MONO HYDROXY UNSATURATED DIESTERS

DIESTERS DE COMPOSES MONOHYDROXYINSATURES

English Abstract

ABSTRACT OF THE DISCLOSURE
Hydroxy unsaturated diesters, and process for their production,
of formula I
R1 - O2C - CH = CH - CO2 - R2
wherein R1 represents
(a) an alkyl group of two to six carbon atoms containing one
free hydroxyl group,
(b) a 2,3-dihydroxypropyl group, or
(c) a group of formula II
<IMG> II
wherein n = 2 or 3, x = 2 or 3, and m is from 1 to 800; R2 represents an
alkyl group of linear or branched configuration containing two to twelve
carbon atoms, which process comprises reacting together a polyol of formula
R1OH, a primary alcohol of formula R2OH, and an acid of formula HO2C-CH=CH-
CO2H, or an anhydride of such acid, in the presence of para-toluene sulphonic
acid as esterification catalyst, in the proportions of 1 mole of polyol of
formula R1OH, to 1.1 moles of primary alcohol of formula R2OH, to 1 mole of
acid of formula HO2C-CH=CH-CO2H, or anhydride thereof, and isolating the
monomeric unsaturated diester so produced. These compounds are copolymer-
izable by free radical processes with acrylic or vinyl acetate monomers.
These polymers can be cross-linked with amino resins to provide thermo-
setting film forming compositions.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the preparation of hydroxy group containing unsat-
urated diesters of formula I
R1 - O2C - CH = CH - CO2 - R2
wherein R1 represents
(a) an alkyl group of two to six carbon atoms containing one
free hydroxyl. group;
(b) a 2,3-dihydroxypropyl group; or
(c) a group of formula II
<IMG> II
wherein n = 2 or 3, x = 2 or 3, and m is from 1 to 800; R2 represents an
alkyl group of linear or branched configuration containing two to twelve car-
bon atoms, which process comprises reacting together a polyol of formula R1OH,
a primary alcohol of formula R2OH, and an acid of formula HO2C-CH=CH-CO2H, or
an anhydride of such acid, in the presence of para-toluene sulphonic acid as
esterification catalyst, in the proportions of 1 mole of polyol of formula
R1OH, to 1.1 moles of primary alcohol of formula R2OH, to 1 mole of acid of
formula HO2C-CH=CH-CO2H, or anhydride thereof, and isolating the monomeric
unsaturated diester so produced.
2. Process according to claim 1 wherein the excess primary alcohol
of formula R2OH is removed by distillation.
3. Process according to claim 1 wherein the alcohol, polyol, and
acid or anhydride combination used is chosen from one of the following groups:
(i) isobutanol, ethylene glycol, and maleic acid or anhydride;
(ii) butanol, ethylene glycol, and maleic acid or anhydride;
(iii) 2-ethylhexanol, ethylene glycol, and maleic acid or anhydride;
(iv) isobutanol, 1,2-propylene glycol and maleic acid or anhydride;
(v) isobutanol, glycerol, and maleic acid or anhydride;
(vi) isobutanol, ethylene glycol, and fumaric acid.
19

4. A copolymer capable of crosslinking to provide a thermosetting
system characterised in that the copolymer is derived from monomers of the

following classes in the weight proportions given:
(a) from 11% to 30% of a diester of formula (I):
R1 - O2C - CH = CH - CO2 - R2 (I)
wherein R1 represents (a) an alkyl group of two to six carbon atoms containing
one free hydroxyl group,
(b) a 2,3-dihydroxypropyl group or
(c) a group of formula II
<IMG> (II)
wherein n = 2 or 3, x = 2 or 3, and m is from 1 to
800 ; and which has been prepared by
reacting together 1 mole of polyol R1OH, 1.1 moles
of primary alcohol R2OH and one mole of acid of
formula HO2C - CH = CH - CO2H, or the anhydride
thereof in the presence of para-toluene sulphonic
acid as catalyst;
R2 represents a linear or branched primary alkyl group with 4 to 12 carbon
atoms;
(b) from 2% to 35% of an alkyl acrylate having up to eight carbon atoms
in the alkyl group, which group may be of linear or branched config-
uration, and
(c) remainder an olefinically unsaturated monomer of the styrene, vinyl,
acrylic, or methacrylic classes.
5. Copolymer according to claim 4 characterised in that the unsaturated
diester used is the reaction product of one of the following combinations of
reactants:
(i) isobutanol, ethylene glycol, and maleic acid or anhydride;
(ii) butanol, ethylene glycol, and maleic acid or anhydride;
(iii) 2-ethylhexanol, ethylene glycol, and maleic acid or anhydride;
(iv) isobutanol, 1,2-propylene glycol, and maleic acid or anhydride;
(v) isobutanol, glycerol, and maleic acid or anhydride;
(vi) isobutanol, ethylene glycol and fumaric acid.
21

6. Copolymer as claimed in claim 4 characterised in that the alkyl
acrylate is chosen from butylacrylate and 2-ethylhexylacrylate.
7. Copolymer as claimed in claim 4 characterised in that the olefini-
cally unsaturated monomer is chosen from at least one of methyl methacrylate,
acrylic acid, vinyl acetate, and styrene.
8. Process for the preparation of a copolymer capable of crosslinking
to provide a thermosetting system, characterised in that monomers of the
following classes are reacted in solution or suspension in the presence of
a free-radical catalyst and at temperature of from 50°C to 100°C
(a) from 11% to 30% of a diester of formula (I):
R1 - O2C - CH = CH - CO2 - R2 (I)
wherein R1 represents (a) an alkyl group of two to six carbon atoms containing
one free hydroxyl group;
(b) a 2,3-dihydroxypropyl group; or
(c) a group of formula II
<IMG> (II)
wherein n = 2 or 3, x = 2 or 3, and m is from 1 to
800 carbon atoms; and which has been prepared by
reacting together 1 mole of polyol R1OH, 1.1 moles
of primary alcohol R2OH and one mole of acid of
formula HO2C - CH = CH - CO2H, or the anhydride
thereof in the presence of para-toluene sulphonic
acid as catalyst;
R2 represents a linear or branched primary alkyl group with 4 to 12 carbon
atoms;
(b) from 2% to 25% of an alkyl acrylate having up to eight carbon atoms
in the alkyl group, which group may be of linear or branched
configuration; and
(c) remainder an olefinically unsaturated monomer of the styrene, vinyl,
acrylic, or methacrylic classes.
22

9. Process according to claim 8, characterised in that the reaction
is carried out in isopropanol solution under reflux.
10. Process according to claim 8, characterised in that the reaction
is carried out in water in the presence of sufficient surfactant to provide
an aqueous emulsion.
11. Process according to claim 10, characterised in that the reaction
is carried out at a temperature of from 65 - 75°C.
12. Process according to claim 8, characterised in that the unsaturated
diester used is the reaction product of one of the following combinations of
reactants:
(i) isobutanol, ethylene glycol, and maleic acid or anhydride;
(ii) butanol, ethylene glycol, and maleic acid or anhydride;
(iii) 2-ethylhexanol, ethylene glycol, and maleic acid or anhydride;
(iv) isobutanol, 1,2-propylene glycol, and maleic acid or anhydride;
(v) isobutanol, glycerol, and maleic acid or anhydride;
(vi) isobutanol, ethylene glycol, and fumaric acid.
13. Process according to claim 8, characterised in that the alkyl
acrylate is chosen from butylacrylate and 2-ethylhexylacrylate
14. Process according to claim 8, characterised in that the olefinically
unsaturated monomer is chosen from at least one of methyl methacrylate,
acrylic acid, vinyl acetate, and styrene.
15. Process according to claim 8, characterised in that the free radical
catalyst is chosen from t-butyl peroctoate and ammonium persulphate.
23

Description

105~;'Z7
Maleic anhydride, maleic acid, fumaric acid, and itaconic acid
are used on a commercial scale for the synthesis of (a) unsaturated pol~esters
and (b) monoesters and diesters with monobasic fatty alcohols.
Group ~a) products can be synthesized so that they contain termi-
nal hydroxy groups. Such hydroxy terminated unsaturated polyesters are
capable of polymerizing with acrylic and vinyl monomers, and of reacting with
amino resins. m eir reaction with amino resins leads to crosslinking under
the influence of heat. Iherefore, such polyesters can form thermosetting
compositions. On the other hand, the group (a) polyesters are polymeric with
regard to their unsaturation (that is, many double bonds per molecule) and,
therefore, their copolymerization with other monomers, such as acrylic esters,
; and vinyl acetate, leads to rapid crosslinking and gellation.
Consequently, copolymerization of polymeric unsaturated poly-
esters with other unsaturated monomers, such as acrylic and methacrylic
esters, and vinyl acetate, carnot apparently yield commercially useful solu-
tion or emulsion copolymers.
I Group (b) monoesters and diesters are used as comonomers in
I solution, and in emulsion copolymers. However, they cannot impart hydroxy-
f~,nctionality and therefore crosslin~ a~ility, to any of their copolymers. ;
m e present invention relates to the synthesis of hydroxyl
group containing mono unsaturated diesters which overcome many of these dis-
advantages. m us this invention provides a process for the preparation of
mo~ohydroxy unsaturated diesters of form~la I
Rl - O2C - Z - CO2 R2
wherein Rl represents
(a) an alkyl g~oup of two to six carbon atoms containing one
~, ..
, free hydroxyl grou~
(b) a 2,3,dihydroxypropyl group; or
(c) a group of formula II
_~ (CH2)n ]m [ (CH2)x~
~-:7 > .
,~-
,:'': ' ' ' : .

~S~6~7 ::
wherein n = 2 or 3~ x = 2 or 3, and m ls from 1 to 800; R2 represents an
alkyl group of linear or branched configuration containing two to twelve car-
bon atoms, which process comprises reacting together a polyol of formula
RlOH, a primary alcohol of formula R20H, and an acid of formula H02C-CH=CH-
' C02H, or an anhydride of such acid, in the presence of para-toluene sulphonic
acid as esterification catalyst3 in the proportions of 1 mole of polyol of
~ormula RlOH, to 1.1 moles of primary alcohol of formula R20H, to 1 mole of
c acid of formula H02C-CH=CH-C02H, or anhydride thereof, and isolating the mono-
meric unsaturated diester so produced.
Preferably any remaining excess alcohol is removed from the
product after esterification has been carried out, conveniently by distil~
;( lation.
3 No particular attention has been given to the synthesis of
the subject co~pounds, possibly because they have been considered an indis-
31 tinguishable part of the widely known hydroxy terminated unsaturated poly-
~;, esters.
., ,: ~.
i However, the sub~ect compounds differ from the said polyesters
(group a) in one very important manner, due to their primarily monomeric
nature.
20 ~ Ihe subject hydroxy terminated unsaturated diesters are co-
polymerlzable with both acrylic and methacrylic ester monomers and vinyl
acetate to give solution and en~lsion polymers with commercially acceptable
. ~
physic:al properties (low viscosity, filn formers).
Furthermore, these polymers can be crosslinked with amino
resins to give thermosetting protective co~tings. The sub~ect ccmpounds
t! possess a chemical structure with unique chemical properties, namely, they
;3 can yield acrylic and polyvinyl acetate solution and emulsion copolymers
i~ with the D setting capabilities.
:-
mus in a further embodiment this invention provides a co-
polymer capable of crosslinking to provide a the D setting system character~
~ - 2 -
, ~7', ~
t,s~
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~054627
~ ised in that the copolymer is derived from monomers of the following
s classes in the weight proportions given: ~ :
(a) from 11% to 30% of a diester of formula (I):
:~ Rl - 02C - CH = CH - C02 - R2 (I) . :
`~ '.
:;
J~ ~ _
i
;3
.. ~
~::
,:~. '
2a ~
' ~:
~b: ~ 3,
,: , ' , ',. . : ' ' ' ~

~05~L6~
wherein Rl represents ~a~ an alkyl group of t~o to six carbon atoms containing
one free hydroxyl group; Cb~ a 2,3~dihydroxypropyl group or Ccl a group of ~ :
formula II
-~(CH2)nO ~m [(.CH2)x -~-OH
wherein n = 2 or 3, x = 2 or 3, and m is from 1 to 800 carbon atoms; and which
~, has been prepared by reacting together 1 mole of polyol R10}l, 1.1 moles of
primary alcohol R20H and one mole of acid of formula H02C - CH = CH - C02H,
~ or the anhydride thereof in the presence of para-toluene sulphonic acid as
, catalyst;
R2 represents a linear or branched primary alkyl group with 4 to 12 carbon atoms;
(b) from 2% to 35% of an alkyl acrylate having up to eight carbon atoms
- in the alkyl group, which group may be of linear or branched configuration; and
~i ~c) remainder an olefinically unsaturated monomer of the styrene, vinyl, -:-
:~ acrylic, or methacrylic classes.
-~ And in a third embodiment this invention provides a process for
the preparation of a copolymer capable of crosslinking to provide a thermo~
setting system, characterised in that monomers of the following classes are
reacted in solution or suspension in the presence of a free~radical catalyst
; and at temperature of from 50C to 100C : --
20 : ~a3 : from 11% to 30% of a diestcr of formula ~
Rl - 02C CH = CH - C02 - R2 ~I3
`~ wherein Rl represents Ca) an alkyl group of two to six carbon atoms containing ~;~
.,~ .
i one free hydroxyl group; ~b) a 2,3-dihydroxypropyl group; or (c) a group of
formula II
(CH2)n ~ ~CH2)x ~~ OH (II) ~
wherein n = 2 or 3, x = 2 or 3 and m is from 1 to ~00 carbon atoms; and which : -
,~
has been prepared by reacting together 1 mole of polyol RlOH, 1.1 moles of
primary alcohoI R20H and one mole of acid of formula H02C - CH = CH - C02H, or
l the anhydride thereof in the presence of para-toluene sulphonic acid as catalyst; .
J 30 R2 represents a linear or branched primary alkyl group with 4 to 12 carbon atoms;
. J - 3
~:
... . . .
,.:,. . . . . . . . .

~5~
~b) from 2% to 25% o an alkyl acrylat~ having up to eight carbon atoms
in the alkyl group, which group may be of linear or branched configuration; and
~c~ remainder an olefinically unsaturated monomer of the styrene, vinyl,
acrylic, or methacrylic classes.
The general synthesis of the subject compounds is based on the ;~
following procedure.
One mole of unsaturated acid or an~ydride is reacted with one mole
` of a diol or a triol and with 1.1 mole of alkanol at 150-170C in the presence
` of paratoluenesulfonic acid ~0.2% on total loaded reactants). The water of ~;
esterification is continuously removed by decantation while the fatty alcohol
is continuously returning to the reacting mixture. The following diols and
triols were used for the subject synthesis~
Ethylene glycol
Propylene glycol ~the 1,2-isomer)
Diethylene glycol
Glycerol
~ Polypropylenoxydio:L (Voranol ~trademark) Pl010) ~ ;
:, In general all diols would give monomeric unsaturated diesters with ~ ~
`~ pending hydroxy groups. `.
Instrumental ~LCJ IR, NMR~ and wet techniques were used to deter- ;~
mine the predominant chemical structure of the subject compounds. The analy-
~- tical results confirmed the predominately monomeric ~one double bond per
molecule) structure, given herein. ~
The subject compounds were copolymerized with acrylate esters, meth- ,`
acrylate esters, styrene and vinyl acetate in propanol and in butyl cellosolve
in the presence of butyl peroctoate or benzoyl peroxide at 92-97C.
The resulting copolymers contained 70-75% polymer at viscosities of
9000-20000 cps. These copolymers were crosslinkable and thermosetting in the
` presence of amino resins.
The subject compounds were copolymerizable with vinyl acetate, -~
. ::
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.' ~
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~OS~
styrene, acrylate and methacrylate esters in an aqueous phase containing
; surface-active agents at 60-75C. The resulting emulsion copolymers contained
44-55% polymer at viscosities of 500 - 2000 cps.
These emulsion copolymers were crosslinkable and thermosetting in
the presence of amino resins.
The following examples set forth specific embodiments of the
instant invention. However~ the invention is not to be construed as being
." . ~
limited to these embodiments for there are, of course, numerous possible
` variations and modifications. All parts and percentages in the examples as
well as throughout the specification are by weight.
EXAMPLE 1.
A round bottom cylindrical reactor vessel equipped with glycol
column-condensor, fatty alcohol - water separator decanter, stirrer, thermo-
:, ,
~3 meter and a heating means was charged with the following materials:
Maleic anhydride588 g. 6.0 moles
~, Isobutanol 590 g. 6.6 moles
Ethylene glycol372 g. 6.0 moles
~;~ Paratoluenesulfonic acid 3 g. ---
~ater 5 g. ---
~i :,. .
Z0 The reactants were heated to 105C. A strong exotherm brought the ~ `
reaction ternperature to 120C within 30 minutes. As soon as the exotherm ran
~; its course, the temperature was increased to 135-140C. Most of the esterifica-
:;. : : ~
, tion reaction took place at 140C. During this period 75 g. of water were
colIected. Then the temperature increased to 165-170C. During this period
an additional 21 g. of water were collected. Then 45 g. of isobutanol were
,
distilled off. During this last period the Acid Number dropped to 8.
,, The analysis of the resulting product gave the following results: -~
, Acid Number 8
Hydroxyl Number 230
Viscosity 120 cps.
,'; ~, .

~5~6'~7 :
2~ droxyeth~l Iso~utyl Ester
Content 82%
Other Ester Species 15%
o Free Isobutanol 3%
EXAMPLE 2.
A round bottom cylindrical reactor vessel equipped with glycol ;
column-condensor, fatty alcohol - water separator decanter, stirrer, thermo-
meter and a heating means was charged with the following materials:
Maleic anhydride 588 g. 6.0 moles
N-butanol 590 g. 6.6 moles
` 10 Ethylene glycol 372 g. 6.0 moles ~ -
- Paratoluenesulfonic acid 3 g. --~
Water 5 g- ---
The reactants were heated to 105C. A strong exotherm brought
the reactlon ten~perature to 120C within 30 minutes. As soon as the exotherm
~i, ran its course, the temperature was increased to 135-140C. Most of the
esterifica~cion reaction took place at 140C. During this period 75 g. of
water were collected. Then the temperature increased to 165-170C. During
this period an additional 21 g. of water were collected. I~en, 45 g. of :
~; ~ n-butanol were distilled off. During this last period the Acid Number dropped
to 8.
The~anaIysis of the resulting product gave the foll~wing results~
Acid ~mber 8 ~ ~ -
Hydroxyl Number 230
; :~1
Viscosity 120 cps.
~ 2-Hydroxyethyl Isobutyl Ester ~
-~ Content 82% ?
Other Ester Species 15%
Free N-butanol 3%
EXAMPLE 3
:, .
Equipment and reaction conditions were identical to those of
Example l. However, the reactor was loaded with the following materials~
. .......................................................................... .
,4 ~, ';,
~ ~ 6 ~ ~
,
, ~ ~
" " ': . : : , ' , , , " " ~ J,

~s~
Maleic anhydride 490 g. 5.0 moles
;` Octanol* 715 g. 5.5 moles
Ethylene glycol 310 g. 5.0 ~oles
Paratoluenesulfonic acid 3 g.
Water 5 g. ---
Esterification water collected = 85 g.
Octanol* distilled off =57 g.
Analysis: ; ;
Acid number 10
- 10 Hydroxyl number 185
Viscosity 120 cps.
2-Hydroxyethyl octyl ester content85% ~;
Other ester species 10%
. ~
~ Free octanol 5%
'I
. i ~
EXAMPLE 4.
Equipment and reaction conditions were identical to those of
Example 1. However, the reactor was loaded with the following materials:
Maleic anhydride 588 g. 6.0 moles
, . .
,~ 1,2-Propylene glycol 456 g. 6.0 moles
-~ 20 Isobutanol 490 g. 6.6 moles
Paratoluenesulfonic acid 3 g.
Water 5 g-
Esterification water collected ~ 96 g.
Isobutanol distilled off = 75 g.
Analysis:
Acid number 10 ~;
~Iydroxyl number 180
' Viscosity llO cps.
(2-Hydroxy)-propyl isobutyl
ester content 81%
Other ester species 16%
*The octanol used is 2-ethylhexanol.
~::
7 -
." ~; ~.

7 :~
:
Isobutanol 3
EXAMPLE 5.
Equipment and reaction conditions were identical to those of
Exarnple 1. However, the reactor was loaded with the following materials:
Maleic anhydride 588 g. 6.0 moles
Isobutanol 490 g. 6.6 moles
Diethylene glycol 636 g. 6.0 moles
Paratoluenesulfonic acid3 g.
Water 5 g- ---
, 10 Esterification water collected = 94 g.
-` Isobutanol distilled off= 73 g.
`, Analysis:
~`1 Acid number 12
Hydroxyl number 167
Viscosity 160 cps.
2-(2-hydroxyethoxy~ethyl isobutyl
~ ester con'cent 80%
j Other ester species 16%
1 Free Isobutanol 4%
EXAMPLE 6.
Equipment and reaction conditions were identical to those of `~
Example 1. However, the reactor was loaded with the following materials: ;~`
1 Maleic anhydride 588 g. 6.0 moles
3, Isobutanol 490 g. 6.6 moles
-~, Glycerol 552 g. 6.0 moles
Paratoluenesulfonic acid 3 g.
i Water 5 g. --- , ~ ;
, Esteriication water collected = 90 g.
Isobutanol distilled off = 70 g.
Analysis: `
;~ 30 Acid number 10 ;~ -
; ' ~ `~,;,
, ~ ~,,
f ~

~54~iZ7
Hydroxyl number 230 '
Viscosity 600 cps.
- Di~hydroxy propyl) isobutyl
ester content 70%
Other ester species 27%
Free isobutanol 3% '~`
_AMPLE 7.
;, Equipment and reaction conditions were identical to those of
f Example 1. However~ the reactor was loaded with the following materials: -
~. ~
Maleic anhydride 98 g. 1.0 moles ~`
Isobutanol 82 g. 1.1 moles
Eprlypropyleneoxydiol ~Voranol
P.1010) 1000 g. 1.0 moles -~ ;
Paratoluenesulfonic acid2 g.
Water 5 g. -~
Esterification water collected = 20 g.
Isobutanol distilled off= 10 g.
: j ::
Analysis~
Acid number 12 ~ `
Hydroxyl number 64 ~ ;
Viscosity 900 cps.
1 20 ~Iydroxy ~polypropylene~xy)isobutyl
ester content 72%
Other ester species 20% ~;;
~: .
~ Free Voranol P.1010 5%
", Free Isobutanol 3% -
I ~XAMPLE 8.
' Equipment and reaction conditions were identical to those of
J` Example 1. ~le reactor was loaded with the following materials:
F~maric acid 696 g. 6.0 moles
, Isobutanol 490 g~ 6.6 moles
Ethylene glycol 372 g. 6.0 moles
, 30 Paratoluenesulfonic acid 3 g. -~
:~ ". .: '
~ ~ 9 _.
' ~
~'' '

~L0546~7
-~,.:- .
Water 5 g~
Esterification started taking place at temperature higher than 130C.
Water of esterification colledted = 200 g.
Isobutanol distilled off= 70 g.
Analysis~
, Acid number 11
;' Hydroxyl number 190
Viscosity 130 cps. ~;
1 2-Hydroxy ethyl isobutyl ester 84%
;' 10 Other ester species 12% ~ ;
Free isobutanol 4%
.,, ~ . .,
EXAMPLE ~
Equipment and reaction conditions ~ere identical to those of
Example l. The reactor was loaded with the following materials:
Itaconic acid 650 g. 5.0 moles
1 Isobutanol 407 g. 5.5 moles
.,~ ..
``~ Ethylene glycol 310 g. 5.0 moles `~
:,1 ' :
i, P.T.S.A. 3 g. ---
~`~ Water 5 g~
~; 20 Toluene hyd~oqUinne }5 g, ---
~ 5% in isobutanol
- The esterification reaction was slower than of maleic anhydride.
Esteriflcation water collected = 170 g.
, Isobutanol = 35 g. '~;
~:! This product tends to homopolymerize when exposed to sunlight. `
Analysis~
Acid number 15
l ~ydroxyl number 180
l Viscosity 200 cps.
1 Hydroxy ethyl isobutyl ester
'-~ 30 content 80% ~
-. 10 ~ ,:. " ;',

~5~ 7
Other ester specie~ 16%
Free isobutanol 4%
The following examples illustrate ~he solution copolymerization of
the compounds outlined in Examples 1 through 9, with acrylic, methacrylic and
styrene monomers.
EXAMPLE 10.
A cylindrical reactor equipped with a condenser, stirrer, thermo-
meter, two addi~ion vessels and a heating means was charged with 825 g. pro-
panol. The temperature was bro~ght to 90C and a monomer blend and a catalyst
solution were added to the reactor over a period of five ~5) hours. ;~
Monomer Blend:
~ Methyl methacrylate 1000 g.
; Acrylic acid 300 g. ~ -
Butyl acrylate 800 g. \ ~:
Intermediate of Example 1. 700 g. J
Catalyst Solution:
, Propanol 90 g.
`. t-Butyl peroctoate 13 g. ~
;' Free radical copolymerization was maintained at 96C under propanol
reflux. The finished product had the followîng properties: :
Liquid viscosity = 13,000 cps.
Polymer content = 70% ;~
The intermediate was found to be completely copolymerized.
. Thermosetting Composition~
~: Polymer of Example 12. 100
Water reducible amino resin ~60%210
- Dimethylethanolamine 3
Water 30
A 3 mil film obtained from the above composition and exposed to
350F for five (5) minutes showed the following properties:
-,:' ~'
, ~ .
- 1 1 -
.,
, . ., - ~ . .
:, . . , .. . ~. ,
,, , , : .
' . ~ ' ~ ; . ' ' . " ' .

~05~27
Pencil hardness = 2H
MEK extractibles = 12% on solids
Test Methods: A. Pencil Hardness
In this test, the hardness of a cured paint film is related to the
hardness of a graphite pencil. A series of standard pencils, ranging from 4B
to 4H is supplied by Staedtler ~Germany). ~;
About l/4" of lead is "squaredl' by rubbing aga;nst fine abrasive
paper ~400 carbide)~ The pencil is held at normal writing angle (45) and
pushed forward against the film, using pressure short of breaki~g the lead.
. ~
Any marks or scratches, visible at an oblique angle under strong light, indi-
cate that the pencil is harder than the film. The hardness is expressed as
.
the grade of next softer pencil.
Grades in increasing order of hardness are:
4B, 3B, 2B B, HB, F, H, 2H, 3~1, 4H.
:;: .
:-. :
B. MEK Ex~ractibles - ~
:; ~
', The solubility of a PVA - acrylic or acrylic polymer in methyl ethyl
~ ketone decreases as the degree of crosslinkîng of this polymer increases. ~-~
Therefore, the extractibility of a polymer in MEK can be used as an inverse
~ measure of the degree of crosslinking.
; 20 A 3 mil film of the polymer is deposited from suspension or solution
on an aluminum foil. 3 - 5 g of th;s film is submitted to Sàhxlet extraction .
~ by MEK for 24 hours.
: ; ' ::
The insoluble part is dried and weighed. Thus, the MEK extractibles
or insolubles are determined as percent by weight.
EXAMPLES 11 - 18
Example 11 - as 10 but with Intermediate of Example 2. -
` Example 12 - As 10 but with Intermediate of Example 3.
Example 13 - As 10 but with Intermediate of Example 4.
Example 14 - As lO but with Intermediate of Example 5.
E Example 15 - As 10 but with Intermediate of Example 6.
?~
:, . . .
- 12 -
. ` , ~,
' ~ '; '

Z7
Example 16 - As 10 but w;t~ Intermediate of Example 7. ~ -
Example 17 - As 10 but wit~ Intermediate of Example 8.
Example 18 - As 10 but with Intermediate of Example 9.
Thus ~he solution polymers obtained in examples 11 - 18 give
copolymers within the following propert~ rangas-
Liquids viscosity range = 9,000 - 18,000 cps.
Polymer content ~N.V.) = 67 - 72% ;~
Film properties of thermosetting compositions ~Example 10)
Pencil hardness = H - 3H
~, 10 MEK extractibles = 8 - 15% on solids
The above examples show that the invented compounds would give
solution copolymers with thermosetting properties. -
I EXAMPLE 19.
'' Equipment and reaction conditions were identical to those of
! Examplc 10. The monomer blend was made up of the following materials. The
`?, remaining materials were not changed~
l Styrene 1000
~?
` Butyl acrylate 800
i:?, Acrylic acid 300
; 20 Intermediate - Examples 1. 700
Analysis~
~ Viscosity =17,000 cps. `~
;~ Polymer content =68%
'~ Film properties of the thermosetting composition of Example 10.
Pencil hardness = 3H
' MEK extractibles = 13%
3 This copolymer is also thermosetting.
The following examples illustrate the emulsion copolymerization of
some of the compounds outlined in the Examples 1 to 9, with acrylic, meth-
acrylic, styrene and vinyl acetate monomers. -~
.:. . ,
-'
~ 13 -
d~ ~ ` .
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1~15~27
EXAMPLE 20.
A cylindrical reactor equipped with three addition vessels Cfor
monomer7 catalyst and activator), a condenser, stirrer and a thermometer was ~ ;
charged with the following materials: ; ~
Water 540 ~ ~ -
; Nonionic surfactants 34 1 ~ ,: Anionic surfactants 26 ~ aqueous phase - Protective colloid 8 ~
In the monomer addition vessel the following materials were blended:
~; lO Vinyl acetate 655 ~
Intermediate - Example 1 100 ~ monomer blend
., ., ~
2-Ethylhexyl acrylate 28 ;
In the catalyst addition vessel the following materials were blended~
Ammonium persulfate 3 l , `
. Ammonia ~26%) 2.5 ~ catalyst solution
Water 27.5
`I In the activator addition vessel, the following materials were
blended:
Formopon ~trademark) 1
Water 32 3 activator solution ;'~
~, The aqueous phase was heated to 72C and then 72 g. of the monomer ~ -~
`' blend-were added to it. 1 g. of ammonium persulfate was added there and the
i emulsion polymerization was thus initiated. The exotherm pushed the reaction
~;i temperature to 77C. The monomer blend, catalyst solution and activator sol-
ution were added to the reactor over a period of six (6) hours. The resulting
;~ emulsion polymer showed the following properties:
Polymer content (% N.V.) = 55
, ' ,. ~ ; .
Viscosity (RVF #3/60 rpm) = 1000 cps. :
, Free monomer = 0.4% `~
'~, 30 Particle Size - 0.2 - 0.4 microns
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1059L6;~7
Film = Continuous~ clear.
_e osetting Composî~ion: ;-
Emulsion pol~mer - Example 20. lO0 g.
Water reducible UF resin 10 g.
A 3 mil film cast from the above blend was exposed to 350F for
five (5) minutes. It was found to have the following properties:
Pencil hardness = H ~
MEK extractibles = 15% ~; `
From the above results, it is concluded that the emulsion polymer 1`
, ~
of Example 20 is crosslinkable in the presence of amino resins.
EXAMPLES 21 - 28
Equipment and reaction conditions were identical to those of
; Example 20, except that the intermediate from Example 1 ~as substituted by
~' those of Example 2, 3, 4, 5, 6, 7, 8 and 9. .
''à ~ Example 21 - The interme;diate of Example 2 was used.
Example 22 - The intermediate of Examp~e 3 was used.
Example 23 - The intermediate of Example 4 was ased. ~ `
~ Example 24 - The intermediate of Example 5 was used.
;. Example 25 - The intermediate of Example 6 was used.
Example 26 - The m termediate of Example 7 was used. `~
Example 27 - The intermediate of Example 8 was used.
: . ~: ,-
i Example 28 - The intermediate of Example 9 was used.
Emulsion polymer products were obtained in Examples 21 to ~8.
Th:ese emulsion polymers had the following properties: ;.
Polymer content ~% N.V.) = 54 - 56 ~ -
Viscosit~ C#3/60 rpm) =800 ~ 1,500 cps.
Particle Size =0.2 - 0.5 microns `
` Film = Clear, continuous ~ ;;;
Crosslinkability~
; 30 The thermosetting composition of Example 20 gave films with ~he ` ~`
'':' : :, , ~., ,
.: ` ' .
:, ~
., :

i4~Z7
following properties: ?
: Pencil hardne~s = H - 2H
MEK extractibles = 12 - 17%
EXAMPLE 29.
: The intermediate of Example 1 was copolymerized with acrylic
monomersJ using identical equipment and conditions to those of Example 20,
except for the following changes:
Monomer Blend:
Methyl methacrylate 300
Butyl acrylate 240
. .
Acrylic acid 50
Intermediate of Example 1 100 :;
Aqueous Phase:
Water 540 g.
.~ Nonionic surfactants 18 g. `~
Anionic surfactants 42 g. ,, ~,
. The reaction temperature was held at 68-70C. The resulting emuls- ~;
ion polymer showed the following properties~
: Polymer content C% N.V.) = 47.5
Viscosity = 500 cps.
pH = 7-5
~ Particle size =0.1 - 0.2 microns
.~ Film =Clear, continuous
j ~ . . .
~ Free monomer = 0.5%
; ~:
~ Crosslinka~ility~
.' The thermosetting composition of Example 20 gave films with the :.
following properties:
Pencil hardness = H .~
MEK extractibles = 20% . ;:
~ 16 ~ ,
. ~
',' : :

~05~ 7
EX~1PLE 30
Equipment and conditions, werc identîcal to those of Example 29
except that the methyl meth~crylate ~as replaced by styrene, weigh~ by weight.
The resulting 0mulsion polymer showed the following properties:
Polymer content ~% N.V.) = 47.6
Viscosit~ = 700 cps.
pH = 7-5
Particle Size = Q.l - 0.2 microns '~
Film = Clear, continuous
Fre0 Monomer = 0.5%
Crosslinkability: :~
With the thermosetting composition of Example 20.
Pencil hardness = H .,,
MEK extractibles = 18%
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46~7
SUPPLEMENTARY DLSCLOSURE
, ~
In the disclosure of this application are mentioned, in respect of
Examples 11 - 18 and 21 - 28~ summaries of polymer composition properties.
The actual properties of each individual polymer composition obtained were as
summarised in the following tables. :
i TABLE I .
;SOLUTION COPOLYMERS OF EXAMPLES 14 - 18
Intermediate Example Viscosity, Polymer Content Pencil MEK .
used from: No.cps. % HardnessExtractibles :~
Example 2 1115,000 72 2H 10
3 129,000 67 H 15
4 1317,000 67 2H 11 .~ :
: ,: .
t 5 1410,000 67 H 14
;1 6 1518,000 67 3H 8
7 1610,000 68 H 14
8 1713,000 70 2H 12
~. . 9 18 '~
:~'' ' ,. .
-" TABLE II `;~ :~
EMULSION COPOLYMERS OF EXAMPLES 21 ~ 28
Intermediate Example ~iscosity Particle Size Film Pencil MEK
~ used from No._ cps.microns Hardness Extractibl s
- Example 2 211200: 0.3 - 0.4 P H 13 .
3 221500~ 0.2 - 0.4 t H 17 : ;~
i 4 231500~ 0.3 - 0.5 ~ 2H 16
.i 5 241500 :`0.3 - 0.5 ~ H 17
6 251500 0.3 0.5 ~t 2H 12
~ 7 261500 0.3 - 0.5 ~ H 17 :
.~ 8 271000 0.2 - 0.4 H 12
9 281500 ~0.2 - 0.4 H 15 -
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