 1 Heating was continued until 140° C. was reached.
at which point'2 mols. of water were splitout and
any apparent
of changm
The resln
is easily
softened evidence
on heating
and is 60 the residue in the ?ask cooled down. This yield
permanently thermoplastic.
ed a water-soluble,‘ viscous resin which was hard;
slightly yellow, transparent and non-hygroscopic
Example 4.—104 parts of hydroxy ethyl ethyl
in nature. The resinous, compound is 1' easily‘
ene diamine (1 mol) were mixed with 62 parts of
boric acid
upon heating
(1 mol) and gradually heated until 55 in
water solutions,
water was collected in the sidearm tube;
ing was continued until 195° C. at which pointv
11/2 mols of water were split out and the residue
in the ?ask cooled down. This ‘yielded a wa
ter-soluble. sticky,‘ vviscous resin which was.
and does not hydrolyze
, ,
Cotton cloth to. be finished for white sheeting
was back-sized by'running the fabricv through a
quetch, squeeze ‘roll and drying machine with a
formula prepared by boiling in _100 gallons 01"
slightly yellow. transparent, and non-hygroscopic 70 water, 130# ‘of cornstarch, 2253i"v talc,"50# of
in nature. The resin is readily soluble in water
saponi?ed tallow and 20#- of the above water v
soluble resin. The sheeting‘ was satisfactorily
and from such aqueous solutions the resin can be
again secured by drying down, thus indicating ~ back-sized and the starch well bound in the fab
that the product is stable and does not hydrolyze. 75
_ Example 9.—’88 parts of butylene diamine (1*
access:amino ‘compound 'of the~ following. general’ for-
Incl) were mixed with 62 partsc! boric acid (1 ~
gradually heatedv until water was-c'ol- '
moi)v and
lectedin the sidearm tube. Heating‘ was contin
v'ued until 135° C; at which point2 mols of water,
,, were'isplit out and the residue in the flask
a‘ water?
when and
to 6pand
are small
' integers;
w ‘
p‘ rrpmgotoiaand
Y is a p
i. ,
radical‘ selected from the-group consisting ofsai‘ '
g down“ The condensate obtained was
an taminoamm)
which formula R. represents ‘a; radica selected ‘
the group consistingoijhydrogen {and - V
Example '10.-To 62 parts or boric acid (may m'irom'
solubler‘viscous resin, ‘transparent and- non-hy
groscopic in nature.
‘ '
were added 102 ‘parts ‘ ('1 idol) of 'amylene di-f
amine‘ and the ‘temperature gradually raised un- ‘
1 inqwhich n and'p are small-integers,‘ with vary
'. til the‘ water "was collected inathe?sidcarln tube.
in'g vfrom 2 ‘to, sand p from O'toi 6;’ and Y is a
" .; Heating
point 2 molsof
water were‘split
until 1i0°
out "Crat
which I ‘5
.5i lradicalfselected from the vgroup consisting of a
and theresihydroxyl _(0H)- and an amino (NI-I2).
leddown. _ This‘ yielded a
‘due inuthe ?ask c
water’ soluble, hardjttransparent :resin. which-"is '
_ w . 3._ Theprocess for forming a water solubleres- .
in’ which consists-of condensing/boric acid v‘and '
no'hydr'oly'sis on , '
soluble in waterandundergoes
laces it is nééerssarya 7‘ monoethanolamine
above 100
long‘ standing. o'f knitted-shoe
‘-. .4. A water solubleatresinous
of re
Inthe sizing
act'ants consisting of boric acid and. monoethanol
"to secureja' smoothsurface which will take a 20 » amine
_ condensed by heating at , temperatures
high polish. This-eifect‘ was satisfactorily se
bath of the follow- I ‘
or forming a water soluble ’
ing composition. ,In 50 vgallons voi! water were ,7 13 ‘.5, ,The process. ‘of- condensingboric acid and
resin which consists
above 100° “C;
' cured by sizing shoe-laces in a
boiled 1o#,or wheat starch, 10#'"of'-potato starch;
temperatures. above 100”
ethylenediamine at
V 10# of corn starch; 3# Japan'wax,
' Q 6. The process for forming a watefisoluble res
‘nut oil and ‘1‘0#
The shoe' laces thus: sized possessed a" smooth > vin which consists'of condensing-;boric-__acid vand V
‘a j24amino-2-methyl-1-propanol; -.' at
. surface which on rubbing 'gave?a’high lustre.
- The above examples 'are given‘ onlyiby lwa'y oi’
'above 7100' C.
1'7. A water soluble resinous‘ jcondensate'lof're
illustration ‘and-the use" of various other amines 30
of boricjacid'and-yethylenedh I
result in various 'other'type resinous products. _ .
actants consisting
byreaction of boric acid with either an amine or ,
above 100'’ 'c.
suggested reactions- as the source of the water '
resinous‘condensate of boric’acid and ‘anian'iino
'In view'of the fact that water mayo-chef split out '‘ ‘amine condensed by , heating fat I'Iten'ipe'raturas
/ ‘
8. A water solubleresinouscondensateof re
hydroxyl group, it. isvto'ebe presumed thatlthe
resinous products are formed in this manner. It‘ . -' actants consisting of boricgacid and‘ Z-amino-Z
Y is apparent that high polymeric chain resins
9. Textile materials sized :‘with a composition
7 formed must have rather‘ complex chemicalfor- . in which the binder consists of a water soluble
mulas and itis-not my intention in offering these
eliminated that this is necessarily ‘the only typev 40 compound of the following general'for'mula; ‘
.of combination which occurs, ‘and this applica-l
tion is not to be limited interms of this type of
v in which n and p are small integers, with n vary- 1
ing from 2'to 6 and p from‘o to 6,‘ and Y is a
The above .descriptionand examples are in
7 tended to illustrate the‘nature of this invention
radical selected‘ from the group consisting ‘of a
hydrox'yl (OH) and an'aminqfiNI-‘fzi, and in
but-theinvention is vnot restricted to these Vex
' , whichformula R representsfa: radical selected
amples. a
. from ‘the v group consisting of,‘ hydrogen and.
I claim:
_ 1. VThe process Fionthe‘ manufacture of water
a soluble resins which-consists of condensingboric
acid and an amino compo d oi’ ' the ‘followins
l- '
> I >
“nuglsavradr- f ‘ "
'‘ ing from 2 to 6 and pifrom 0t
cal selectedyfromj the group's-i}
' ' dI'OXYI (0H)~and an amino, (N112);
10. Textile material sized witha‘composition' in
m which ‘a and pare small mistreatment vary-j
which the binder consists of {a water soluble‘ resin
‘ ing from 2 to 6 and p from Q tc'6,yand_Y is a radi- Q
cal selected from'the group consisting of a hy_- '
secured by the-reaction of boriciaci'd .andar'n'on'o
dream (on) and mamimmnn, and in which I'
_' formula It represents a radical selected'from the
‘11. Textile material sized‘with'j’a ornpcsition
' ethanolamine;
‘in which the ‘binder consistsfof ,7 a water- soluble 7
resin securedlby ‘the reaction {boric acid‘ and _
group consisting of hydrogen: and .,
#40111‘) ,.-mmcm)g1r-'Yj
ethylene diamine. ,
, >
Textilematerial sizedwith ‘composition in
i‘ in which a and paresmallintesersi with '1.‘ W3?- , > 1.12..
consists of alwater soluble resin ,
“ ing from 2 to'o/vand'p froin’i) to annex is a‘radi
‘secured'by the reaction ‘of boric 'acidiand 255ml; -_ I ‘
- cal selected from th _' group consisting ot a _hy-_
nc-Z-methvl- i-propanol. ’
idroxyl (OH) and an aminoiNHa) .
2. A water soluble resinous condensation
of reactants consisting o! boric .aeidz'm'd 9n :
WILLARD nitroaoim.
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