Note: Descriptions are shown in the official language in which they were submitted.
73 -19
lO~V~l
- This invention relates to the use of lo~ molecular
weight salts of partially hydrolyzed polymers of methacrylic
~ esters as vehicles for the formulation ~f aqueous high
gloss essentially water clear finishes with autoredispersible
properties, for example, in a~ueous floor polishes.
Conventional floor polishes contin-~e to build up
on reapplication to the floor and ultimately require a
laborious, objectionable stripping operation to res,ore
a uniformly clean floor. The polish films based on
products from this invention are self-dispersible. During
polish reapplication, the previous film is dissolved and
the embedded soil removed leaving a film which on drying
is comparable in thickness to the original film. Thus,
without film build-up the three separate steps normally
involved in floor maintenance are accomplished (cleaning, -~
stripping previous coats of polish and repolishing) in a
single step.
- Other polymers of relatively low molecular weight
and aqueous alkali solubility, such as rosin acid adducts -
and styrene/maleic anhydride are found to impart good
leveling and flow properties to polishes containing higher
molecular weight polymeric vehicles, but are unsatisfactory
when used solely as the major polymeric constit~lent in
aqueous soluble floor polishes. ~heir defects include: ~ -
unacceptable low water resistance, unsatisfactory recoat-
ability and poor wear properties and in the first two
classes, p~or ir.itial color and color stability. Although
the addition of 1GW levels of polyvalent metal ions (e.~.,
Zn) may be nsed to improve these properties, it does so at
,~' '
,
~ . .
~0~3l~1
the expense of gloss; in those cases, the degree of property
improvement remalns inferior to the performance of the oligomers
disclosed herein.
The tris-, tetra- and higher acids prepared by hydrolysis
of the polymers of methacrylic esters have previously been
described in Canadian Patent 959,999 of S.N. Lewis and R.A.
Haggard, issued December Z4, 1974.
We have found that saIts of the tris-, tetra- and
higher carboxy containing methacrylate polymers must fall within
n specific molecular weight ranges and acid number ranges to
afford improved finishes. The acid number, which is the number - ~-
of milligrams of potassium hydroxide required to neutralize the
acidic constituents in one gram of material, is in the range of
from about 75 to about 200 with a preferred acid number in the
range of from about 100 to about 160. The weight average
molecular weight (Mw) of the oligomer is in the range of from
about 1300 to about 2500 with the preferred weight average
molecular weight being in the range of from about 1400 to about
1750.
The present invention resides in aqueous finish compositions
with autoredispersable properties, which include as a vehicle therefor, ~:
a partially hydrolyzed oligomer of one or more methacrylic :
esters having a carboxy content of at least 2.7 functionality per -
~. average chain and an average chain length of from about 6 to
about 25 mer units; said oligomer being in the form of a carboxy-
late salt and having the following structural formula: .
RO~--C~2--~ C~12 C--C02Z
wherein RO is a residue of a chain regulating alcohol; R is
~ ~ ~3-
l... .. ., , ,
.. ~ . . . .
03~
the alcohol portion of one or more monomeric esters of metha-
crylic acid; n is an integer consistent with the aforesaid
functionality per average chain; R is hydrogen or the residue of
a comonomer or comonomers; x is an integer having a value such that the sum of x+ n
is consistent with the aforesaid average chain length; and Z is a cation derived
from an alkali metal, ammonia or a tertiary amine; said oligomer
further having an acid number in the range of from about 75 to about
200 and a weight average molecular weight in the range of from
about 1300 to about 2500.
m e polishing compositions comprising a further aspect
of the present invention can generally be defined as follows:
CONSTITUENT
(A) The oligomer as defined above -
parts by weight----------------25-100
(B) Wax - parts by weight----------------------- 0-25
tC) Alkali Soluble Resin----------------------_- Q-50 :
(D) Wetting, emulsifying, plasticizing
and coalescent agents------------------ 0.1-50% based on
the wt. of A,B
and C
''~' ' . .
.
3~1
(E) Polyvalent metal compound 0-5% based on
wt. of A
(F) Water to make total solids of 5-45%
The total of A, B and C should be 100.
The invention, in still another aspect, resides in a
method for preparing water clear transparent finishes which
comprise admixing the following ingredients:
(A) 25-100 parts by weight of a partially hydrolyzed oligomer
of one of more methacrylic
esters having a carboxy content of at least 2.7 functionality
per average chain and an average chain length of from about
6 to about 25 mer units; said oligomer being in the form
of a carboxylate salt and having the following structural
. formula:
. --
RO ~ - ~ 2 t ~ C~2-C2 C02Z
wherein RO is a residue of a chain regulating alcohol; Rl is
the alcohol portion of one or more monomeric esters of metha-
crylic acid; n is an integer consistent with the aforesaid
functionality per average chain; R2 is hydrogen or the
residue of a comonomer or comonomers; x is an integer havin~
a value such that th~ sum of x+ n is consistent with the aforesaid average
chain length; and Z is a cation derived from an alkali metal, ammonia or a
tertiary amine; said oligomer further having an acid number
in the range of from about 75 to about 200 and a weight
average molecular weight in the range of from about 1300 to
about 2500;
~ -4-
ai
.. ....... . . . . . ... . .. .. . . . . . . .. . . . .... . ~. . .. . . .
tB) 0-25 parts by weight of a wax;
(C) 0-50 parts by weight of an alkali solu~le resin; with the
total of (A), (B) and (C) amounting to 100 parts by weight;
(D) 0.1-50%, based on the weigh. of (A), (B) and (C), of wetting,
emulsifying, plasticizing and coalescent agents; and
(E) 0-5~, based on the weight of (A), of a polyvalent metal
compound; and admixing therewith sufficient water to make up a
composition having a total solids content of 5-45% by ~eight.
The oligomers are generally employed at a
range of from 50 io about 100% of the total non-agueous
formulation with the preferred range being in the range of
from about 75 to about 100% of the total non-aqueous
formulation.
The wetting, plasticizing, emulsifying and dispers-
ing agents employed are well known in the art and are
disclosed in Canadian Patent No. 871,173 of Fiarman et al,
: issued May 18l 1971.
The polyvalent metal compound, if employed in
the floor polish formulation, may be either a metal complex
or a metal chelate. The polyvalent metal ions may be those
of beryllium, cadmium, copper, calcium, magnesium, zinc,
zirconium, barium, strontium, aluminum, bismuth, antimony,
lead, cobalt, iron, nickel or any other polyvalent metal
which can be added to the composition by means of an oxide,
; hydroxide, or basic, acidic or neutral salt which has
appreciable solubility in water, such as at least about 1%
by weight therein. Tne selection o* the polyvalent metal
and the anion are governed by the solubility of the
resultant metal co~plex in order to insure adequate clarity
of the final formula tea polish. Zinc an~ cadmium are
. ~ .
. ~
especially preferred poly~alent metal ions. The ammonia
and am;ne complexes (and especially those coordinated with
Nr~3) ~f these met-ls are p~rticularly usefulu Amires
c~pable cf complexing in^lude morpholine, monoethanol amine,
-4~- :
. ' . . . . .. - ' . - .' ' . ',: -
33~i
diethylaminoethanol and ethylenediamine. Polyvalent metal
complexes (salts) of organic acids that are capable of
solubilization at an alkaline pH may also be employed.
Such anions include acetate, glutamate, formate, carbonate,
salicylate, glycollate, octoate, benzoate, gluconate,
oxalate, lactate and the like. Polyvalent metal chelates
wherein the ligand is a bidentate amino acid such as
glycine or alanine may also be employed. The polyvalent
metal compound must be such that the metal is available
to serve its crosslinking function, i.e., it is dissociable
- to form polyvalent metal containing ions.
Preferred polyvalent metal compounds, complexes
and chelates include zinc acetate, cadmium acetate, zinc
glycinate, cadmium glycinate, zinc carbonate, cadmium
carbonate, zinc benzoate, zinc salicylate, zinc glycollate
and cadmium glycollate. Although the polyvalent metal
compound may be added to the polish composition in dry form
such as a powder, it is preferred to first solubilize the
polyvalent metal compound using a fugitive ligand such
as ammonia. For purposes of this invention, a ligand is
considered fugitive if at least a portion of the ligand
tends to volatilize under normal film forming conditions.
Since the ammonia may complex with the polyvalent metal
compound, a compound such as zinc glycinate or zinc
carbonate when solubilized in dilute aqueous ammonia
solution, may be named zinc amine glycinate or zinc -
ammonium c~rbonate.
The polyvalent metal compound, when used, is
employed in an amount so that the ratio of polyvalent
metal to the acid of the addition polymer varies from
~ o~
about .05 to 0.5 and preferably from about 0.2 to 0.3.
This is expressed as the ratio of metal, such as Zn++ to
-COOH or -COONH4 groups a ratio of 0.5 being stoichiometric.
In the compositionsof the present invention, the
relative proportions of the oligomer to wax are from 100:0
to 75:25 by weight. The variation on these relative
proportions provides for various buffing characteristics.
The amount of an emulsifying or dispersing agent or agents
when used in the aqueous polish is generally from 0.1 to
30%, and preferably 1 to 20% of the combined weights of the ~ -
oligomer and wax. The concentration of the aqueous polish
is suitably from 5 to 25% solids and is preferably about ~-
10 to 20% by weight of solids.
When finally formulated as a polish, the composi-
tion should have a pH in the range of from about 7.0 to
about 10Ø Most advantageously for an autoredispersible
polish, its pH is from about 9.0 to about 10Ø Suitable
alkaline or buffering agents such as borax, sodium hydrox-
ide, ammonia, or amines such as diethylamine, triethylamine,
morpholine or triethanolamine may be introduced to adjust
the pH to the desired value.
For a non-buffable, self-polishing composition,
the wax should not be over 25 parts by weight, preferably ~
up to 15 parts by weight in 100 parts total of polymer plus ~ -
wax according to the above table. Satisfactory non-
buffable floor polish formulations have been prepared - -
without the inclusion of a wax.
If the wax (when used) is separately dispersed,
common dispersing agents may be used, but amine salts of a
soap, such as ethanolamine oleate or stearate, are
also quite useful. Suitable homogenizing mills may be used
to assist in forming the dispersion.
The waxes or mixtures of waxes which may be used
include waxes of a vegetable, animal, synthetic, and/or
mineral origin, or mixtures thereof, such as carnauba,
candelilla, Fischer-Tropsch wax, microcrystalline wax,
lanolin, cocoa butter, cottonseed, stearin, Japan wax,
bayberry, myrtle, mace, palm kernel, beeswax, spermaceti,
Chinese insect, mutton tallow oxidized polyethylene
emulsions, polypropylene, copolymers of ethylene and
acrylic esters, waxes obtained by the hydrogenation of
coconut oil or soybean oils, and the mineral waxes such
as paraffin, ceresin, montan, ozokerite and the like.
Care should be taken in selecting the wax if water clarity
is desired.
Wax soluble resins or gums may be substituted for
up to 50% of the wax, by weight. Natural or synthetic
materials, including terpene-phenolic resins, heat
processed (run) Congo, wood rosin, oxidized petroleum wax,
and the like, are also suitable.
The compositions are adapted to form clear glossy
coatings. However, if desired, a colored appearance
may be obtained by the introduction of water soluble or oil
soluble dyes in suitable proportions. Examples of suitable
dyes which may be used include iron blues, phthalocyanine
blues and greens and organic maroons. The amount of dye may
be varied widely, depending on the effect desired.
For optimum gloss, water and wear resistance, the
final polish formulation must contain sufficient wetting
agents and coalescent film plasticizer solvent to insure
--7--
lO~V~81
uniform film contlnuity, film touyhness and adhesion to the
applied substrate. From about 0.5 to 30~ by weight of these
solvents, based on the weight of oligomer and wax, wax soluble
and alkali soluble resins when present, is used. The composition
may include from 1 to 50 percent by weight of a wetting agent of
the non-ionic type selected from an ethylene oxide modi~ied
alkylphenol, an ethylene oxide modified higher fatty alcohol, an
ethylene oxide modified long chain mercaptan, an ethylene oxide
modified fatty acid or an ethylene oxide modified amine.
Since the purpose of these solvents is usually- to facili-
tate film formation and since it is not always necessary to im-
part flexibility to the oligomer composition when it is inherently
tough and flexible, as is often the case, a fugitive or semi-
fugitive plasticizer is preferred, rather than a permanent plast-
icizer. However, permanent plasticizers may be used without the
production of films having poor wear-resistance and poor resist-
ance to water. Plasticizers may also serve as an aid in obtaining
clarity and improving gloss. Certain plasticizers, such as tri-
butoxyethyl phosphate, serve also as leveling agents. Mixtures
of fugitive and permanent plasticizers may also be used. Certain
fluorocarbon surfactants also act as leveling agents and these
materials are described in U. S. Patent No. 2,937,098, of Henry
C. Geen, issued May 17, 1960.
Examples of fugitive plasticizers or coalescents include - ~ -
the monobutyl, monoethyl, monomethyl or other monoalkyl ether of
diethylene glycol or dipropylene glycol, isophorone, benzyl
alcohol, diglyme, butyl "Cellosolve*" and 3-methoxybutanol-1.
Broadly, these materials may be described as water soluble higher
boiling (about 150-200C.) monohydric and polyhydric alcohols
and lower (Cl-C5)alkyl monoethers and diethers of glycols and
diglycols. When the polymer is prepared by solution polymeriza-
tLon, as described above, these oxygenated solvents may serve as a
~*~iademark. Butyl nCellosolve" is ethylene glycol monobutyl ether.
u ~
fugitive plasticizer in the floor polish composition, i.e.,
the polymer solution may be simply diluted with ammonia
water to the desired solids content. Such fugitive
plasticizers are well known, as is shown by the patents
cited above.
Examples of essentially permanent plasticizers
that are suitable at low levels include benzyl butyl
phthalate, dibutyl phthalate, dimethyl phthalate, tri-
phenyl phosphate, 2-ethyl hexyl benzyl phthalate, butyl
cyclohexyl phthalate, mixed benzoic acid and fatty oil
acid esters of pentaerythritol, poly(propylene adipate)
dibenzoate, diethylene glycol dibenzoate, caprolactam,
tetrabutylthiodisuccinate, butyl phthalyl butyl glycolate,
acetyl tributyl citrate, dibenzyl sebacate, tricresyl
phosphate, toluene ethyl sulfonamide, the di-2-ethylhexyl -- -
ester of hexamethylene glycol diphthalate, di(methyl-
cyclohexyl)phthalate, tributoxyethyl phosphate and tri-
butyl phosphate. The particular plasticizer and the amount
thereof used are chosen in accordance with the demand for
compatibility and efficiency in insuring optimum performance
and polish clarity.
Besides containing the oligomer, and the coalescent,
a suitable wetting or emulsifying agent, and the optional
wax, metal complex, wax soluble resin and dye mentioned
hereinabove, the compositionof the present invention may
also contain alkali soluble resins in an amount of from 0%
to 50% of the total weight of the copolymer, wax, wax
soluble resin and alkali soluble resin. Generally the
alkali soluble resins have acid numbers varying from --
_g _
1 V ~
about 100 to 300 and average number moleculAr weights
ranging from about 500 to about 10,000 and preferably about
800 to 2000.
Examples of alkali soluble resins include copolymers
of styrene or vinyltoluene with ~
~ ' .
~ , . . . .. .
at least one ~,~-monoethylenically unsaturated acid or -~-
anhydride such as styrene-maleic anhydride resins, rosin-
maleic anhydride re~ction products esterified with pGly- -.-
hydric alcohols, and alkali-soluble alkyds, which are
essentially polyesters of aliphatic dicarboxylic acids
with aliphatic polyhydric alcohols which may be modi~ed
with C8-C18 fatty acids and glycerol esters of C8-C18
fatty acids. Examples of the dicarboxylic acids include
maleic, fumaric, ad~pic and sebacic acids, including ~ -
anhydrides thereof. The polyhydric alcohols may b_
glycerol, pentaerythritol, trimethylolethane and glycols
having 2 to 8 carbon atoms including diethylene glycol and
triethylene glycol. Other alkali soluble resins such as
Manila gum, shellac, alkyl acrylate-shellac copolymers
containing enough shellac to be alkali soluble (see Example 4 of
Canadian Patent 668,945 of Zdanowski et al, issued August 20, 1963,
Loba gum, styrene-acrylic acid or styrene-methacrylic acid copo-
lymers oontaining, for example, 50 % by weight of each monomer,
maleic anhydride copolymerized with an equimolar amount of
diisobutylene, and the like.
The concentration of the aqueous dispersion for
application purposes may be from 5 to 45% solids and is
preferably from about 10 to 25~ by weight of solids.
--10--
~- - :-'- -' .' ,' . .. . -
~V~(33~L
The compositions may be used for impregnating
_xtiles, leather, paper or other porous or fibrous
materials. They may also be applied to plastic sheets such
as "Cellophane*", polyethylene, "Formica**", polyethylene
terephthalate, saran and the like. They may also be
applied to rigid surfaces, including metals such as steel,
aluminum, copper, b-ass, bronze, ti~, chromium, wrought
iron and the like and also to wood, stone, ~asonry, brick,
ceramic tile, glass, asbestos cement shingles or siding,
terrazzo, cement and conc~ete surfaces such as floors.
The compounds are especially valuable for polishing floors
including those made of wood, linoleum, rubber and plastic
tiles, such as linoleum, asphalt, vinyl and vin-rl-asbestos.
Examples of wetting and dispersing agents which
may be added in formulating the polish include alkali metal
and amine salts of higher fatty acids having I2 to 18 carbon
atoms, such as sodium, potassium, ammonium or morp~oline
oleate or ricinoleate, as well as the com~on nonionic
surface active agen~s. (Certain fluorocarbon surfactants
also act as wetting agents and these materials are described
in U. S. Patent No. 2,937,098 of Henry C. Geen, issued May 17,
1960). Additional wetting agent improves the spreading action ~
of the polish. ~ -
For polishing floors, the coating obtained from the
composition, should have, or develop in a short period of time,
a Knoop hardness number of 0.5 to 16 or greater when measured
on a film thereof 0.5-2.5 mil thick on glass, as has been mentioned
above. This range of hardness provides good resistance to
abrasion and wear and can be obtained by the appropriate selection
of monomers to be polymerized.
*Trademark for a brand of regenerated cellulose film produced
from viscose by treatment with sulfuric acid and/or ammonium salts.
**Trademark for high pressure laminated sheets of melamine and
phenolic plastics for decorative applications.
-11- !1 -
.
( ( 73-19
~ 3~1
The coalescing agent, oligomer and polyvalent
metal compound, wax and/or resin when used may be mixed
in any order desired.
~ne polyvalent metal complex, if used, may be
incorporated into the com~osition at any time; generally,
however, it is added last.
The compositions have good storage stability.
They are applied in the normal manner by, for example,
cloths, by brushes or mops. Tney dry rapidly to clear,or
if pigmented, colored films, having hard, tough exceptiOn-
ally glossy surfaces. There is substantially no dis- ~-
coloration of the films on aging The application of the
compositions to surfaces carrying previously applied coatings~
of alkali/removable compositions does not remove appreciable
amounts of such coatings nor is the viscosity or consistency
of the composition of the present invention detrimentally
affected. Hence, the compositions go on the surface
uniformly and with ease but without streakiness or other
irregularities.
The compositiDns containing oligomers having
carboxylat~ (acid or salt) groups are removable by alkaline
detergents. When crosslinking metals are used, the metal
crosslinked coating is insoluble in water, ordinary soap
solutions and most detergent solutions, and, being soluble
~5 in ammonium hydroxide, ammonia solutions are necessary for
their removal.
The following an~lytical method was established
to quantitatively define the clarity of the polishing
compos1tions. For purposes of this invention, the terms
"essentially water clear'l or "substantially-clarified"
~ - 12 -
73-19
designate the appearance of polishing compositions, con-
taining 15 to 18~ solids, having a re~ding of at least
50% light transmission on a B~usch and Lomb Spectronic 20
Colorimeter that is calibrated to the range of from 0 to
- 5 100% with e~ther methanol or distilled water at a wave-
- length of 600 millimicrons (mu.)~ ~ne terms "water clear"
or "clarified" designate the appearance of a polishing
composition, contain ng 15 to 18% solids, having a reading
of at leas~ 85~.
Gloss of the dried coatings is determined by both
subjective visual means and by a Leeds and Northrup
- Photovolt Glossmeter (Cat. No. 766~) using a 60D head.
~he oligomers are prepared b~ the methods dis-
closed in Canadian Patent No. 959,999 of S.N. Lewis and
R.A. Haggard, issued December 24, 1974.
-; The oligomers employed in the finish compositions of the
present invention have the following structural formula
I C~2-C - CC2Z
~o wherein R0 is a residue of a chain regulating alcohol;
Rl is the alcohol portion of one or more monomeric esters
of methacrylic acid; n is an integer consistent with a carboxy
functionality of at least 2.7 per average chain, for example,
2-4; R is hydrogen or the residue of a comonomer or comonomers;
x is an integer having a value such that the sum of n~ x is consistent with
J the aforesaid average chain length, which afford polymers having a M of about. 1300 to about 2500; and Z is a cation derived from an alkali ~etal such as sodium,
- 13 -
.
-. . . . . : ~
- . - . , .
potassium and the like, ammonia or a tertiary amine such
as an alkanolamine including dimethylethanolamine, diethyl-
ethanolamine, triethanolamine, N-methylmorpholine and
the like.
A preferred procedure for preparing the polymers
(I, supra) is by a two-stage process. In the first
stage of the reaction, the polymer having all ester -
functions and a low molecular weight distribution, is
prepared by a batch or gradual addition technique using
from about 20 to about 60% by weight of the total monomer
charge and using a relatively high alcohol concentration
generally in the range of from about 20 to about 50 mole
percent of the initial monomer charge. The remainder
of the monomer charge is then added to the reaction mixture.
The addition of the remaining monomer is exothermic and
leads to a revised molecular weight distribution. The
reaction is generally conducted at a temperature in the range
of from about 40 to about 130C. and preferably at a
temperature in the range of from about 60 to about 95C.
Although the polymerization can be conducted without a
solvent, improved yields are obtained when a solvent is
employed in the later stages of the polymerization. The
solvents which may be employed include the aromatic
solvents such as toluene, xylene and the like. Catalysts
which may be employed include the alkoxides, for example,
the alkali metal alkoxides, such as sodium alkoxide,
potassium alkoxide and the like, including sodium methoxide,
potassium methoxide, potassium tert-butoxide and the like,
at a concentration in the range of from about 0.4 to about 4
-14-
., . -
73-19
~ 0 ~ 3 ~
mole percent and preferably from about 0.6 to about 3 mole
percent based on the total monomer charge.
The tris-, tetra- and higher acids of these
oligomers may be prepared by treating the oligomeric esiers
with a base such as an alkali metal base, including sodium
hydroxide, potassium hydroxide and the like. The conversion
of the oligomeric estersto the mono- and biscarboxy polymers
is relatively rapid and generally occurs within one hour
at a temperature in the range of from about 70 to about
75co The tris-, tetra- and higher carboxy containing
oligomes are obtained by further heating the basic reaction
mixture at a temperature in the range of from ab~ut 80 to
about 120C. for a period of time from about 2 to about 5
hoursO The alkali metal salts obtained are either used
directly or converted to the free acid by dissolving acid
salt in water in the presence of a water insoluble organic
liquid, acidifying the aqueous solution and collecting the
organic layer which will contain the desired acid. The
acids may then be converted to other bases and employed as
leveling agents. Examples of someother bases include
those obtained from ammonia, tertiary amines such as
alkanolamines including dimethylethanolamine, diethyl- -
ethanolamine, triethanolamine, N-methylmorpholine and
the like.
The following examples illustrate the preparation
of various salts of the partially hydrolyzed methacrylate
esters and salts thereof.
- 15 -
., , . ~.. .... ... ..
0~8~
EXAMPLE 1 - Partially Hydrolyzed Oligomer of Methyl
methacrylate
-
Step A - Oligomeric Methyl methacrylate
To a two-liter, three-necked flask equipped
with a stirrer, thermometer and reflux condenser are
added, under a nitrogen blanket, toluene (115 g.), methanol
(2.4 g.), 30% methanolic potassium methoxide (20.2 g.) and
methyl methacrylate (216 g.). The temperature of the
reaction mixture rises to 27C. over a 25 minute period.
The mixture is then warmed to 33C. within 20 minutes and
within another 20 minutes the temperature reaches 42C.
and requires cooling. After 40 minutes, the reaction
mixture is warmed to maintain the temperature at about
40C. After 1-1/2 hours, the reaction temperature is
increased to 60C. at which time a solution of methyl
methacrylate (649 g.) and toluene (265 g.) is added while
maintaining the temperature at 60-62C. After a 45 minute
hold period, conversion exceeds 99%. An aliquot of the -
reaction mixture (300 g.) is treated with concentrated
sulfuric acid (1.05 g.) and diatomaceous earth (1.5 g.) and
filtered to afford a clear, light yellow oil at 70.5% solids.
Molecular weight determination by gel permeation -~
chromatography discloses MW1,700 and Mnl,350-1400.
Step B - Partially Hydrolyzed Oligomer of
Methyl methacrylate
To oligomeric methyl methacrylate (1,200 g.) in a
two-liter Parr bomb fitted with a sampling tube, pressure
gauge, stirrer shaft, pressure release valve and hose
connection to a dry ice condenser is added sodium hydroxide
(161 g., 2.049 m., 50.9%). The bomb is heated by an oil
-16-
73-19
~ 3 ~ 1
bath at 130-135C. with the vent valve opened for 1,'2 hour.
The vent valve is then closed and the temperature of the
reaction mixture is raised to 110C. and 1~ psl. After
two hours, the heating is discontinued and toluene (12C g.)
and deionized water (240 g.) is added. When the temperature
reaches 80C. and the pressure zero, the stirring isstopped
- and the bomb opened. The contents are transferred to a
three-liter, three-necked flask. To this is added toluene
(306 g.), water (219 g.) and _-butanol (67 g.). Tne
reaction mixture is maintained at 55C. while formic acid
(219.7 g., 2.54 m., 90~) is added over a 15 minute period.
Stirring is maintained for an additional 20 minutes and
the phases are separated. To the organic phase, in a
three-liter flask, are added water (905 g.) and concentrated -
ammonium hydroxide (11.7 g.). This mixture is heated to
reflux to remove the organic distillate. The reaction
mixture is cooled to 95c. and treated with additional
ammonium hydroxid~ (106.9 g.). Stirring is continued for
20 minutes as the ~lution is cooled to 60C. The product
has the following characteristics: clear and essentially
colorless (AP~AC 100) at ~8% solids content; pH 8.7; acid
No. 123 (100~ solids); viscosity ~ 5,000 cps at 25c,
By following essentially the procedure as -
dsscribed in Example 1, the following products of Table I
are prepared:
- 17 - -
73 19
10803~1
Approx.A rox. % of
CarboxyActu~l Acid ~igomer Equivalent
Example Mw ContentNumber _ MMA MAA
2 1600 4 123 78 - 22
3 1600 3 98 83 - 17
~ 1350 ~ 160 73 - 27
135~ 3 120 - 80 - 20
6 2000 ~ 81 82 - 18
EXAMæLE 7 - Oligomeric Methyl methacrylate/Butyl methacrylate
Havinz a Carboxy Content of ~
Step A - Oligomeric Methyl methacrylate/Butyl
methacr~late (7~/2~ b,-r wei~ht)
To a three-liter, three-necked flask equipped
with a condenser, paddle stirrer, thermometer,addition
funnel and Y~tube is added, under nitrogen, toluene
(60 g.), n-butanol (22.5 g.; 0.30 m.), sodium methoxide ~
in methanol (25~ solution, 29.4 g., 0.136 m) and potassium ~-
methoxide in methanol (30% solution, 12.7 g., 0.055 m.).
To this clear solution at 60C. is added with stirring
- methyl methacrylate (310 g., 3.1 mole) and butyl methacryl-
ate (103 g., 0.73 m.) over a 30 minute period. Tne light
yellow mixture is maintained at about 61C. until the
reaction mixture exotherms (about 35 minutes after addition). ~
The temperature is maintained at about 65C. After the --
exotherms subsides, there is then added over a one hour
period methyl methacrylate (1,067 g., 10.6 m.), butyl ~ -
methacrylate (355 g., 2.42 m.) an~ toluene (414 ga ) while
maintaining the reaction temperature at 60-63~C. with ice
bath cooling. Tne product obtained at ~98% conversion after
a 1/2 hour hold following the second stage addition is
oligomeric methyl methacryl2te/butyl methacrylate (75/25)
of Mw ca. 1450, Mn ca. 1300, and is employed in the follow-
ing step without further purification.
- 18 _
. ,~.
()3~1
Step B - Oligomeric Methyl methacrylate/Butyl
methacrylate Having a Carboxy Content
of Four
To the oligomeric methyl methacrylate/butyl methacrylate
of part A (1,000 g., 80.1~ oligomer) in a three-liter
three-necked flask equipp~d with a bottom stopcock, reflux
condenser, stirrer and thermometer, under a nitrogen
atmosphere, at 63C. is added aqueous sodium hydroxide
(185 g.; 50.3%). The reaction mixture is held at 73 - 78C.
for one hour and then heated to reflux for 4.5 hours.
Titration discloses 84% conversion at this point. The
yellow viscous oil is cooled and diluted with water (200 g.)
and toluene (200 g.). A heterogeneous distillate (400 g.)
is removed over a 1-1/2 hour period. To the remaining
clear yellow-orange solution is added toluene (200 g.) and
the mixture refluxed for 5-1/2 hours. At this time, toluene i-~
(200 g.), isobutanol (100 g.) and water (710 g.) are added
and the reaction mixture cooled to 50-60C. Su~furic
acid (179 g., 97~, 1.78 m.) is added over 15 minutes with
cooling. The reaction mixture becomes a white, mobile,
two-phased mixture and is agitated an additional 15-20
minutes. After removing the aqueous layer 9 additmonal water
(700 g.~ is added and the reaction mixture heated at 60-
70C. with sufficient vacuum to remove the toluene. The
pressure is adjusted to atmospheric pressure after collect- -~
ing about 400 g. of distillate while increasing the
temperature to 100C. To the remaining white, two phased,
soft-gun mixture at 90C. is added aqueous ammonia (148 g.,
2.45 m., 28.2%). After two-thirds of the ammonia is added,
solubilization occurs. The solution is cooled to 60-65C.
and the remaining ammonia added. The product solution is
. .
--19--
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10803~
clear and pale yellow (AP~A color ca. 100); solids are 50%
at pH 9.2; viscosity at 25C. is 20,000 cps and product
acid number is 150 + 5 (100%; representing an average carboxy
content of ~).
By following substantially the procedure as
described in Example 7 there is prepared the following
products described in ~able I.
- 20 -
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The following data in Table II summarizes the
key application properties of the series of ~ ~/MAh
oligomers evaluated as sole vehicles in high gloss water
clear floor polishes. The data shows that water resistant
properties decrease with increasing polymer acid concentra-
tion and also slightly decreases with decreasing oligomer
molecular weightO ~he data also shows that polish gloss
properties vary inversely with polymer molecular weight
and directly with acid content at equal molecular weight ;~
10 within the scope of this series. At equal molecular weight, -
oligomer film hardness varies directly with its degree
of hydrolysis which explains the better wear resistance
of ~tra-acid aligomers over the tris-acid analogs. Tnese
experiments indicate that relatively low molecular weight
and high acid content is preferred for best gloss and
autoredispersibility while a higher molecular weight
oligomer offers potential for better water and wear
resistance.
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FORMULATION EXAMPLES
The following examples illustrate various
formulations which can be employed (all percentages by weight).
A
Oligomer (15%~ ----100.0
"Carbitol" -------------- 4.0
Caprolactam-------------- 1.0
"FC-128"1 (1%)----------- 1.0
"KP-140" ---------------- 0.4
Oligomer (15%)------------100.0
"Carbitol"---------------- 5.0
"FC-128" (1%)------------- 1.0
"KP-140"------------------ 0~4
C
Oligomer (15~)-----------100.0
"Carbitol"--------------- 3.0 ---
Hexylene Glycol---------- 4.0
"FC-128 (1%)------------- 1.0 --:
D -~ -
Oligomer (15%)-----------100.0
"Carbitol---------------- 5.0
Hexylene Glycol---------- 1.5 : -
"FC-128" (1%)------------ 1.0
"KP-140"----------------- 0.8
~ -26-
108l~381
Oligomer (12%)~ ------100.0
"Carbitol"--------------- 4.0
Hexylene Glycol---------- 1.0
"FC-128" (1%)------------ 1.0
"KP--140"----------------------- 0.4
Oligomer (12%)-----------70
Alkali Sol Resin--------~30
"Carbitol"---------------3.0
"KP--140"------------------0.4
"FC-128"-----------------0.5
G
Oligomer-----------100.0
Zn(NH3) CO3 (8.4% zinc)-3.0
Methyl "Carbitol"-4-5.0
Hexylene glycol----l.0
"KP-140"~ ----1.0
"FC-128" (1%)------0-.5 -
Oligomer (14%)------------------93.0
Polyethylene AC 392 (14%)------- 7.0
Methyl "Carbitol"--------------- 5.0
Hexylene glycol-------~ ---- 1.0
"KP-140"------------------------ 0.4
"FC-128) (1%)-------------------- 1.0
-"FC-128 - A fluorocarbon surfactant, Minnesota Mining &
Manufacturing Co.-trademark.
2"KP-140" - Tributoxyethyl phosphate, FMC - trademark.
nCarbitol" - Diethylene glycol monoethyl ether, Union Carbide
Corporation - trademark.
Methyl "Carbitol" - Diethylene glycol monomethyl eth6~r, Union
Carbide Corporation - trademark.
- --27--
