CA1139031A - Process for the production of aqueous polymer dispersions - Google Patents
Process for the production of aqueous polymer dispersionsInfo
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- CA1139031A CA1139031A CA000335946A CA335946A CA1139031A CA 1139031 A CA1139031 A CA 1139031A CA 000335946 A CA000335946 A CA 000335946A CA 335946 A CA335946 A CA 335946A CA 1139031 A CA1139031 A CA 1139031A
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- weight
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
A PROCESS FOR THE PRODUCTION OF AQUEOUS
POLYMER DISPERSIONS
A process for the production of an aqueous plastics dispersion, which comprises emulsion polymerisation of at least one olelfinically unsaturated polymerisable monomer in the presence of a water-soluble polymerisation initiator comprising an azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidine corresponding to the general formula (I):
(I) in which R and R', which may be the same or different, represent linear or branched alkylene radicals containing from 2 to 4 carbon atoms, and X represents hydrogen or R'-OH-.
Le A 19 058
POLYMER DISPERSIONS
A process for the production of an aqueous plastics dispersion, which comprises emulsion polymerisation of at least one olelfinically unsaturated polymerisable monomer in the presence of a water-soluble polymerisation initiator comprising an azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidine corresponding to the general formula (I):
(I) in which R and R', which may be the same or different, represent linear or branched alkylene radicals containing from 2 to 4 carbon atoms, and X represents hydrogen or R'-OH-.
Le A 19 058
Description
Q~.
This invention relates to a process for the production o~ polymer dis-persions in which new a~o-di-isobutyric acid-(N,N'-hydroxyalkyl)-a~idines or their salts are used as water-soluble polymerisation initiators, and to the use of the polymer dispersions obtained as aqueous coating agents in ccmbination with products corltaining methylol ether groups or in the production of aqueous coating agents.
US Patent No. 2,599,299 describes a process for producing the dihydro-chloride of azo-di~isobutyric acid amidine.
In addition, German Auslegeschrift No. 1,693,164 describes a process for producing acid-free azo-di-isobutyric acid amidine. In this known process~
ho~ever, special precautions have to be taken to ensure that the water-moist pro-duct does not decompose.
The use of these compounds as polymerisation initiators has also been described (cf. US Patent No. 2,599,300~.
However, they have never been adopted for use on a commercial scale both on account of the instability of the initiators themselves and on acc~unt of the corrosion and coagulation problems involved in their use as initiators.
This is attributable above all to the hydrolysis of the free amidine group which leads to ammonia, amide groups and ammonium salts groups:
~ ~ NH -~ R-C ~ H2O ~ 4 R = residue of the initiator molecule.
Although the solubility of the above-mentioned radical formers in water is basically a highly desirable prcperty for polymerisation in aqueous suspensions or emllsions, the appearance of salts freq~lently interferes with the polymerisation reaction. In the case of sensitive emulsions, this can give rise "~ ~
~3~3~
to premature undesirable coagulation of the emulsions. Furthermore, the incorporation o salt-like groups in the polymer also causes problems in man~
cases and can have an e~tremely adverse ef~ect upon the properties of the poly~er.
It has now surprisingly been found that ~le disadvantages reerred to above can be obviated by using the new azo-di-isobutyric acid-(N,N'-hydroxyaIkyl)-amidines corresponding to the formula (I):
HO-R-N ~ , 3 , 3 ~ N-R-OH
C-C-N=N-C-C (I) \
HO-R'-N CH3 CH3 N-R'-OH
X X
in which R and R', which may be the same or different, represent linear or branched alkyle~e radicals oontaining from 2 to 4 carbon atoms, and X rep~esents hy~rogen or -R'-OHt as polymerisation initiators. In additicn, polymers having very special and desixable pxopexties through incorporation of the hydrophilic hydroxyalkyl groups are obtained.
In the formula (I), R and Rl preferably represent linear or branched alkylene radicals containlng 2 or 3 carbon atams such as -C~I2-CH2--; -CH2-C12-C~2-or C~I3 and X represents hydrogen or R'-OH.
CH --CH--More particularl~, R and R' in the formula (I) are the same and repre-sent a linear alkylene ra~ical containing 2 car~on atoms (= ethylene radical) whilst X represents hydrcgen or a ~-hydroxyethyl radical.
m e present invention relates to the use of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines corresponding to the formula (I) above as radical )3~
formers in the polymerisation of unsaturated ccmpounds and/or in the crosslink-ing of polyunsaturated polymerisable co~pounds.
The azo-di-isobutyric acid-~N,N'-bis-hydroxyalkyl)-amidines and azo-di-isobutyric acid-(N,N'-tris-hydroxyaIkyl)-amidines used according to the inven-tion may be produced by A) reacting azo-di-isobutyric acid amidine unsubstituted on th~ N-atoms, or the amidine substituted on the N-atoms by 1 -to 5 hydroxyalkyl radicals containing from 2 to 4 carbon atoms, with alkylene oxides (C2 C4), or B) rea~ting azo-di-isobutyric acid iminoalkyl ethers corresponding to the general formula (II) below with monoalkanolamines or with mLXture of manoaIkanolamines and dialkanolamines.
~ C-C-N=N-C-C ~ (II) In the formula (II), R represents lower alkyl radicals co.ntaining -from 1 to 4 carbo.n atoms.
The reaction of azo-di-isobutyric acid imincmethyl ether with mono-ethanolamine [reaction scheme (IIIa)] and ~he reaction of azo-di-.isobutyric acid iminoethyl ether with a mixture of mono- and di-ethanok~mm e ~reaction sche~.e (IIIb)] are shown by way of example in the following equations:
~f i 3~
( IIIa) HN CH CH NH
~, 3 , C-C-N=N-C-C ~ 4 N~I2 C~2 C~2 0~1 CH30 CH3 CX3 OC~3 HO-C~2~CH2-N~ I 1 3 N-CH -CE -OH
7 C-N=N C-C ~ 2 2 ~ 2 NH3 + 2 CH30H
H-C~2 C~ -N CH3 CH3 -CH2-CH2-OH
.
( IIIb ) I ~ ,C~I2- CE~ OH
~ C-C-N=N-C-C ~ , 2 NH -CE -CH -OH + 2 E~N
C2H5-O IH 1~ C2~I5 2 2 2 CH2-CH2-OH
CH CH
HO- C~l2- CH2-N I ~ ; N- CH~- CH~- OH
~ C-C-N=N C-C \ ~ 2 NH3 ~ 2 C H -OH
H-CH2-CH2-N I~I3 IH N\ CH2 CH2 OH 2 5 CH2 CH2 C~12-CH2-OH
lt is readily possible t,o produce azo-di-isobutyric acid-(N,N'-bis- or ~,N'-tris-hydro~yalkyl)-amidines by initially subjecting azo-di-isobutyric acid amidine to a partial reaction with an alkylene oxide, followed by condensation with a mono- and/or di~al~anolamine up to the required clegree o~ substitution, or vice versa~ On the other hand, the imino groups of the azo-di-isobutyric acid iminoalkyl ether may initially be co~pletely or partly reac-ted with an alkylene o~ide ancd the alkyl ether gro-ups and residual imino groups; i~ any, subsequerltly Le A 19 05B
condensed with a mono- and/or di-alkanolamine to -~orm the N,N'-~is-(hydroxyalkyl)- or N,N',N'-tris-(hydroxy-alkyl)amidine o~ azo-di-isobutyric acid.
The azo-di-isobutyric acid-(N,N'-bis- or N7N',N7-tris-hydroxyalkyl)-amidines are preferably obtained by reacting azo-di~isobutyrio acid iminoalkyl ether with mnnoalkanolamines or with mixtures o~ monoalkanolamines an.d dialka~olamines (molar ratio 1:1).
The addition reaction with the alkylene o~ides and the condensation reaction with mono- and/or dialkanol~
am.ine is carried out at 0 to 50~ and preferably at 20 t~ 45C. The reactions may be carried out in the absence of solvents or in the presence of organic solvents which are inert to the reactants under the reaction conditions, ~or e~ample in alcohols such as methanol or ethanol; in ethers such as diethyl ether or dioæane; in ketones such as acetone or ethylmethyl ketone; and also in aliphatic or aromatic hydrocarbons.
The reactions may be carried out in the absence of applied pressure or under pressures of up to 50 bars.
Suitable alkylene oxides are ethylene oxide, propylene oxide, 1,2-epo~y butane, 2,3-epoxy butane and 1,2-epoxy-2-methyl propane, pre~erably e-thylene oxide and propylene oxiae and, more particularly~
et]lylene oxide.
The ~ollowing amines may be used for the reaction wiGh the iminoalkyl ethers: ethanolamine, diethanolamine, l-amino-2 propanol, bis-(2-hydroxypropyl)-amine, 1-amino-3-propanol, bis-(3-hydroxypropyl)-amine, isopro-3o panolamine, diisopropanolamine, 1-amino-4-bu~anol, bis-(4--hydro~ybutyl)-amine, 1-amino-3 butanol, bis-(3-hydroxybutyl)-amine, l-amino-2-butanol, bis-(2-hydroæy-butyl~ amine, l-amino-2-methyl-2-propanol, bis-(2-hydroxy~
This invention relates to a process for the production o~ polymer dis-persions in which new a~o-di-isobutyric acid-(N,N'-hydroxyalkyl)-a~idines or their salts are used as water-soluble polymerisation initiators, and to the use of the polymer dispersions obtained as aqueous coating agents in ccmbination with products corltaining methylol ether groups or in the production of aqueous coating agents.
US Patent No. 2,599,299 describes a process for producing the dihydro-chloride of azo-di~isobutyric acid amidine.
In addition, German Auslegeschrift No. 1,693,164 describes a process for producing acid-free azo-di-isobutyric acid amidine. In this known process~
ho~ever, special precautions have to be taken to ensure that the water-moist pro-duct does not decompose.
The use of these compounds as polymerisation initiators has also been described (cf. US Patent No. 2,599,300~.
However, they have never been adopted for use on a commercial scale both on account of the instability of the initiators themselves and on acc~unt of the corrosion and coagulation problems involved in their use as initiators.
This is attributable above all to the hydrolysis of the free amidine group which leads to ammonia, amide groups and ammonium salts groups:
~ ~ NH -~ R-C ~ H2O ~ 4 R = residue of the initiator molecule.
Although the solubility of the above-mentioned radical formers in water is basically a highly desirable prcperty for polymerisation in aqueous suspensions or emllsions, the appearance of salts freq~lently interferes with the polymerisation reaction. In the case of sensitive emulsions, this can give rise "~ ~
~3~3~
to premature undesirable coagulation of the emulsions. Furthermore, the incorporation o salt-like groups in the polymer also causes problems in man~
cases and can have an e~tremely adverse ef~ect upon the properties of the poly~er.
It has now surprisingly been found that ~le disadvantages reerred to above can be obviated by using the new azo-di-isobutyric acid-(N,N'-hydroxyaIkyl)-amidines corresponding to the formula (I):
HO-R-N ~ , 3 , 3 ~ N-R-OH
C-C-N=N-C-C (I) \
HO-R'-N CH3 CH3 N-R'-OH
X X
in which R and R', which may be the same or different, represent linear or branched alkyle~e radicals oontaining from 2 to 4 carbon atoms, and X rep~esents hy~rogen or -R'-OHt as polymerisation initiators. In additicn, polymers having very special and desixable pxopexties through incorporation of the hydrophilic hydroxyalkyl groups are obtained.
In the formula (I), R and Rl preferably represent linear or branched alkylene radicals containlng 2 or 3 carbon atams such as -C~I2-CH2--; -CH2-C12-C~2-or C~I3 and X represents hydrogen or R'-OH.
CH --CH--More particularl~, R and R' in the formula (I) are the same and repre-sent a linear alkylene ra~ical containing 2 car~on atoms (= ethylene radical) whilst X represents hydrcgen or a ~-hydroxyethyl radical.
m e present invention relates to the use of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines corresponding to the formula (I) above as radical )3~
formers in the polymerisation of unsaturated ccmpounds and/or in the crosslink-ing of polyunsaturated polymerisable co~pounds.
The azo-di-isobutyric acid-~N,N'-bis-hydroxyalkyl)-amidines and azo-di-isobutyric acid-(N,N'-tris-hydroxyaIkyl)-amidines used according to the inven-tion may be produced by A) reacting azo-di-isobutyric acid amidine unsubstituted on th~ N-atoms, or the amidine substituted on the N-atoms by 1 -to 5 hydroxyalkyl radicals containing from 2 to 4 carbon atoms, with alkylene oxides (C2 C4), or B) rea~ting azo-di-isobutyric acid iminoalkyl ethers corresponding to the general formula (II) below with monoalkanolamines or with mLXture of manoaIkanolamines and dialkanolamines.
~ C-C-N=N-C-C ~ (II) In the formula (II), R represents lower alkyl radicals co.ntaining -from 1 to 4 carbo.n atoms.
The reaction of azo-di-isobutyric acid imincmethyl ether with mono-ethanolamine [reaction scheme (IIIa)] and ~he reaction of azo-di-.isobutyric acid iminoethyl ether with a mixture of mono- and di-ethanok~mm e ~reaction sche~.e (IIIb)] are shown by way of example in the following equations:
~f i 3~
( IIIa) HN CH CH NH
~, 3 , C-C-N=N-C-C ~ 4 N~I2 C~2 C~2 0~1 CH30 CH3 CX3 OC~3 HO-C~2~CH2-N~ I 1 3 N-CH -CE -OH
7 C-N=N C-C ~ 2 2 ~ 2 NH3 + 2 CH30H
H-C~2 C~ -N CH3 CH3 -CH2-CH2-OH
.
( IIIb ) I ~ ,C~I2- CE~ OH
~ C-C-N=N-C-C ~ , 2 NH -CE -CH -OH + 2 E~N
C2H5-O IH 1~ C2~I5 2 2 2 CH2-CH2-OH
CH CH
HO- C~l2- CH2-N I ~ ; N- CH~- CH~- OH
~ C-C-N=N C-C \ ~ 2 NH3 ~ 2 C H -OH
H-CH2-CH2-N I~I3 IH N\ CH2 CH2 OH 2 5 CH2 CH2 C~12-CH2-OH
lt is readily possible t,o produce azo-di-isobutyric acid-(N,N'-bis- or ~,N'-tris-hydro~yalkyl)-amidines by initially subjecting azo-di-isobutyric acid amidine to a partial reaction with an alkylene oxide, followed by condensation with a mono- and/or di~al~anolamine up to the required clegree o~ substitution, or vice versa~ On the other hand, the imino groups of the azo-di-isobutyric acid iminoalkyl ether may initially be co~pletely or partly reac-ted with an alkylene o~ide ancd the alkyl ether gro-ups and residual imino groups; i~ any, subsequerltly Le A 19 05B
condensed with a mono- and/or di-alkanolamine to -~orm the N,N'-~is-(hydroxyalkyl)- or N,N',N'-tris-(hydroxy-alkyl)amidine o~ azo-di-isobutyric acid.
The azo-di-isobutyric acid-(N,N'-bis- or N7N',N7-tris-hydroxyalkyl)-amidines are preferably obtained by reacting azo-di~isobutyrio acid iminoalkyl ether with mnnoalkanolamines or with mixtures o~ monoalkanolamines an.d dialka~olamines (molar ratio 1:1).
The addition reaction with the alkylene o~ides and the condensation reaction with mono- and/or dialkanol~
am.ine is carried out at 0 to 50~ and preferably at 20 t~ 45C. The reactions may be carried out in the absence of solvents or in the presence of organic solvents which are inert to the reactants under the reaction conditions, ~or e~ample in alcohols such as methanol or ethanol; in ethers such as diethyl ether or dioæane; in ketones such as acetone or ethylmethyl ketone; and also in aliphatic or aromatic hydrocarbons.
The reactions may be carried out in the absence of applied pressure or under pressures of up to 50 bars.
Suitable alkylene oxides are ethylene oxide, propylene oxide, 1,2-epo~y butane, 2,3-epoxy butane and 1,2-epoxy-2-methyl propane, pre~erably e-thylene oxide and propylene oxiae and, more particularly~
et]lylene oxide.
The ~ollowing amines may be used for the reaction wiGh the iminoalkyl ethers: ethanolamine, diethanolamine, l-amino-2 propanol, bis-(2-hydroxypropyl)-amine, 1-amino-3-propanol, bis-(3-hydroxypropyl)-amine, isopro-3o panolamine, diisopropanolamine, 1-amino-4-bu~anol, bis-(4--hydro~ybutyl)-amine, 1-amino-3 butanol, bis-(3-hydroxybutyl)-amine, l-amino-2-butanol, bis-(2-hydroæy-butyl~ amine, l-amino-2-methyl-2-propanol, bis-(2-hydroxy~
2-methyl-propyl)-amine~ 2-amino-2-methyl l propanol, bis-Le A 19 058 ~.
~L~3~
t~ono-hYdroxy tert.-butyl)-amine, l-amino-2-~ethyl-3-propanol and bis-(3-hydroxy-2-methylpropyl)-amine or mL~tures of the above-men-tioned amines.
It is preferred to use ethanolam m e, diethanolamune, l-amino 2-pro-panol, bis-(2-hydroxypropyl)-amlne, 1-amino-3-propanol, bis-(3-hydroxypropyl)-am me, isopropanolamine, diisopropanolamine or mixtures -~hereof; ethanolamine or diethanolamine or mlxtures thereof are particularly preferred.
me alkylene oxides are preferably used in such quan-tities that approxImately 1 mole of alkylene oxide is present per ~mo group of the amidines or iminoethers and approximately 2 moles of alkylene oxide per amino group of the ~midines. m e alkanolamines and diaIkanolamines are preferably used in a quantity of 1 mole per imino, amino or alkylether group of the amidines or iminoethers.
The reaction of iminoaIkyl ethers with amines to form amidines is known in principle from the literature (cf. Methoden der organischen Ch~mie, Houben-Weyl, 4th Edition ~1952), Vol. 8r page 703); the hydroxyalkylation of amidines with alkylene oxides is also kncwn (cf. US Patent Nc. 2,980,554, column3, lines 41 to 43).
Th~ production of the azo-di-isobutyric acid iminoalkyl ethers used as starting materials is also known from the literature and may be carried out~ forexample, by the process according to GQrman Offenlegungschrift No. 2,242,520 (pages 31 to 32).
me following are mentioned as examples of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines pro~uced by the cited processes:
azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine, azo-di-isobutyric acid-(N,N'-bis~3-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N,N'-bis-2-hydrDxypropyl)-amidine, azo-di-isobutyric acid-(N-2-hydroxyethyl-N'-3-hy~roxypropyl)-amidine, .
~.3~
azo-di-isobutyric acid-(N-2-hydroxyethyl-N'-2-h~droxyprcpyl)-~midine, azo-di-isobutyric ad d-(N,N'-bis-3-hydroxybutyl)-amidine, azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine, azo-di-isobutyric acid-(N,N',N'-tris-3-hydroxypropyl)-amidine, azo~di-isobutyric acid-(N,N',N'-tris-2-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N-2-hydroxyethyl-N',N'-bis-3-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N-2-~lydroxyethyl-N',N'-bis-2-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N-3-hydroxypropyl-N',N'-bis 2-hydroxyethyl)-amidine, and azo-di-isobutyric acid-(N-2-hydro~ypropyl-N',N'-bis-2-hydroxyethyl)-amidine.
The azo-di-isobutyric a~id-(N,N'-hydroxyalkyl~-amidines are obtained in a smooth high-yield reaction under the above-mentioned reaction conditions and are water-soluble, yellcw to yellow-orange oils. m ey may be used as radical formers in the polymerisation of unsaturated compounds. They may also be used in the crosslinking of, or in crosslinking pro oesses involving, unsatur-ated ccmpoun~s or prcducts, optionally with foaming. They are also suitable for use as blcwing agents in the production of foams.
me use of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines in the production of aqueous polymer dispersions is described in the following and in Examples 7 to 19.
Polymer dispersions are frequently prepared for use as coating mate-rials or, in ccmbination with pigments and fillers, as coatings for wof~d, metals, ceramics, plastics materials and the like. If the coatings are to adhere firmly to the substrate, even in a moist atmosphere or in the presence of water, the content of water-soluble salts in a polymer film has to be as lcw as possible.
m e salts not only impair the adhesion of the films to the slibstate, but they also pramote separation of the film from the surface. 1~is is part-icularly critical when the polymer is hard and substantially non-tac~y. In this .~
.3~ a.;~
case, small quantities of salts have a particularly serious affect upon the ooalescence of the latex particles. In the presence of water, the salts passing into solution build up osmotie pressures at the diffusion interfac~s of the latex partieles which can give rise to chaLking of the binder and can cause it to soften to the point where it dissolves.
~ ccordingly, it has been proposed to earry out polymerisation with hydrogen peroxide or with water-soluble, non-salt-like derivatives of perhydrDl, sueh as tert.-butyl hydroperoxide. However, the latices obtained in this wav show very poor ion and shear stability. In addition, it has frequen-tly been reccmmended to carry out polymerisation with very small quantities of per-sulphates. Unfortunately, this leads to substantially non-reprodueible latices which, in some cases, ean completely coagulate.
It has now been found that polymer dispersions ean be obtained without the æ sistance of inorganie salts whieh adversely affect the adhesion and resist-ance to water of the polymers, providing azo-di-isobutyric acid-(N,N'-hydro~yalkyl)-amidines corresponding to th~
~ormula (I) above are used a~ polymerisation initiators instea~ of the usual alkali metal or ammonium per~
sulphates or other salt-like peroxy compounds.
These amidines are a valuable addition to thc already known water solubl~ a,a'-a~o (~-methyl-y-sulpho)-butyric acid dinitrile (IV) (c~. German Auslegeschri~t No. 1,111,395j, to the azodinitrile~ o~
the a,a~-azo-(a-methyl-r-diethylamino)-butyric acid dinitrile type (V) (cf. US Patent No. 2,605,~60) and o.
the ~ y'-azo-(~-cyano)-valeric acid = ~,a'-azo (~
meth~l y-sulpho)-butyric acid dinitrile typs (VI) ~c~
US Patent No. 2,520,338) or, ~inally, to the 2,2'-a~o (2-methyl-propion-amidine), (VII), (cf. US Patents hro~i.
2~599,299 and 2~599,300).
H03S-CX2~CH2-C_N=N_C_cH2_cH2_so3H (I~) C--N C-N
C2H5 ~ , 3 , 2 f 2~5 ~ H2 CH2-c~N=N-c-c~I2-cH2-N
C2H5 C-N C_N C2.H5 , 3 , 3 E00C-CH2-CH2_C_N=N_,C_GH2~cH2 (VI) C_N C_N
HN ~H
_ _ ' ~ (VII) C-C-N=N-C-C \
~I2N 3 3 N~2 ~!~ .
The amidines corresponding to the formula (VII~
are generally used in the form of hydrochloric acid salts (cf. US Patent No. 2,599,300). However, they have ~ -to be used in ice-cooled form in order to a~oid undesir-able decomposition and hydrolysis (cf. the example of the production of a polyethylene latex with the amidine of an azodinitrile in: Houben-Weyl, Methoden der Organischen Chemie, 4th Edition, Vol. XIV/l (1961), pages 222 et seq). However, chloride io~s are particularly troublesome in a latex intended for corrosion prevention, because they accelerate rust formation to a considerable e~tent. In addition, the amidines of the formula (VII) can only develop a favourable e~fect in a neutral or acid mi~ture.
By contrast, the initiators~~use~ acc_rding to_the invention corresponding to the formula (I) above are stable in a~ueous solution at room temperature. They are active both in acid and in alkaline medium and are highly soluble in water.
The compounds of the formula (VI) are only soluble in an alkaline or neutral medium and are unsuitable for monomers which are to be polymerised in an acid or midly acid medium.
The initiators according to -the invention have a major advantage over the compounds corresponding to the formula (V), i.e. they contain in the molecule free OH-groups which are incorporated at the beginning and end of a polymer chain. These OH-groups provide ~or improved adhesion~ are accessible as reactive groups ~or crosslinking reactions and are desirable ~or numerous applicationsO
Although the compounds corresponding to the formula (IV) give stable latices, the sulpho groups which they introduce into the polymer adversely affect the resistance Le A 19 05~ -to Water of the ~ilms obtam able from dispersions ~uch as these.
In addition, the acid groups of the initiabors corresponding to the formula (IV) have to be buffered with bases so that, ultimately, they do not have any particular advantages over the potassium or ammonium persulphate normally used.
m e initiators used according to the mvention corresponding to the formula (I) ~ay be used m alkaline medium ~nd also in acid medium.
Even when used in small quantities/ they lead to high ~ields of polymer, as can be seen from the Examples.
It has proved to be particularly advantageous to use the initiators correspondiny to the formula (I) in the form of salts or adducts of polymerisable ad ds. This measure enables polymerisation to be carried out at any pH-values in the range of from about 3 to 9.
Examples of suitable polymerisable acids are saturated and mono-olefinically unsaturated sulphonic and carboxylic acids particularly ~hcse containing from 3 to 5 carbon atoms, such as acrylic acid, meth-acrylic acid, crotonic acid, maleic acid and itaoonic acid. It is also possible to use semiesters of maleic acid, itaconic acid and fumaric acid containing from 1 to 18 car~on atoms in the alcohol component.
Vinyl sulphonic acid, methallyl sulphonic acid or 2-N-acrylam~do-2-methyl propane sulphonic acid may also be used ~or adjus-ting the pH-value in cases where the electrolyte stability of the dispersions is of primary importance.
Finally, the alkaline reaction of the initiators correspond m g to the formula (I) may also be reduced by additions of alk~l sulphonic acids and/or alkylaryl sulphonic acids, in which case salts with emulsifier properties are formed. Aliphatic m~nocarboxylic acids may also be used with advantage.
~3~ 3~
Polymerisation with the initiators cor~espcnding to the ~ormwla (I) is preferably carried out at tJ3mperatures in the range of frcm 50 to 90C and, m~re particularly, at tempera-tures of from 50 to 80C, and in the absen oe of applied pressure or under pressures of up to 200 bars.
The initiators may be used in quantities oE frcm 0.2 to 10 % by weight, based on the moncmer total. In general, they are used in quantities of frcm 0.3 to 2 ~ by weight. Where importance is attached to an increased incorporation of hydroxyl groups and to a low molecular weight, correspondingly higher quantities are used.
The initiators may be added in various ways during the polymerisation reaction. The initiator may be added linearly at a rate which just compensates for the decomposition of the initiators at the particular polymerisation tempera-ture applied~ However, the entire quantity of initiator may also be introduced at the outset. Alte m atively, most of the initiator may be kept for the last fractions of monomer. The products obtained dif~er in their molecular weight distribution and in their properties according to the manner in which the initiator is added.
In the case of dispersions which are to be used as binders for the pro-duction of aqueous stoving lacquers, it is favourable, for example, to add most of the OH-group-containing initiators of the formula (I) towards the e~nd of the introduction of the monomers so that polymer fraetions of high molecular weiyht and low in hydroxyl groups are obtained at the beginning of polymerisation~
whereas low molecular weight polymer fractions which improve levelling and gloss and which, by virtue of their higher terminal hydroxyl group content, can be effectively crosslinked ~ith formaldehyde resins are obtained towards the end of polymerisation.
It has now surprisingl~ b~en found that the stability of the polymer i~
dispersions produoed with the initiators according to the invention is extremely good, even when aN onic emulsifiers are used, although the incorporation of cationic groups into a polymer can generally be expected to give rise to floc-culations where anionic emulsifiers are present.
Accordingly, standard anionic, non-ionic or cationic emulsifiers may be added in addition to the polymerisation initiators according to the invention.
Standard cationic, anionic or non-ionic emMlsifiers are described, for example, in Methoden der Organischen Chemie, Houben~Weyl, 4th Edition (1961), Vol. XIV/l, pages 190 - 208 and 4th Edition (1959), Vol. II/2, pages 113 - 138 and in "Surface Active Agents" by A.M. 5chwartz and J.W. Perry, Interscien oe Pulb. Inc., New York, 195B, pages 25 to 171. Ccmbinations of anionic emLlsifiers with non-ionic emulsifiers in a ratio of from 7:3 to 3:7 (molar ratio) or corresponding cQmbinations of cationic emulsifiers ~ith non-ionic emulsifiers are also possi~le.
However, polymerisation may also be carried out in the absen oe of standard emulsifiers in cases where cumpounds which form oligomers with an emulsifier-like effect or which perform a dual function of emulsifier and monomer are used.
Cc~pounds such as these are, for example, alkali metal or ammonium or amine salts of maleic acid semiesters with an alcohol residue containing more than 5 carbon atoms, for example maleic acid cyclohexyl semiester/maleic acid dodecyl semiester saLts. ~k~ever, polymerisation may also be carried out in the absence of emulsifiers using protective colloids, such as polyvinyl alcohol for example.
Suitable polymerisation nomers are any unsaturated m~nomers which can be polymerised in the usual way with æodiisobutyronitrile in nQn-aqueaUs solution, for example, styr~ne, ~-methyl styrene, butadiene, acrylic acid esters '~
~l~3~3~
containing from 1 to 8 carbon atoms in the alcohol component, methacrylic acid esters contaim ng frcm 1 to 8 carbon c~toms in the alcohol component, acryloni-trile, methacrylonitrile, vinyl chloride, vinyl acetate, ethylene chloroprene, etc.
In addi~ion to the above-mentioned m~nomers, water-soluble com~ounds, such as methacrylic acid, acrylic ad d, maleic acid semiester, itaconic acid and itaconic acid semiester; acrylamide, methacrylcl~ide, etc., may also be incorpor-ated in the polymers in smaller quantities. It is also possible to use comonomers still containing functional groups, for example OH-groups or epoxy groups, such ~s ~-hydroxyethyl (meth)acrylate, ~-hydroxypropyl-(meth)acrylate, glycidyl (meth)acrylate and N-methylol- or N-methylol-alkyl ethers of (meth)-acrylic acid amide.
The p~lymer dispersions may be used for a variety of applications.
The way in which the ne~ initiators act is illustrated in Examples 7 to 19, al-though the potential applications of the polymer dispersions ar~ in no way limited by these Examples.
Where the described dispersions are film~forming, they are eminently suitable for coating, particularly for coatings req~lired to show increased anti-corrosion activity, improved behaviour in the salt-spray test, firm adhesion, improved compatibility and crosslinking with products containing methylol or methylol ether groups, for example with aminoplasts, such as melam me-formal-dehyde resins or urea-formaldehyde resins, or with ~henoplasts, such as resols.
In the context of the invention, polymers are understoGd to be hom~-polymers and copolymers. Copolymers are understood to be not only copolymers with copolymerised monomers in statistical distribution or block copolymers, but also graft copolymers in which monomers have been grafted anto a preformEd hom~-polymer or copolymer. Of the copolymers, statistical copolymers are preferred.
~, ~ ~ ~4~ 3'~
m e azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines corresponding to the formula (I) are also eminently suitable for homogeneous phase poly~.erisa-tion pro oe sses kno~n per se, i.e. preferably solution and bulk polymerisation processes. However, polymerisation may also merely begin in homogeneous phase, the polymer accumulating in finely divided form during the polymerisation reac-tion (precipitation polymerisation).
Virtually an~ olefinically unsaturated mono~lers which may be used for p~lymerisation with radical-forming azo ccmpounds are suitable for homopolymerisa-tion and copolymerisation in homogeneous phase~ The following are examples of 10 monomers such as these:
a) ~ Dnoolefins containing from 2 to 8 carbon atoms, such as ethylene, propylene, l-butene, isobutylene and diisobutylene;
b) conjugated diolefins containing frcm 4 to 6 carbon atGms, such as butadiene, isoprene, 2,3-dimethylbutadiene and 2-chlorobutadiene, pre-ferably butadiene;
c) (me.th)acrylic acid, (meth)acrylonitri].e, (meth)acrylamide, alkyl (meth)-acrylates containing from 1 to 18 and preferably from 1 to 8 carbon atoms in the alcohol ca~ponent, such as me-thyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acryl.ate, _-butyl acrylate, -tert.-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the corres-ponding ~.ethacrylic acid alkyl esters preferably -~J
.3~ 3:~
acrylic acid, acrylonitrile, acrylamide, methyl-acrylate~ butyl acrylate, ter-t.-butyl acrylate, 2-ethylhe~yl acrylate and methyl methacrylate; - _ d) vinyl esters of organic monocarboxylic acid3, the acid component containing from 1 to 18 a~d pre-fer- -ably from 2 to 4 carbon atoms, such as vinyl acetate, and vi~yl propionate, pre-~erably vinyl acetate;
e) monoole~inically un~aturated halo~enated hydro-carhons, ~uch as vinyl chlori~e or vinylidene chloride, pre~erably vinyl chloride;
aromatic vinyi compounds, such as styrene, o- or ~-methyl styrene, ~-methyl styrene~ a-methyl p-isopropyl styrene, a-methyl-m-isopropyl s-tyrene and p-chlorostyrene, pre~erably styrene. ~~
In this case, it is pre~erred always to use the less polymerisable monomers~ such as a-methyl-styrene and m- or ~-isopropyl a-methyl styrene, in admi~ture with at least one other o~ the copoly-merisable mo~omers mentioned.
g) Monoesters oY a,~-monoolefinically unsa~urated mono-carboxylic acids containing 3 or 4 carbon atoms with dihydric saturated aliphatic alcohols contain-ing -~rom 2 to ~ carbon atoms, such as 2-hydroxyeth~l methacrylate, 2 hydroxypropyl methacrylate, 4-hydroxy-butyl methac.rylate, 2-hydro~yethyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate~
h) N-methylol ethers of acrylic and methacrylic acid amide corresponding to the general formula:
2 C - C0 - N - CH2 ~ ~2 (YIII) R Rl 3o i~ which . ~
R represents hydrogen or methyl, ~13~
Rl represents hydrogen, alkyl, aralkyl or aryl, and R2 represents alkyl or cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or -~ -cyclohe~yl (cf. German Auslegeschri~t No. 1,035, 363).
It is pre~erred to use the N-methylol methylether o~ methacrylic acid amide. The monomers o~ group h) are used and incorporated into the copolymer in quantities o-f ~rom 1 to 20 ~ by weight, based on the monomer total.
i) Diesters and monoesters of a,~-monoole~inically unsaturated C3-C5-dicarboxylic acids, such as maleic acid, ~umaric acid and itaconic acid with 1 to 18 carbon atoms in the alcohol component, and 7 5 also maleic acid anhydride, maleic or ~umaric acid, amides of maleic and fu~aric acid~ maleic imides and unsaturated copolymerisable polyesters which contain the residues of maleic and/or -~u~aric acid as polymerisable constituents. Maleic acid anhydride 2G is preferred.
j) Vinylalkyl ethers containing from 1 to 4 carbon atoms in the alkyl group, such as vinylmethyl ether, vinyl-ethyl ether, vinylpropyl ether and vinylbutyl ether.
k) Crosslinking monomers containing several unconjugated olefinically unsaturated carbon-carbon bonds, such as divinyl benzene, diallyl phthalate, divinyl adipate, acrylic and/or methacrylic acid allyl ester, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallyl cyanurate, triallyl isocyanurate, triacryloyl -~ perhydroHS-t~iazine, bis-acrylates and bis-methacryl-ates o~ glycols and polyglycols containing ~rom 2 ~o 20 carbon atoms, such as ethylene glycol di(meth) acrylate, propylene glycol di(meth)acrylate, butylene glcyol-1,4-di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris-(meth)acrylates o~ trimethylol ~'3L3t~
propane and glycerol.
~ he crosslinking monomers of group k) are pre~erably used ~or copolymerisation in quantities of Yrom 0.1 to 12 % by weight, based on the monomer total. They are incorporated into the copolymer in the same quantities.
In ~ddJtion, primary, secondary or tertiary amino-alkyl esters o~i (meth)acrylic acid preferably containing ~rom ~ tc 4 carhon atoms in the alkyl group and glycidol-~meth)ac~ylate may also be used as comonomers and may optional~y oe crosslinked through the amino or epo~ide group du;rinc, or a~te!r copolymerisation.
Monomnrs of groups b), c), d), e), f), and i) are preferahly used ~or copolymerisation.
W~lere polymerisation is carried out in solution, water ~nd orGanic sc~lvents, ~or example ~imethyl ~ormamide, ter~.-butanol, chlorobenzenes, etc., may be used as solvents.
The poly~;erisation reaction may be carried out at temperatures o~ ~rom 50C to 90C and preferably at temperatu:r~s c-~ from 55C to 75~C, depending on the decomposition characteristics of the azo compounds according ~o the invention. The quantity in which the initiator is us~d may be adapted to the required molecular weight and may amount to between 0.05 and 10 /0 by weight or more, based on the monomers used~ It is, of course~ also possible to deviate ~rom these ~igures on the quantity o~ inifiator and the temperature. The polymerisation reactions in homogeneous phase may be carried out in the absence oi pressure or under pressure of up to 1500 kars.
In every case, the polymers obtained contain at least 2 hydro~yl groups, emanating ~rom the initiator ~ragments, incorporated at the beginning and end o~ each polymer chain.
Le A 19 058 ~l~ 3~3 'rhe introduction o~ hydroxyl groups at the beginning and end of polymer chains is oE considerable practical importance to a variety o~ propertit~s. On the one hand, ~--the reactivity o~ the poly~ers enables them to be reacted with compounds which generally react with hydro~yl ~roups and ~orm wide--mesh ntatworksO Compounds such as these are, ~r example, polyisocyanates~ polyepo~ides, polycarboxylic acid anhydride, and co~pounds containing mtathylol and/or methylol ether groups~ In addition, the hydro~yl groups considerably improve t~le a~hesion of pol~mer films.
Examples 20 to 27 illustrate bulk and solution polymerisation reactio~ L`.Si~lg the azo~ isobutyric acid-(N,N~-hydroxyalkyl)~a;~idines corresponding to the ~ormula (I).
The parts and percen-tages quoted in the Examples are by weight, unless othtarw~se indicated. 'rhe intrinsic viscosity [~], L dl ] was measured in the solvents indicated at a temperature o~ 25C.
Production of the a~o-di ~
-alkyl)-amidines EXAMPLE 1:
Azo-di-isobutyric acid-~N,N'-~is-2-llydro.Yye-thyl)-amidine:
114 g (0.5 mole) o~ azo-di-isobutyric a~d imino-methyl ether9 300 ml oE methanol and 122 g (2 moles) o~
ethanolamine were stirred ~or 8 hours a-t 50C. 'rO remove methanol and ammonia (1 mo~a)~ the mi~ture was distilled out in a water jet vacuum (12 m~ar) a-t temperatures o~
up to at most 50C, leaving 165 g _ 88.2 /0 o~ the theoretical yield of a yellow-orange, water soluble oil;
3o ~ 1.4880.
Analysis calculated ~or C16I-I~4N604, molecular weight 374:
calculated C: 51.~4 o~b; H: 9.09 7h; N: 22.46 %; 0: 17.11 %
observed C: 51.5 ~O ; H: 9.~ //o; N: 22.8 %; 0: 17.4 %~
~:~ 3~93~
EXPMPLE 2:
Azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine (two stage process):
8.8 g (0.2 mole) of ethylene oxide were introduced while cooling with ice/water at 20 to 30 & into 37.4 g (0.1 mole) of the azo-di-isobutyric acid-(N,N'-bis-hydroxyethyl)-amidine obtained in accordance with F~ample 1. The mix-ture was then stirred for 5 hours at rocm temperature (approximately 25C). A
yellow, viscous, water-soluble oil (n20 1.4910) was obtained in a yield of 46 g or 99 % of the theoretical.
Analysis calculated for C20H42N606, molecular weight 462;
calculated C: 51.95 %; H: 9.09 %; N: 18.18 %; O: 20.78 %
abserved C: 52.2 % ; H: 9.2 % ; N: 18.5 % ; O: 20.4 %O
The same azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine is also obtained by the following process according to Exa~ple 3:
EX~MPLE 3:
Azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine (one-stage process):
45.6 g (0.2 mole) of azo-di-isobutyric acid im m oethyl ether, 200 ml of methanol, 42 g (0.4 mole) of diethanolamine and 26 g (0.4 mole) of ethanolamine were stirred for 8 hours at 50C. To remDve methanol and am~nia (0.4 mole), the mixture was distilled out m vacuo (12 mbar) at temperatures of up to at most 50C, leaving 91 g = 98 % of the theoretical yield of a yellow, viscous, water-soluble oil which had the same refractive index as the oil of the preced-ing Example and was identical therewith.
EXPMPLE 4:
Azo-di-isobutyric acid-(N,N'-bis-2-hydrcxypropyl)-amidine:
57 g (0.25 mole) of azo-di-isobutyric acid iminomethyl ether, 200 ml of methanol and 75 g (1 mole) of 1-amino-2-propanol were heated for B ho~lrs to 50C in a water bath, 0.5 mole of ammonia being released. The mixture was dis-:
~3~3~
tilled at 50 &, first under a pressure of 12 mbar and then under a pressure of 0.1 mbar, in order to re~ve the volatile fractions. A yellcwish wa~er-soluble oil (nD: 1.4691) was left behind as a residue in a quanti-ty of 93 g, corres-ponding to a yield of 87 ~ of the theoretical.
Analysis calcuLated for C20H42N604, mDlecular weight 430:
calcula~ed C: 55.81 %; H: 9.76 %; N: 19.53 %; O: 14.88 %
observed C: 56.1 ~ ; H: 10.0 %; N: 19.7 ~ ; O: 14.7 ~.
If the l-amuno-2-propanol in the above nlxture is replaced by l-amino-
~L~3~
t~ono-hYdroxy tert.-butyl)-amine, l-amino-2-~ethyl-3-propanol and bis-(3-hydroxy-2-methylpropyl)-amine or mL~tures of the above-men-tioned amines.
It is preferred to use ethanolam m e, diethanolamune, l-amino 2-pro-panol, bis-(2-hydroxypropyl)-amlne, 1-amino-3-propanol, bis-(3-hydroxypropyl)-am me, isopropanolamine, diisopropanolamine or mixtures -~hereof; ethanolamine or diethanolamine or mlxtures thereof are particularly preferred.
me alkylene oxides are preferably used in such quan-tities that approxImately 1 mole of alkylene oxide is present per ~mo group of the amidines or iminoethers and approximately 2 moles of alkylene oxide per amino group of the ~midines. m e alkanolamines and diaIkanolamines are preferably used in a quantity of 1 mole per imino, amino or alkylether group of the amidines or iminoethers.
The reaction of iminoaIkyl ethers with amines to form amidines is known in principle from the literature (cf. Methoden der organischen Ch~mie, Houben-Weyl, 4th Edition ~1952), Vol. 8r page 703); the hydroxyalkylation of amidines with alkylene oxides is also kncwn (cf. US Patent Nc. 2,980,554, column3, lines 41 to 43).
Th~ production of the azo-di-isobutyric acid iminoalkyl ethers used as starting materials is also known from the literature and may be carried out~ forexample, by the process according to GQrman Offenlegungschrift No. 2,242,520 (pages 31 to 32).
me following are mentioned as examples of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines pro~uced by the cited processes:
azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine, azo-di-isobutyric acid-(N,N'-bis~3-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N,N'-bis-2-hydrDxypropyl)-amidine, azo-di-isobutyric acid-(N-2-hydroxyethyl-N'-3-hy~roxypropyl)-amidine, .
~.3~
azo-di-isobutyric acid-(N-2-hydroxyethyl-N'-2-h~droxyprcpyl)-~midine, azo-di-isobutyric ad d-(N,N'-bis-3-hydroxybutyl)-amidine, azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine, azo-di-isobutyric acid-(N,N',N'-tris-3-hydroxypropyl)-amidine, azo~di-isobutyric acid-(N,N',N'-tris-2-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N-2-hydroxyethyl-N',N'-bis-3-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N-2-~lydroxyethyl-N',N'-bis-2-hydroxypropyl)-amidine, azo-di-isobutyric acid-(N-3-hydroxypropyl-N',N'-bis 2-hydroxyethyl)-amidine, and azo-di-isobutyric acid-(N-2-hydro~ypropyl-N',N'-bis-2-hydroxyethyl)-amidine.
The azo-di-isobutyric a~id-(N,N'-hydroxyalkyl~-amidines are obtained in a smooth high-yield reaction under the above-mentioned reaction conditions and are water-soluble, yellcw to yellow-orange oils. m ey may be used as radical formers in the polymerisation of unsaturated compounds. They may also be used in the crosslinking of, or in crosslinking pro oesses involving, unsatur-ated ccmpoun~s or prcducts, optionally with foaming. They are also suitable for use as blcwing agents in the production of foams.
me use of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines in the production of aqueous polymer dispersions is described in the following and in Examples 7 to 19.
Polymer dispersions are frequently prepared for use as coating mate-rials or, in ccmbination with pigments and fillers, as coatings for wof~d, metals, ceramics, plastics materials and the like. If the coatings are to adhere firmly to the substrate, even in a moist atmosphere or in the presence of water, the content of water-soluble salts in a polymer film has to be as lcw as possible.
m e salts not only impair the adhesion of the films to the slibstate, but they also pramote separation of the film from the surface. 1~is is part-icularly critical when the polymer is hard and substantially non-tac~y. In this .~
.3~ a.;~
case, small quantities of salts have a particularly serious affect upon the ooalescence of the latex particles. In the presence of water, the salts passing into solution build up osmotie pressures at the diffusion interfac~s of the latex partieles which can give rise to chaLking of the binder and can cause it to soften to the point where it dissolves.
~ ccordingly, it has been proposed to earry out polymerisation with hydrogen peroxide or with water-soluble, non-salt-like derivatives of perhydrDl, sueh as tert.-butyl hydroperoxide. However, the latices obtained in this wav show very poor ion and shear stability. In addition, it has frequen-tly been reccmmended to carry out polymerisation with very small quantities of per-sulphates. Unfortunately, this leads to substantially non-reprodueible latices which, in some cases, ean completely coagulate.
It has now been found that polymer dispersions ean be obtained without the æ sistance of inorganie salts whieh adversely affect the adhesion and resist-ance to water of the polymers, providing azo-di-isobutyric acid-(N,N'-hydro~yalkyl)-amidines corresponding to th~
~ormula (I) above are used a~ polymerisation initiators instea~ of the usual alkali metal or ammonium per~
sulphates or other salt-like peroxy compounds.
These amidines are a valuable addition to thc already known water solubl~ a,a'-a~o (~-methyl-y-sulpho)-butyric acid dinitrile (IV) (c~. German Auslegeschri~t No. 1,111,395j, to the azodinitrile~ o~
the a,a~-azo-(a-methyl-r-diethylamino)-butyric acid dinitrile type (V) (cf. US Patent No. 2,605,~60) and o.
the ~ y'-azo-(~-cyano)-valeric acid = ~,a'-azo (~
meth~l y-sulpho)-butyric acid dinitrile typs (VI) ~c~
US Patent No. 2,520,338) or, ~inally, to the 2,2'-a~o (2-methyl-propion-amidine), (VII), (cf. US Patents hro~i.
2~599,299 and 2~599,300).
H03S-CX2~CH2-C_N=N_C_cH2_cH2_so3H (I~) C--N C-N
C2H5 ~ , 3 , 2 f 2~5 ~ H2 CH2-c~N=N-c-c~I2-cH2-N
C2H5 C-N C_N C2.H5 , 3 , 3 E00C-CH2-CH2_C_N=N_,C_GH2~cH2 (VI) C_N C_N
HN ~H
_ _ ' ~ (VII) C-C-N=N-C-C \
~I2N 3 3 N~2 ~!~ .
The amidines corresponding to the formula (VII~
are generally used in the form of hydrochloric acid salts (cf. US Patent No. 2,599,300). However, they have ~ -to be used in ice-cooled form in order to a~oid undesir-able decomposition and hydrolysis (cf. the example of the production of a polyethylene latex with the amidine of an azodinitrile in: Houben-Weyl, Methoden der Organischen Chemie, 4th Edition, Vol. XIV/l (1961), pages 222 et seq). However, chloride io~s are particularly troublesome in a latex intended for corrosion prevention, because they accelerate rust formation to a considerable e~tent. In addition, the amidines of the formula (VII) can only develop a favourable e~fect in a neutral or acid mi~ture.
By contrast, the initiators~~use~ acc_rding to_the invention corresponding to the formula (I) above are stable in a~ueous solution at room temperature. They are active both in acid and in alkaline medium and are highly soluble in water.
The compounds of the formula (VI) are only soluble in an alkaline or neutral medium and are unsuitable for monomers which are to be polymerised in an acid or midly acid medium.
The initiators according to -the invention have a major advantage over the compounds corresponding to the formula (V), i.e. they contain in the molecule free OH-groups which are incorporated at the beginning and end of a polymer chain. These OH-groups provide ~or improved adhesion~ are accessible as reactive groups ~or crosslinking reactions and are desirable ~or numerous applicationsO
Although the compounds corresponding to the formula (IV) give stable latices, the sulpho groups which they introduce into the polymer adversely affect the resistance Le A 19 05~ -to Water of the ~ilms obtam able from dispersions ~uch as these.
In addition, the acid groups of the initiabors corresponding to the formula (IV) have to be buffered with bases so that, ultimately, they do not have any particular advantages over the potassium or ammonium persulphate normally used.
m e initiators used according to the mvention corresponding to the formula (I) ~ay be used m alkaline medium ~nd also in acid medium.
Even when used in small quantities/ they lead to high ~ields of polymer, as can be seen from the Examples.
It has proved to be particularly advantageous to use the initiators correspondiny to the formula (I) in the form of salts or adducts of polymerisable ad ds. This measure enables polymerisation to be carried out at any pH-values in the range of from about 3 to 9.
Examples of suitable polymerisable acids are saturated and mono-olefinically unsaturated sulphonic and carboxylic acids particularly ~hcse containing from 3 to 5 carbon atoms, such as acrylic acid, meth-acrylic acid, crotonic acid, maleic acid and itaoonic acid. It is also possible to use semiesters of maleic acid, itaconic acid and fumaric acid containing from 1 to 18 car~on atoms in the alcohol component.
Vinyl sulphonic acid, methallyl sulphonic acid or 2-N-acrylam~do-2-methyl propane sulphonic acid may also be used ~or adjus-ting the pH-value in cases where the electrolyte stability of the dispersions is of primary importance.
Finally, the alkaline reaction of the initiators correspond m g to the formula (I) may also be reduced by additions of alk~l sulphonic acids and/or alkylaryl sulphonic acids, in which case salts with emulsifier properties are formed. Aliphatic m~nocarboxylic acids may also be used with advantage.
~3~ 3~
Polymerisation with the initiators cor~espcnding to the ~ormwla (I) is preferably carried out at tJ3mperatures in the range of frcm 50 to 90C and, m~re particularly, at tempera-tures of from 50 to 80C, and in the absen oe of applied pressure or under pressures of up to 200 bars.
The initiators may be used in quantities oE frcm 0.2 to 10 % by weight, based on the moncmer total. In general, they are used in quantities of frcm 0.3 to 2 ~ by weight. Where importance is attached to an increased incorporation of hydroxyl groups and to a low molecular weight, correspondingly higher quantities are used.
The initiators may be added in various ways during the polymerisation reaction. The initiator may be added linearly at a rate which just compensates for the decomposition of the initiators at the particular polymerisation tempera-ture applied~ However, the entire quantity of initiator may also be introduced at the outset. Alte m atively, most of the initiator may be kept for the last fractions of monomer. The products obtained dif~er in their molecular weight distribution and in their properties according to the manner in which the initiator is added.
In the case of dispersions which are to be used as binders for the pro-duction of aqueous stoving lacquers, it is favourable, for example, to add most of the OH-group-containing initiators of the formula (I) towards the e~nd of the introduction of the monomers so that polymer fraetions of high molecular weiyht and low in hydroxyl groups are obtained at the beginning of polymerisation~
whereas low molecular weight polymer fractions which improve levelling and gloss and which, by virtue of their higher terminal hydroxyl group content, can be effectively crosslinked ~ith formaldehyde resins are obtained towards the end of polymerisation.
It has now surprisingl~ b~en found that the stability of the polymer i~
dispersions produoed with the initiators according to the invention is extremely good, even when aN onic emulsifiers are used, although the incorporation of cationic groups into a polymer can generally be expected to give rise to floc-culations where anionic emulsifiers are present.
Accordingly, standard anionic, non-ionic or cationic emulsifiers may be added in addition to the polymerisation initiators according to the invention.
Standard cationic, anionic or non-ionic emMlsifiers are described, for example, in Methoden der Organischen Chemie, Houben~Weyl, 4th Edition (1961), Vol. XIV/l, pages 190 - 208 and 4th Edition (1959), Vol. II/2, pages 113 - 138 and in "Surface Active Agents" by A.M. 5chwartz and J.W. Perry, Interscien oe Pulb. Inc., New York, 195B, pages 25 to 171. Ccmbinations of anionic emLlsifiers with non-ionic emulsifiers in a ratio of from 7:3 to 3:7 (molar ratio) or corresponding cQmbinations of cationic emulsifiers ~ith non-ionic emulsifiers are also possi~le.
However, polymerisation may also be carried out in the absen oe of standard emulsifiers in cases where cumpounds which form oligomers with an emulsifier-like effect or which perform a dual function of emulsifier and monomer are used.
Cc~pounds such as these are, for example, alkali metal or ammonium or amine salts of maleic acid semiesters with an alcohol residue containing more than 5 carbon atoms, for example maleic acid cyclohexyl semiester/maleic acid dodecyl semiester saLts. ~k~ever, polymerisation may also be carried out in the absence of emulsifiers using protective colloids, such as polyvinyl alcohol for example.
Suitable polymerisation nomers are any unsaturated m~nomers which can be polymerised in the usual way with æodiisobutyronitrile in nQn-aqueaUs solution, for example, styr~ne, ~-methyl styrene, butadiene, acrylic acid esters '~
~l~3~3~
containing from 1 to 8 carbon atoms in the alcohol component, methacrylic acid esters contaim ng frcm 1 to 8 carbon c~toms in the alcohol component, acryloni-trile, methacrylonitrile, vinyl chloride, vinyl acetate, ethylene chloroprene, etc.
In addi~ion to the above-mentioned m~nomers, water-soluble com~ounds, such as methacrylic acid, acrylic ad d, maleic acid semiester, itaconic acid and itaconic acid semiester; acrylamide, methacrylcl~ide, etc., may also be incorpor-ated in the polymers in smaller quantities. It is also possible to use comonomers still containing functional groups, for example OH-groups or epoxy groups, such ~s ~-hydroxyethyl (meth)acrylate, ~-hydroxypropyl-(meth)acrylate, glycidyl (meth)acrylate and N-methylol- or N-methylol-alkyl ethers of (meth)-acrylic acid amide.
The p~lymer dispersions may be used for a variety of applications.
The way in which the ne~ initiators act is illustrated in Examples 7 to 19, al-though the potential applications of the polymer dispersions ar~ in no way limited by these Examples.
Where the described dispersions are film~forming, they are eminently suitable for coating, particularly for coatings req~lired to show increased anti-corrosion activity, improved behaviour in the salt-spray test, firm adhesion, improved compatibility and crosslinking with products containing methylol or methylol ether groups, for example with aminoplasts, such as melam me-formal-dehyde resins or urea-formaldehyde resins, or with ~henoplasts, such as resols.
In the context of the invention, polymers are understoGd to be hom~-polymers and copolymers. Copolymers are understood to be not only copolymers with copolymerised monomers in statistical distribution or block copolymers, but also graft copolymers in which monomers have been grafted anto a preformEd hom~-polymer or copolymer. Of the copolymers, statistical copolymers are preferred.
~, ~ ~ ~4~ 3'~
m e azo-di-isobutyric acid-(N,N'-hydroxyalkyl)-amidines corresponding to the formula (I) are also eminently suitable for homogeneous phase poly~.erisa-tion pro oe sses kno~n per se, i.e. preferably solution and bulk polymerisation processes. However, polymerisation may also merely begin in homogeneous phase, the polymer accumulating in finely divided form during the polymerisation reac-tion (precipitation polymerisation).
Virtually an~ olefinically unsaturated mono~lers which may be used for p~lymerisation with radical-forming azo ccmpounds are suitable for homopolymerisa-tion and copolymerisation in homogeneous phase~ The following are examples of 10 monomers such as these:
a) ~ Dnoolefins containing from 2 to 8 carbon atoms, such as ethylene, propylene, l-butene, isobutylene and diisobutylene;
b) conjugated diolefins containing frcm 4 to 6 carbon atGms, such as butadiene, isoprene, 2,3-dimethylbutadiene and 2-chlorobutadiene, pre-ferably butadiene;
c) (me.th)acrylic acid, (meth)acrylonitri].e, (meth)acrylamide, alkyl (meth)-acrylates containing from 1 to 18 and preferably from 1 to 8 carbon atoms in the alcohol ca~ponent, such as me-thyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acryl.ate, _-butyl acrylate, -tert.-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the corres-ponding ~.ethacrylic acid alkyl esters preferably -~J
.3~ 3:~
acrylic acid, acrylonitrile, acrylamide, methyl-acrylate~ butyl acrylate, ter-t.-butyl acrylate, 2-ethylhe~yl acrylate and methyl methacrylate; - _ d) vinyl esters of organic monocarboxylic acid3, the acid component containing from 1 to 18 a~d pre-fer- -ably from 2 to 4 carbon atoms, such as vinyl acetate, and vi~yl propionate, pre-~erably vinyl acetate;
e) monoole~inically un~aturated halo~enated hydro-carhons, ~uch as vinyl chlori~e or vinylidene chloride, pre~erably vinyl chloride;
aromatic vinyi compounds, such as styrene, o- or ~-methyl styrene, ~-methyl styrene~ a-methyl p-isopropyl styrene, a-methyl-m-isopropyl s-tyrene and p-chlorostyrene, pre~erably styrene. ~~
In this case, it is pre~erred always to use the less polymerisable monomers~ such as a-methyl-styrene and m- or ~-isopropyl a-methyl styrene, in admi~ture with at least one other o~ the copoly-merisable mo~omers mentioned.
g) Monoesters oY a,~-monoolefinically unsa~urated mono-carboxylic acids containing 3 or 4 carbon atoms with dihydric saturated aliphatic alcohols contain-ing -~rom 2 to ~ carbon atoms, such as 2-hydroxyeth~l methacrylate, 2 hydroxypropyl methacrylate, 4-hydroxy-butyl methac.rylate, 2-hydro~yethyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate~
h) N-methylol ethers of acrylic and methacrylic acid amide corresponding to the general formula:
2 C - C0 - N - CH2 ~ ~2 (YIII) R Rl 3o i~ which . ~
R represents hydrogen or methyl, ~13~
Rl represents hydrogen, alkyl, aralkyl or aryl, and R2 represents alkyl or cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or -~ -cyclohe~yl (cf. German Auslegeschri~t No. 1,035, 363).
It is pre~erred to use the N-methylol methylether o~ methacrylic acid amide. The monomers o~ group h) are used and incorporated into the copolymer in quantities o-f ~rom 1 to 20 ~ by weight, based on the monomer total.
i) Diesters and monoesters of a,~-monoole~inically unsaturated C3-C5-dicarboxylic acids, such as maleic acid, ~umaric acid and itaconic acid with 1 to 18 carbon atoms in the alcohol component, and 7 5 also maleic acid anhydride, maleic or ~umaric acid, amides of maleic and fu~aric acid~ maleic imides and unsaturated copolymerisable polyesters which contain the residues of maleic and/or -~u~aric acid as polymerisable constituents. Maleic acid anhydride 2G is preferred.
j) Vinylalkyl ethers containing from 1 to 4 carbon atoms in the alkyl group, such as vinylmethyl ether, vinyl-ethyl ether, vinylpropyl ether and vinylbutyl ether.
k) Crosslinking monomers containing several unconjugated olefinically unsaturated carbon-carbon bonds, such as divinyl benzene, diallyl phthalate, divinyl adipate, acrylic and/or methacrylic acid allyl ester, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallyl cyanurate, triallyl isocyanurate, triacryloyl -~ perhydroHS-t~iazine, bis-acrylates and bis-methacryl-ates o~ glycols and polyglycols containing ~rom 2 ~o 20 carbon atoms, such as ethylene glycol di(meth) acrylate, propylene glycol di(meth)acrylate, butylene glcyol-1,4-di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris-(meth)acrylates o~ trimethylol ~'3L3t~
propane and glycerol.
~ he crosslinking monomers of group k) are pre~erably used ~or copolymerisation in quantities of Yrom 0.1 to 12 % by weight, based on the monomer total. They are incorporated into the copolymer in the same quantities.
In ~ddJtion, primary, secondary or tertiary amino-alkyl esters o~i (meth)acrylic acid preferably containing ~rom ~ tc 4 carhon atoms in the alkyl group and glycidol-~meth)ac~ylate may also be used as comonomers and may optional~y oe crosslinked through the amino or epo~ide group du;rinc, or a~te!r copolymerisation.
Monomnrs of groups b), c), d), e), f), and i) are preferahly used ~or copolymerisation.
W~lere polymerisation is carried out in solution, water ~nd orGanic sc~lvents, ~or example ~imethyl ~ormamide, ter~.-butanol, chlorobenzenes, etc., may be used as solvents.
The poly~;erisation reaction may be carried out at temperatures o~ ~rom 50C to 90C and preferably at temperatu:r~s c-~ from 55C to 75~C, depending on the decomposition characteristics of the azo compounds according ~o the invention. The quantity in which the initiator is us~d may be adapted to the required molecular weight and may amount to between 0.05 and 10 /0 by weight or more, based on the monomers used~ It is, of course~ also possible to deviate ~rom these ~igures on the quantity o~ inifiator and the temperature. The polymerisation reactions in homogeneous phase may be carried out in the absence oi pressure or under pressure of up to 1500 kars.
In every case, the polymers obtained contain at least 2 hydro~yl groups, emanating ~rom the initiator ~ragments, incorporated at the beginning and end o~ each polymer chain.
Le A 19 058 ~l~ 3~3 'rhe introduction o~ hydroxyl groups at the beginning and end of polymer chains is oE considerable practical importance to a variety o~ propertit~s. On the one hand, ~--the reactivity o~ the poly~ers enables them to be reacted with compounds which generally react with hydro~yl ~roups and ~orm wide--mesh ntatworksO Compounds such as these are, ~r example, polyisocyanates~ polyepo~ides, polycarboxylic acid anhydride, and co~pounds containing mtathylol and/or methylol ether groups~ In addition, the hydro~yl groups considerably improve t~le a~hesion of pol~mer films.
Examples 20 to 27 illustrate bulk and solution polymerisation reactio~ L`.Si~lg the azo~ isobutyric acid-(N,N~-hydroxyalkyl)~a;~idines corresponding to the ~ormula (I).
The parts and percen-tages quoted in the Examples are by weight, unless othtarw~se indicated. 'rhe intrinsic viscosity [~], L dl ] was measured in the solvents indicated at a temperature o~ 25C.
Production of the a~o-di ~
-alkyl)-amidines EXAMPLE 1:
Azo-di-isobutyric acid-~N,N'-~is-2-llydro.Yye-thyl)-amidine:
114 g (0.5 mole) o~ azo-di-isobutyric a~d imino-methyl ether9 300 ml oE methanol and 122 g (2 moles) o~
ethanolamine were stirred ~or 8 hours a-t 50C. 'rO remove methanol and ammonia (1 mo~a)~ the mi~ture was distilled out in a water jet vacuum (12 m~ar) a-t temperatures o~
up to at most 50C, leaving 165 g _ 88.2 /0 o~ the theoretical yield of a yellow-orange, water soluble oil;
3o ~ 1.4880.
Analysis calculated ~or C16I-I~4N604, molecular weight 374:
calculated C: 51.~4 o~b; H: 9.09 7h; N: 22.46 %; 0: 17.11 %
observed C: 51.5 ~O ; H: 9.~ //o; N: 22.8 %; 0: 17.4 %~
~:~ 3~93~
EXPMPLE 2:
Azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine (two stage process):
8.8 g (0.2 mole) of ethylene oxide were introduced while cooling with ice/water at 20 to 30 & into 37.4 g (0.1 mole) of the azo-di-isobutyric acid-(N,N'-bis-hydroxyethyl)-amidine obtained in accordance with F~ample 1. The mix-ture was then stirred for 5 hours at rocm temperature (approximately 25C). A
yellow, viscous, water-soluble oil (n20 1.4910) was obtained in a yield of 46 g or 99 % of the theoretical.
Analysis calculated for C20H42N606, molecular weight 462;
calculated C: 51.95 %; H: 9.09 %; N: 18.18 %; O: 20.78 %
abserved C: 52.2 % ; H: 9.2 % ; N: 18.5 % ; O: 20.4 %O
The same azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine is also obtained by the following process according to Exa~ple 3:
EX~MPLE 3:
Azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine (one-stage process):
45.6 g (0.2 mole) of azo-di-isobutyric acid im m oethyl ether, 200 ml of methanol, 42 g (0.4 mole) of diethanolamine and 26 g (0.4 mole) of ethanolamine were stirred for 8 hours at 50C. To remDve methanol and am~nia (0.4 mole), the mixture was distilled out m vacuo (12 mbar) at temperatures of up to at most 50C, leaving 91 g = 98 % of the theoretical yield of a yellow, viscous, water-soluble oil which had the same refractive index as the oil of the preced-ing Example and was identical therewith.
EXPMPLE 4:
Azo-di-isobutyric acid-(N,N'-bis-2-hydrcxypropyl)-amidine:
57 g (0.25 mole) of azo-di-isobutyric acid iminomethyl ether, 200 ml of methanol and 75 g (1 mole) of 1-amino-2-propanol were heated for B ho~lrs to 50C in a water bath, 0.5 mole of ammonia being released. The mixture was dis-:
~3~3~
tilled at 50 &, first under a pressure of 12 mbar and then under a pressure of 0.1 mbar, in order to re~ve the volatile fractions. A yellcwish wa~er-soluble oil (nD: 1.4691) was left behind as a residue in a quanti-ty of 93 g, corres-ponding to a yield of 87 ~ of the theoretical.
Analysis calcuLated for C20H42N604, mDlecular weight 430:
calcula~ed C: 55.81 %; H: 9.76 %; N: 19.53 %; O: 14.88 %
observed C: 56.1 ~ ; H: 10.0 %; N: 19.7 ~ ; O: 14.7 ~.
If the l-amuno-2-propanol in the above nlxture is replaced by l-amino-
3-propanol, azo-di-isobutyric acid-(N,N'-bis-3-hydroxypropyl)-amidine is ob-tained in the form of a yellow oil which, on standLng, solidifies into ayellowish paste.
EXAMPLE 5:
Aæo-di-isobutyric acid-(N,N'-bis-3-hydroxybutyl)-amidine:
45.6 g (0.2 mole) of azo-di-isobutyric acld imunome~hyl ether, 200 ml of methanol and 73.2 g (0.8 mole) of 1-amino-3-~utanol were heated for 8 ho~lrs to 40&, 0.4 mole of ammonia being released. The mixture was distilled at 50&, first under a pressure of 12 mbar and then under a pressure of 0.1 mbar, to re-move the volatile fractions. A yellow oil (nD: 1.4801) was left behind as a residue in a quantit~ of 91 g, corresponding to a yield of 93 % of the theoretical.
Analysis calculated for C24H50N60~, m~lecular weight 486:
calculated C: 59.26 %; H: 10.29 %; N: 17.28 %; O: 13.13 %
observed C: 59.1 % ; H: 10.5 % ; N: 17.4 % ; O: 13.6 %.
~XPMPLE 6:
A2o-di-isobutyric acid-(N-2-hydroxypropyl-N',N'-bis-2-h~droxyethyl)-amidine:
~3 3a~
~ 23 ~
128 g (0.5 mole) of azo-di-isobutyric acid iminoethyl ester, 400 ml o~ methanol, 75 g (1 mole) o~ 1-amino-2-propanol and 105 g (1 mole) of bis-~2-hydro~yethyl)- -~
amine were heated for 8 hours to 503C, 1 mole of ammonia being releasedO The mi~ture was distilled, ~irst at . .
50C/12 mbar and then at 50C/0.1 mbar, to remove the volatile constituents. A yellow water-soluhle oil ( ~ : 1.4780) was left behind as a residue in a quantity o~ 224 g, corresponding to 92 % of the theoretical yield.
1~ Analysis calculated ~or C22~6N606, molecular weight 490:
calcula-ted C: 5~.88 /0; H: 9.39 %; N: 17 14 %; 0: 19.59 % ~~
observed C: 53.6 % ; H: 9.7 % ; N: 17.0 ~ ; 0: 19.8 /0.
APplicat-i-o-n ~ les ~ to 19 relatin~ to he production of aqueous poly~ ersions 15 E~AMPLE ?
The emulsion polymerisation reaction is carried out in a 4-litre 5-necked flask of Jena glass equipped with a Dimroth re~lu~ condenser, a gas-bubble counter (with a three-way cock between condenser and sealing ~luid), a water-cooled stirrer (with a drive motor and centri-fugally spreading blade~ at 90~ intervals apart) provided with a nitrogen inlet cock and a ground thermometer or thermosensor cartridge inserted into the ~lask.
Two Ansch~tz heads are fit-ted to the two remainlng ground necks, either carrying four dropping funnels with pressure equalisation ~or the introduction of Solutions I to IV specified hereinafter or having one dropping funnel for Solution I and three feed spouts (consisting of a ground cap and core and of a glass dropping tube which is centrally ~used in, being bent downwards at its upper end and provided with a cock) The hoses leading via three miniature metering pumps to the supply vessels ~or solutions or mi~tures II, III and IV
are -then optionally connected to these closeable feed Spouts.
Le A 19 058 ~ 313~3~
~ he ~olution of initial reaction mi~ture is then introduced into the ~lask. After the ~lask has been evacuated through the three-way cock (with the cocks --~-of the ~eed spouts and the nitrogen feedpipe closed)~
nitrogen is introduced for equalisation. A T-tube with _~
a non-return valve incorporated in the nitrogen feed - pipe and dipping into water prevents excess pressure from builcling up in the glass flask~
Evacuation and gassing with nitrogen are carried 1~ out t;hree -times9 after which all the air has been dispIaced from the reac~ on zone. The initial reaction mi~tl:lre is then heated with stirring (appro~imately 250 to 300 rpm) to the required pol~erisation -temperature (70C') under a slight nitrogen eYcess pressure ~two bubbles -J5 per seco~d).
To this end, the flask is immersed in a thoroughly insulated waterbath with an overflow which can be heated by an immersion heater and cooled through a valve, which allows ¢old water to flow i~, the m~imum heating rate and ma~imum cooling rate substantially corresponding to one ~nother.
The immersion heater and cooler are manipulated vari~bles of a control system of which the controlled vari~ble i5 the internal temperature (i.e. the temperature of the dispersion) and o~ which the disturbance variable is primarily the exothermic reaction.
In this way, the internal temperature can be very accurately adjusted~ The deviation from the required temperature is less -than 1 given a uniform reaction.
3~ Once the required polymerisation temperature has been reached, Solution I is added all at once, after which polymerisation generally begins immediately. When a blueish seed late~ has formed and when the heat of polymerisation has abated, Solutions II, III, IV are added Le A 19 058 __ ~. 3~
dropwise over a certain period, in this case 6 hours, or are pumped in through suitable miniature metering pumps which is more accurate.
A~ter all the components have been added, the polymerisætion mixture is a~ter-polymerised ~or a certain time iin thi~l case 2 howrs) at a certai~
temperature ~in thi~ case 85C) in order to complete con~ersior! o-. the monomers~
gparts by weight, based on total components Initial re~lction mi~',;ure: ~ ~~~
Fully d2saI-I,e~ or dic;tilled water 93. 33.646 Sodium laur~]. ~ulpha1;e 6.0 0.217 Acrylic ac.id-~-butyl ester 64.2 2.323 --~
Acryloni1r,.1a 17.05 0.617 Styrene 17.05 0.617 Methacryl~m:!.^le 4.0 0. 11L4 S0lution I
Distill.ed wat,er ~or 1.~ully desalt,ed l~3.ter) 81.0 2.930 Azo~di-iso~utyric ac:i.d-~N,N'-bis-2~hydx~xyethyl)-amidine 2.5 0,090 Methacrylic acid~ 50~, in water 2.2 0~077 Solution J.l Acrylic acid~n-butyl ester715.2 25.875 Acrylonitrile 189.9 6.87 Styrene 189.9 6.87 Methacrylamide 45.7 1~6533 ~,~
g parts by weigh-t, based on total ccmponents Solution III
Water ~see above) 270.0 9.768 A~o-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine 7.0 0.253 Methacrylic acid, 50 % in water 6.2 0.224 . .
Solution IV
Water (see above) 196.0 7.091 Sodium lauryl sulphate 20.2 0.731 Sum total 2,764.1 100 Polymerisation temperature: 70C
Addition time for II, III, IV: 6 hours After-polymerisation: 2 hours at 85 &.
The thinly liquid latex obtained in this way has a solids content of frcm 45 to 46 ~ and passes freely through a 30 ll square-mesh Perlon cloth, only a little coarse-grained coagulate ~approximately 0.5 to 5 g) being retained.
The latex has uniform particles approximately 130 nm in diameter. It dries at 25C to form a clear, non-tacky, highly water-resistant film.
A drop of water left on the surface of the film or about 30 minutes d oe s not cloud or dissolve the film. In order to improve its ion resistance, the latex may be aftertreated with non-ionic emulsifiers. However, this is only necessary for special applications.
The latex may be mixed with standard commercially available water-soluble melamine~formaldehyde resins or urea-formaldehyde resins of the type used for stoving lacquers. In addition, pigments and fillers ~ay be added to these mixtures. Because of the absence of the inorganic solv~rts normally used~
, ~
a~ueous stoving systems of the type in question show improved resistance to water and adhesion to various substrates, particularly metals.
The polymr on which the latex is based is gel-free, soluble in tetra-hydrofuran or dimethyl fornE~nide and has an intrinsic viscosity [n] Of 3.0 dl/g at 25C in tetrahydrofuran.
It consists of:
62.7 % of polymerised butylacrylate units 16.65 % of acrylonitrile units 16.65 % of styrene units
EXAMPLE 5:
Aæo-di-isobutyric acid-(N,N'-bis-3-hydroxybutyl)-amidine:
45.6 g (0.2 mole) of azo-di-isobutyric acld imunome~hyl ether, 200 ml of methanol and 73.2 g (0.8 mole) of 1-amino-3-~utanol were heated for 8 ho~lrs to 40&, 0.4 mole of ammonia being released. The mixture was distilled at 50&, first under a pressure of 12 mbar and then under a pressure of 0.1 mbar, to re-move the volatile fractions. A yellow oil (nD: 1.4801) was left behind as a residue in a quantit~ of 91 g, corresponding to a yield of 93 % of the theoretical.
Analysis calculated for C24H50N60~, m~lecular weight 486:
calculated C: 59.26 %; H: 10.29 %; N: 17.28 %; O: 13.13 %
observed C: 59.1 % ; H: 10.5 % ; N: 17.4 % ; O: 13.6 %.
~XPMPLE 6:
A2o-di-isobutyric acid-(N-2-hydroxypropyl-N',N'-bis-2-h~droxyethyl)-amidine:
~3 3a~
~ 23 ~
128 g (0.5 mole) of azo-di-isobutyric acid iminoethyl ester, 400 ml o~ methanol, 75 g (1 mole) o~ 1-amino-2-propanol and 105 g (1 mole) of bis-~2-hydro~yethyl)- -~
amine were heated for 8 hours to 503C, 1 mole of ammonia being releasedO The mi~ture was distilled, ~irst at . .
50C/12 mbar and then at 50C/0.1 mbar, to remove the volatile constituents. A yellow water-soluhle oil ( ~ : 1.4780) was left behind as a residue in a quantity o~ 224 g, corresponding to 92 % of the theoretical yield.
1~ Analysis calculated ~or C22~6N606, molecular weight 490:
calcula-ted C: 5~.88 /0; H: 9.39 %; N: 17 14 %; 0: 19.59 % ~~
observed C: 53.6 % ; H: 9.7 % ; N: 17.0 ~ ; 0: 19.8 /0.
APplicat-i-o-n ~ les ~ to 19 relatin~ to he production of aqueous poly~ ersions 15 E~AMPLE ?
The emulsion polymerisation reaction is carried out in a 4-litre 5-necked flask of Jena glass equipped with a Dimroth re~lu~ condenser, a gas-bubble counter (with a three-way cock between condenser and sealing ~luid), a water-cooled stirrer (with a drive motor and centri-fugally spreading blade~ at 90~ intervals apart) provided with a nitrogen inlet cock and a ground thermometer or thermosensor cartridge inserted into the ~lask.
Two Ansch~tz heads are fit-ted to the two remainlng ground necks, either carrying four dropping funnels with pressure equalisation ~or the introduction of Solutions I to IV specified hereinafter or having one dropping funnel for Solution I and three feed spouts (consisting of a ground cap and core and of a glass dropping tube which is centrally ~used in, being bent downwards at its upper end and provided with a cock) The hoses leading via three miniature metering pumps to the supply vessels ~or solutions or mi~tures II, III and IV
are -then optionally connected to these closeable feed Spouts.
Le A 19 058 ~ 313~3~
~ he ~olution of initial reaction mi~ture is then introduced into the ~lask. After the ~lask has been evacuated through the three-way cock (with the cocks --~-of the ~eed spouts and the nitrogen feedpipe closed)~
nitrogen is introduced for equalisation. A T-tube with _~
a non-return valve incorporated in the nitrogen feed - pipe and dipping into water prevents excess pressure from builcling up in the glass flask~
Evacuation and gassing with nitrogen are carried 1~ out t;hree -times9 after which all the air has been dispIaced from the reac~ on zone. The initial reaction mi~tl:lre is then heated with stirring (appro~imately 250 to 300 rpm) to the required pol~erisation -temperature (70C') under a slight nitrogen eYcess pressure ~two bubbles -J5 per seco~d).
To this end, the flask is immersed in a thoroughly insulated waterbath with an overflow which can be heated by an immersion heater and cooled through a valve, which allows ¢old water to flow i~, the m~imum heating rate and ma~imum cooling rate substantially corresponding to one ~nother.
The immersion heater and cooler are manipulated vari~bles of a control system of which the controlled vari~ble i5 the internal temperature (i.e. the temperature of the dispersion) and o~ which the disturbance variable is primarily the exothermic reaction.
In this way, the internal temperature can be very accurately adjusted~ The deviation from the required temperature is less -than 1 given a uniform reaction.
3~ Once the required polymerisation temperature has been reached, Solution I is added all at once, after which polymerisation generally begins immediately. When a blueish seed late~ has formed and when the heat of polymerisation has abated, Solutions II, III, IV are added Le A 19 058 __ ~. 3~
dropwise over a certain period, in this case 6 hours, or are pumped in through suitable miniature metering pumps which is more accurate.
A~ter all the components have been added, the polymerisætion mixture is a~ter-polymerised ~or a certain time iin thi~l case 2 howrs) at a certai~
temperature ~in thi~ case 85C) in order to complete con~ersior! o-. the monomers~
gparts by weight, based on total components Initial re~lction mi~',;ure: ~ ~~~
Fully d2saI-I,e~ or dic;tilled water 93. 33.646 Sodium laur~]. ~ulpha1;e 6.0 0.217 Acrylic ac.id-~-butyl ester 64.2 2.323 --~
Acryloni1r,.1a 17.05 0.617 Styrene 17.05 0.617 Methacryl~m:!.^le 4.0 0. 11L4 S0lution I
Distill.ed wat,er ~or 1.~ully desalt,ed l~3.ter) 81.0 2.930 Azo~di-iso~utyric ac:i.d-~N,N'-bis-2~hydx~xyethyl)-amidine 2.5 0,090 Methacrylic acid~ 50~, in water 2.2 0~077 Solution J.l Acrylic acid~n-butyl ester715.2 25.875 Acrylonitrile 189.9 6.87 Styrene 189.9 6.87 Methacrylamide 45.7 1~6533 ~,~
g parts by weigh-t, based on total ccmponents Solution III
Water ~see above) 270.0 9.768 A~o-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine 7.0 0.253 Methacrylic acid, 50 % in water 6.2 0.224 . .
Solution IV
Water (see above) 196.0 7.091 Sodium lauryl sulphate 20.2 0.731 Sum total 2,764.1 100 Polymerisation temperature: 70C
Addition time for II, III, IV: 6 hours After-polymerisation: 2 hours at 85 &.
The thinly liquid latex obtained in this way has a solids content of frcm 45 to 46 ~ and passes freely through a 30 ll square-mesh Perlon cloth, only a little coarse-grained coagulate ~approximately 0.5 to 5 g) being retained.
The latex has uniform particles approximately 130 nm in diameter. It dries at 25C to form a clear, non-tacky, highly water-resistant film.
A drop of water left on the surface of the film or about 30 minutes d oe s not cloud or dissolve the film. In order to improve its ion resistance, the latex may be aftertreated with non-ionic emulsifiers. However, this is only necessary for special applications.
The latex may be mixed with standard commercially available water-soluble melamine~formaldehyde resins or urea-formaldehyde resins of the type used for stoving lacquers. In addition, pigments and fillers ~ay be added to these mixtures. Because of the absence of the inorganic solv~rts normally used~
, ~
a~ueous stoving systems of the type in question show improved resistance to water and adhesion to various substrates, particularly metals.
The polymr on which the latex is based is gel-free, soluble in tetra-hydrofuran or dimethyl fornE~nide and has an intrinsic viscosity [n] Of 3.0 dl/g at 25C in tetrahydrofuran.
It consists of:
62.7 % of polymerised butylacrylate units 16.65 % of acrylonitrile units 16.65 % of styrene units
4.0 % methacrylamide units.
EXAMPLE 8 (Ccmparison) . . _.
A) The procedure is as in Example 7, except that the initiator i5 re-plaoe d by the same quantity of ammonium peroxy disulphate. me coagulate-free latex formed is yellow in colour. Clear films of this latex show poorer adhe-sion to glass and are mDre sensitive to water. Ln analagous co~bination with pigments, melamine-formaldehyde resin mixtures prepared with this latex give distinctly poorer results on storage in water. The layers stoved onto metal separate from the substrate.
B) The procedure is as in Example 7, except tha-t the initiator is re-placed by the same quan-tity of y,y'-azo-(~-cyano)-valeric acid (formula VI) dis-solved in an equivalent quantity of dilute aqueous 10 ~ ammonia solution. The latex has a particle size of approximately 150 nm, is distinctly yellow in colour and contains approximately 15 g of coagulate. ~he clear film dried at 25 &, to whose surface a drop of water was applied with a pipette, clouds and dissolves after a~out 30 minutes.
EX~MP _ ~he procedure is as in Example 7, except that the initiator is re-~3,;r ~f~,, placed by azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxye~hyl)-amidine. A sub-stantially mono- disperse latex havlng similar properties to the latex described in Example 7 is obtained.
EX~MPLE 10 m e solution described below as initial reaction mixture is introduced into the apparatus described in Example 7 and heated under nitnogen to 75 C.
After Solution I has been injected, Solutions II, III and IV æe introduced over a period of 5 hours, after which the temperature is increased to 80C, followed by stirring for 2 hours.
A thinly liquid, coagulate-free latex having a solids content of 46.5 is obtained. After the residual monomers have been removed, the la-tex may be mixed with commercially available water-soluble urea-forn~ildehyde resins or melamine-formaldehyde resins and pigments and used as an aqueo~ls stoving lacquer.
g parts by weight, based on total ccmponents Initial reaction mlxture:
Distilled water 919.0 31.8971 Sodium lauryl sulphate 6.0 0.208 Acrylic acid-n-butyl ester 60.0 2~082 Acrylonitrile 15.0 0.5205 Styrene 15.0 0.5205 Methacrylic acid-2-hydroxy-propyl ester 10.0 0.347 Methacrylamide 2.0 0.0694 Methacrylic acid 2.0 0.0694 ```~;
..
g parts by weight, based on total components -- _ Solution I
Distilled water 100.0 3.471 Azo-di-isobutyric acid-~N,N'-bis-2-hydroxyethyl)- -.
amidine - 3.0 0.104 Methacrylic acid, 50 % in 10 water 2.64 0~0916 Solution II ..
Acrylic acid-n-butyl ester7G0.0 24.296 Acrylonitrile 175.0 6.074 Styrene 175.0 6.074 15 Methacrylic acid-2- .
hydroxy-propyl ester 116.7 4.050 Methacrylamide 23.3 0.809 Methacrylic acid 23.3 0.809 . . _ . ~
Solution III
20 Distilled water 3oo,o 10.412 Azo-di-isobutyric acid-(N,N'-bis-2-hydroxy-ethyl)-amidine 7.0 0.243 Methacrylic acid, 50 % in water 6.2 0.215 Solution IV
Distilled water 200.0 6.941 Sodium lauryl sulphate 20.0 0.694 . _ ,. . .
Sum total 2,881.14 100 Polymerisation temp~raturs: 75C
Addition time ~or II, IIIf IV: 5 hours A~ter-polymerisation: 2 hours at 80C.
Lç A 19 058 ~ .
Since the monomers are copolymerised subst~ntially quantitatively, as in the ~ollowing Examples, the integral composition o~ the polymer corresponds to the eomposition of the monomer mi~ture:
~7.7 % by weight of butyl acrylate units 14. ~5% by weight o~ acrylonitrile units l~t.45% by weight of styrene units 9 . 6 /a by weight of methacrylic acid-2-hydroxypropyl ester units l.9 /~ by weight of methacrylic acid units 1.9 ~ by weight of methacrylamide units ~~-lO0 /~ by weight.
O0 parts by weight of distilled water, l part by weight of an alkyl monosulphonate containing from 12 to lLt carbon atoms and 0.25 part by weight of azo-di-isobutyric acid-(N,NI-bis-2-hydroxyethyl)-amidine are introduced into a three-neckedflask and heated to ~OC .
50 parts by wei~ht of a mix-ture of 200 parts by weight of styrene, 275 parts by weight of acrylic acid-n-butyl ester ~nd 25 part~lby weight of methacrylic acid ~re then added. After stirring for 30 minutes at 80C, the rest of the monomer mixture ~nd a solution of 350 parts by weight o~ distilled water~ lO parts by weight o~ an alkyl monosulphonate containing from 12 to 14 carbon atoms and 5 parts by weight of azo-di-iso-butyric acid-(N,N'-bis-hydro~yethyl~-amidine are uniformly added dropwise over a period of 3 hours at a temperature of 80C, followed by stirring for 2 hours at 80~C. 1230 parts by weight of a coagulate-free dispersion are obtained after degassing. The dispersion has a solids content of 39 % and a mean particle size o~
145 nm. The flowout time from a DIN cup (2 mm ori~ice) amounts to 69 seconds.
Le A 19 058 ~ _ .
The procedure is as in Example 11, except that the monomer mux-ture used in that Example is replaced by a mixture of ]90 parts by weight of styrene, 260 parts by weight of acrylic acid-_-butyl ester, 25 parts by weight of meth-acrylic acid and 25 parts by weight of 2-hydro~ypropyl methacrylate. ~therwise the conditions are the same. 1150 parts by weight of a coagulate-free disper-sion are obtained after degassing. The dispersion has a solids content of 39.5 % and a mean particle size of 138 nm. The flcwout time from a M N cup (2 mm orifice) amounts to 78 seconds.
The dispersion thus obtained dries at 25C to form clear water-resistant films. It may be mLxed with melamine-form~ldehyde resins or urea-formaldehyde resins and pigments. m e resulting m~xtures may be stoved onto metals, forming firmly adhering, water-resistant and solvent-resistant coatings.
EX~MPLE 13 m e procedure is the same as in EXample 12, except that an equivalent quantity of azo-di-isobutyric acid-(N,N'-bis-2-hydroxypropyl)-amidine is used as initiator. 1190 parts by weight of a coagulate-free dispersion are obtained after degassing. The dispersion has a solids content of 37.5 ~, a mean particle size of 132 nm and a flow-out time from a M N cup (2 mm orifioe) of 75 seconds.
Polyvinyl chloride l~tex 3000 parts by weight of distilled water, 7.5 parts by weight of an alkyl monosulphonate containing from 12 to 14 carbon atams, 6 parts by weight of azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine and 10 parts by weight of acetic acid are introduced into a stainless-steel autoclave equipped with an anchor stirrer. me autoclave is evacuated, purged twice with nitro~en (3 bars) and then evacuated again. 1500 parts by weig~t of vinyl chloride are then int~odued into the autoclave and the internal temperature is increased to 65 &. I'his temperature is maintained for 12 hours. The initial pressure amounts to 13 bars. On completion of polymerisation, th2 press~re amounts to 4 bars~
4175 parts by weight of a coagulate~free latex having a particle size of 180 nm are obtained after degassing. The polymer has an intrinsic viscosity of 0.77 (as measured in tetrahydrofuran). The solids content amounts to 29 %
and the flowout ti~le frcm a DIN cup (2 mm orifice) to 75 seconds.
EX~MPLE 1 Polyvinyl a oe tate latex A solution of 12.8 parts by weight of polyvinyl alcohol (partially hydrolysed polyvlnyl aoe tate with a degree of hydrolysis of 88 %) in 125 parts by weight of distilled water is prepared in a three-necked flask.
1. A solution of Q.35 part by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine in 40 parts by weight of distilled wa-ter and 0.8 part by weight of aoe tic acid, and 2. 191 parts by weight of vinyl acetate are sim~ltaneously added drop-wise to the solution heated to 68 C over a period of 3.5 hours, during which thetemperature is kept constant at 68 &. After stirring for another 3.5 hours at 68C, a solution of 0.005 part by weight of azo-di-isobutyric acid~(N,N'-bis-2-hydroxyethyl)-amidine in 10 parts by weigh-t of distilled water is added dropwise over a period of 15 minutes, followed by stirring for 45 minutes at 90 C.
350 parts by weight of a highly viscous dispersion having a solids con-tent of 51 % and a mean particle size of 260 nm are obtained after degassing.
The prooedure is as in Example 15, except that an e~uivalent quantity of azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine is used as initiator.
342 parts ~y weight of a highly viscous dispersion having a solids con-tent of 48 % and a particle size of 245 nm are obtained.
ExAMæLE 17 Polychloroprene latex 120 parts by weigh~ of distilled water, 5 p~rts by weight of the sodium salt of a disproportionated abietic acid and 0.6 part by weight of sodium hydroxide are inltially introduced into a three-necked flask. After purging with nitrogen for 30 minutes at room temperature, 100 parts by weight of a chloroprene stabilised with 180 ppm of phenothiazine are stirred in. m e con-tents of the flask are then heated under nitrogen to 64C, followed by -the drop-wise addition over a period of 2 hours of a solution of 2.5 parts by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine in 100 parts by weight of distilled water. The mixture is then stirred for 3 hours at 64C. The unreacted chloroprene is removed by distillation with steam.
310 parts by weight of a stable dispersion having a solids content of 25.5 % and a mean particle size of 185 nm are obtained.
The procedure is as in Example 17, except that an equivalent quantity of azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine is used as initia~or.
Removal of the unreacted chloroprene by distillation with steam leaves 290 parts by weight of a coagulate-. ~
l~
0~
- 3~ -~ree dispersion haviug a solids content o~ 27 /0 and mean particle size of 170 nm.
2700 parts by weight of distilled water, 70 parts - :
by weight o~ the sodiwm salt~of a disproportio~ated ~~~
abietic a~id, 7.5 parts by weight of n-dodecyl mercaptan and 6 parts by weight o~ azo-di-isobutyric a¢id-(N,N'-bis-2-hydroxyethyl)-~midine are initially introcluced into a stainless-steel autoclave equipped with an anchor stirrer. ~he autoclave is evacuated, purged --twice with nitrogen (3 bars) and then evacuated again.
435 parts by weight of styrene and 1065 parts by weight of butadiene are then successively pumped in. With the stirrer rotating at 150 rpm, the contents of the auto~
clave are heated to 65C, the pressure amounting -to 10.5 bars, and kept at this temperature for 10 hours. ~he pressure then amounts to 8.0 bars. On completion of the reaction, a solution of 1 part by weight of hydroquinone in 50 parts by weight of distilled water is introcluced under pressure for stabilisation.
3450 parts by weight of a coagulate-free late~
are obtained after degassing. The late~ has a solids con-tent o~ 33 %, a mean par-ticle si~e of 190 nm and a flow-out time from a DIN cup (2mm orifice) of 130 seconds.
~ulk and Solution Polymerisation ~xamples 20 to 26) In a glass bomb tube, a solution of o.6 part by 3o weight of azo-di-isobutyric acid-(N,N'~N'-tris 2-hydro~yethyl)-amidine in 30 parts by weight of styrene is gassed with nitrogen for 3 minutes to remove ~~
the air present. After the bomb tube has been sealed by fusing, its contents are heated for 8 hour~ to 75C.
Le A 19 058 ~.~3~
The polymerised contents are dissolved in 300 parts by weight o~ te-trahydrofuran and subsequently precipitated with 10 times the quantity by weight of methanol. 17 parts by weight of a purified polymer are obtained
EXAMPLE 8 (Ccmparison) . . _.
A) The procedure is as in Example 7, except that the initiator i5 re-plaoe d by the same quantity of ammonium peroxy disulphate. me coagulate-free latex formed is yellow in colour. Clear films of this latex show poorer adhe-sion to glass and are mDre sensitive to water. Ln analagous co~bination with pigments, melamine-formaldehyde resin mixtures prepared with this latex give distinctly poorer results on storage in water. The layers stoved onto metal separate from the substrate.
B) The procedure is as in Example 7, except tha-t the initiator is re-placed by the same quan-tity of y,y'-azo-(~-cyano)-valeric acid (formula VI) dis-solved in an equivalent quantity of dilute aqueous 10 ~ ammonia solution. The latex has a particle size of approximately 150 nm, is distinctly yellow in colour and contains approximately 15 g of coagulate. ~he clear film dried at 25 &, to whose surface a drop of water was applied with a pipette, clouds and dissolves after a~out 30 minutes.
EX~MP _ ~he procedure is as in Example 7, except that the initiator is re-~3,;r ~f~,, placed by azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxye~hyl)-amidine. A sub-stantially mono- disperse latex havlng similar properties to the latex described in Example 7 is obtained.
EX~MPLE 10 m e solution described below as initial reaction mixture is introduced into the apparatus described in Example 7 and heated under nitnogen to 75 C.
After Solution I has been injected, Solutions II, III and IV æe introduced over a period of 5 hours, after which the temperature is increased to 80C, followed by stirring for 2 hours.
A thinly liquid, coagulate-free latex having a solids content of 46.5 is obtained. After the residual monomers have been removed, the la-tex may be mixed with commercially available water-soluble urea-forn~ildehyde resins or melamine-formaldehyde resins and pigments and used as an aqueo~ls stoving lacquer.
g parts by weight, based on total ccmponents Initial reaction mlxture:
Distilled water 919.0 31.8971 Sodium lauryl sulphate 6.0 0.208 Acrylic acid-n-butyl ester 60.0 2~082 Acrylonitrile 15.0 0.5205 Styrene 15.0 0.5205 Methacrylic acid-2-hydroxy-propyl ester 10.0 0.347 Methacrylamide 2.0 0.0694 Methacrylic acid 2.0 0.0694 ```~;
..
g parts by weight, based on total components -- _ Solution I
Distilled water 100.0 3.471 Azo-di-isobutyric acid-~N,N'-bis-2-hydroxyethyl)- -.
amidine - 3.0 0.104 Methacrylic acid, 50 % in 10 water 2.64 0~0916 Solution II ..
Acrylic acid-n-butyl ester7G0.0 24.296 Acrylonitrile 175.0 6.074 Styrene 175.0 6.074 15 Methacrylic acid-2- .
hydroxy-propyl ester 116.7 4.050 Methacrylamide 23.3 0.809 Methacrylic acid 23.3 0.809 . . _ . ~
Solution III
20 Distilled water 3oo,o 10.412 Azo-di-isobutyric acid-(N,N'-bis-2-hydroxy-ethyl)-amidine 7.0 0.243 Methacrylic acid, 50 % in water 6.2 0.215 Solution IV
Distilled water 200.0 6.941 Sodium lauryl sulphate 20.0 0.694 . _ ,. . .
Sum total 2,881.14 100 Polymerisation temp~raturs: 75C
Addition time ~or II, IIIf IV: 5 hours A~ter-polymerisation: 2 hours at 80C.
Lç A 19 058 ~ .
Since the monomers are copolymerised subst~ntially quantitatively, as in the ~ollowing Examples, the integral composition o~ the polymer corresponds to the eomposition of the monomer mi~ture:
~7.7 % by weight of butyl acrylate units 14. ~5% by weight o~ acrylonitrile units l~t.45% by weight of styrene units 9 . 6 /a by weight of methacrylic acid-2-hydroxypropyl ester units l.9 /~ by weight of methacrylic acid units 1.9 ~ by weight of methacrylamide units ~~-lO0 /~ by weight.
O0 parts by weight of distilled water, l part by weight of an alkyl monosulphonate containing from 12 to lLt carbon atoms and 0.25 part by weight of azo-di-isobutyric acid-(N,NI-bis-2-hydroxyethyl)-amidine are introduced into a three-neckedflask and heated to ~OC .
50 parts by wei~ht of a mix-ture of 200 parts by weight of styrene, 275 parts by weight of acrylic acid-n-butyl ester ~nd 25 part~lby weight of methacrylic acid ~re then added. After stirring for 30 minutes at 80C, the rest of the monomer mixture ~nd a solution of 350 parts by weight o~ distilled water~ lO parts by weight o~ an alkyl monosulphonate containing from 12 to 14 carbon atoms and 5 parts by weight of azo-di-iso-butyric acid-(N,N'-bis-hydro~yethyl~-amidine are uniformly added dropwise over a period of 3 hours at a temperature of 80C, followed by stirring for 2 hours at 80~C. 1230 parts by weight of a coagulate-free dispersion are obtained after degassing. The dispersion has a solids content of 39 % and a mean particle size o~
145 nm. The flowout time from a DIN cup (2 mm ori~ice) amounts to 69 seconds.
Le A 19 058 ~ _ .
The procedure is as in Example 11, except that the monomer mux-ture used in that Example is replaced by a mixture of ]90 parts by weight of styrene, 260 parts by weight of acrylic acid-_-butyl ester, 25 parts by weight of meth-acrylic acid and 25 parts by weight of 2-hydro~ypropyl methacrylate. ~therwise the conditions are the same. 1150 parts by weight of a coagulate-free disper-sion are obtained after degassing. The dispersion has a solids content of 39.5 % and a mean particle size of 138 nm. The flcwout time from a M N cup (2 mm orifice) amounts to 78 seconds.
The dispersion thus obtained dries at 25C to form clear water-resistant films. It may be mLxed with melamine-form~ldehyde resins or urea-formaldehyde resins and pigments. m e resulting m~xtures may be stoved onto metals, forming firmly adhering, water-resistant and solvent-resistant coatings.
EX~MPLE 13 m e procedure is the same as in EXample 12, except that an equivalent quantity of azo-di-isobutyric acid-(N,N'-bis-2-hydroxypropyl)-amidine is used as initiator. 1190 parts by weight of a coagulate-free dispersion are obtained after degassing. The dispersion has a solids content of 37.5 ~, a mean particle size of 132 nm and a flow-out time from a M N cup (2 mm orifioe) of 75 seconds.
Polyvinyl chloride l~tex 3000 parts by weight of distilled water, 7.5 parts by weight of an alkyl monosulphonate containing from 12 to 14 carbon atams, 6 parts by weight of azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine and 10 parts by weight of acetic acid are introduced into a stainless-steel autoclave equipped with an anchor stirrer. me autoclave is evacuated, purged twice with nitro~en (3 bars) and then evacuated again. 1500 parts by weig~t of vinyl chloride are then int~odued into the autoclave and the internal temperature is increased to 65 &. I'his temperature is maintained for 12 hours. The initial pressure amounts to 13 bars. On completion of polymerisation, th2 press~re amounts to 4 bars~
4175 parts by weight of a coagulate~free latex having a particle size of 180 nm are obtained after degassing. The polymer has an intrinsic viscosity of 0.77 (as measured in tetrahydrofuran). The solids content amounts to 29 %
and the flowout ti~le frcm a DIN cup (2 mm orifice) to 75 seconds.
EX~MPLE 1 Polyvinyl a oe tate latex A solution of 12.8 parts by weight of polyvinyl alcohol (partially hydrolysed polyvlnyl aoe tate with a degree of hydrolysis of 88 %) in 125 parts by weight of distilled water is prepared in a three-necked flask.
1. A solution of Q.35 part by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine in 40 parts by weight of distilled wa-ter and 0.8 part by weight of aoe tic acid, and 2. 191 parts by weight of vinyl acetate are sim~ltaneously added drop-wise to the solution heated to 68 C over a period of 3.5 hours, during which thetemperature is kept constant at 68 &. After stirring for another 3.5 hours at 68C, a solution of 0.005 part by weight of azo-di-isobutyric acid~(N,N'-bis-2-hydroxyethyl)-amidine in 10 parts by weigh-t of distilled water is added dropwise over a period of 15 minutes, followed by stirring for 45 minutes at 90 C.
350 parts by weight of a highly viscous dispersion having a solids con-tent of 51 % and a mean particle size of 260 nm are obtained after degassing.
The prooedure is as in Example 15, except that an e~uivalent quantity of azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine is used as initiator.
342 parts ~y weight of a highly viscous dispersion having a solids con-tent of 48 % and a particle size of 245 nm are obtained.
ExAMæLE 17 Polychloroprene latex 120 parts by weigh~ of distilled water, 5 p~rts by weight of the sodium salt of a disproportionated abietic acid and 0.6 part by weight of sodium hydroxide are inltially introduced into a three-necked flask. After purging with nitrogen for 30 minutes at room temperature, 100 parts by weight of a chloroprene stabilised with 180 ppm of phenothiazine are stirred in. m e con-tents of the flask are then heated under nitrogen to 64C, followed by -the drop-wise addition over a period of 2 hours of a solution of 2.5 parts by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine in 100 parts by weight of distilled water. The mixture is then stirred for 3 hours at 64C. The unreacted chloroprene is removed by distillation with steam.
310 parts by weight of a stable dispersion having a solids content of 25.5 % and a mean particle size of 185 nm are obtained.
The procedure is as in Example 17, except that an equivalent quantity of azo-di-isobutyric acid-(N,N',N'-tris-2-hydroxyethyl)-amidine is used as initia~or.
Removal of the unreacted chloroprene by distillation with steam leaves 290 parts by weight of a coagulate-. ~
l~
0~
- 3~ -~ree dispersion haviug a solids content o~ 27 /0 and mean particle size of 170 nm.
2700 parts by weight of distilled water, 70 parts - :
by weight o~ the sodiwm salt~of a disproportio~ated ~~~
abietic a~id, 7.5 parts by weight of n-dodecyl mercaptan and 6 parts by weight o~ azo-di-isobutyric a¢id-(N,N'-bis-2-hydroxyethyl)-~midine are initially introcluced into a stainless-steel autoclave equipped with an anchor stirrer. ~he autoclave is evacuated, purged --twice with nitrogen (3 bars) and then evacuated again.
435 parts by weight of styrene and 1065 parts by weight of butadiene are then successively pumped in. With the stirrer rotating at 150 rpm, the contents of the auto~
clave are heated to 65C, the pressure amounting -to 10.5 bars, and kept at this temperature for 10 hours. ~he pressure then amounts to 8.0 bars. On completion of the reaction, a solution of 1 part by weight of hydroquinone in 50 parts by weight of distilled water is introcluced under pressure for stabilisation.
3450 parts by weight of a coagulate-free late~
are obtained after degassing. The late~ has a solids con-tent o~ 33 %, a mean par-ticle si~e of 190 nm and a flow-out time from a DIN cup (2mm orifice) of 130 seconds.
~ulk and Solution Polymerisation ~xamples 20 to 26) In a glass bomb tube, a solution of o.6 part by 3o weight of azo-di-isobutyric acid-(N,N'~N'-tris 2-hydro~yethyl)-amidine in 30 parts by weight of styrene is gassed with nitrogen for 3 minutes to remove ~~
the air present. After the bomb tube has been sealed by fusing, its contents are heated for 8 hour~ to 75C.
Le A 19 058 ~.~3~
The polymerised contents are dissolved in 300 parts by weight o~ te-trahydrofuran and subsequently precipitated with 10 times the quantity by weight of methanol. 17 parts by weight of a purified polymer are obtained
5 after drying in YaCuo at 50C. ~_~
Intrinsic viscosity ~as measured in tetrahydrofuran): 0.49.
The polymers may be crosslinked with diisocyanates and polyisocyanates through the terminal hydro~yl group3 incorporated.
2 parts by weight of the polystyrene containing terminal hydro~yl groups obtained in accordance with E~ample 20 are dissolved in 18 parts by weight of anhydrous chlorobenzene. The solution is crosslinked with 0.2 part by weight of he~a~ethylene diisocyanate in the presence of 0.05 part by weight of tin(II) octoate.
After standing for 24 hours at room temperature, a crosslinked gel has formed. A film cast onto glass immediately after mixing is also crossli~ked after drying for 24 hours.
E ~MPLE 21 A solution of o.6 p~rt by weight of azo-di-iso-butyric acid-(N,N',N'-tris-2-hydroYyethyl)-amidine in 30 parts by weight of methyl me-thacrylate is polymerised in the same way as described in Example 20. After dissolution and reprecipitation, 19 g of a polymer having an intrinsic ~iscosity in tetrahydrofuran of 0.45 are obtained.
A solution of 30 parts by weight of acrylonitrile, 3o 70 parts by weight of dimethyl fo~amide and 0.3 part by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydro.Yyethyl)-amidine is stirred for 6 hours at 80C
in a three--necked flask equipped with a thermometer, reflu~ condenser and nitrogen feedpipe. The highly Le A 19 058 ~3~
~iscous solution formed is precipitated in 1000 parts by weight o~ water and dried in vacuo at 50C.
15 parts o~ a polymer having an intrinsic viscosi-ty ~~:.-~s measured in dimethyl formamide) of 0.58 are obtained.
E~AMP~E~
___ Following the procedure of Example 22, a solution ~i 30..parts by weight o~ vinyl acetate, 70 parts by weight of tert.-butanol, 0.3 part by weight o~ azo-di~
-isobutyric acid-(N,N7-bis-~-hydroxyethyl)-amidine and parts by weight of acetic acid is stirred for 6 hours at 80C. After th~ highly viscous solution ha~ been ~recipitated in 1000 parts by weight of water, 13 parts by weight of a polymer having an intrinsic viscosity ~s measured in dimethyl formamide) of 0.35 are obtained af-ter drying.
~AMPLE 24 500 parts by weight of distilled water are i.ltroduced into a three-necked fla~kO The content~ of the flask are then heated under nitrogen to an internal ~s) tempera.ture of 70C, after which a) lU0 parts by weight of acrylonitrile, and b3 a solution o~ 0.5 part by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydro~yethyl)-amidine in 50 parts by weight of distilled water are uni~ormly added dropwise over a period of 2 hours.
0~ completion of the dropwise addition, the mixture is stirred for 2 hours at 70C. The polyacrylonitrile precipitated is filtered off under suction, washed thoroughly with water and dried at 50Co 75 parts by weight of a pol~mer are obtained E.XAMPLE 25 .
o.6 part by weight of azo-di-isobutyric acid-(N~N'-bis-2-hydroxypropyl)-amidine is used as an - initiator under the same test conditions as in E~ample 2l~.
Le A 19 058 62 parts by weight of a polymer are obtained.
_ Following the procedure of Example 20, a mixture of 22.5 parts of styrene and 7.5 parts of acrylonitrile is polymerised in the presence of 0.15 part o azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine. Instead of tetrahydrofuran, dimethyl formamide is used as a solvent for the copolymer.
Drying _ vacuo leaves 19 parts o a purified copolymer consisting of 72 % of styrene units and 28 % of acrylonitrile units and hav m g an intrinsic viscosityof 0.86, as measured in dLmethyl formamide.
EX~MPLE 27 A mixture of 45 parts of styrene and 55 parts of _-butyl acrylate, 400 parts of chlorobenzene and 2 parts of azo-di-isobutyric acid-(N,N'-bis-3-hydroxybutyl~-amidine are polymerised in the same way as in Example 22, but for
Intrinsic viscosity ~as measured in tetrahydrofuran): 0.49.
The polymers may be crosslinked with diisocyanates and polyisocyanates through the terminal hydro~yl group3 incorporated.
2 parts by weight of the polystyrene containing terminal hydro~yl groups obtained in accordance with E~ample 20 are dissolved in 18 parts by weight of anhydrous chlorobenzene. The solution is crosslinked with 0.2 part by weight of he~a~ethylene diisocyanate in the presence of 0.05 part by weight of tin(II) octoate.
After standing for 24 hours at room temperature, a crosslinked gel has formed. A film cast onto glass immediately after mixing is also crossli~ked after drying for 24 hours.
E ~MPLE 21 A solution of o.6 p~rt by weight of azo-di-iso-butyric acid-(N,N',N'-tris-2-hydroYyethyl)-amidine in 30 parts by weight of methyl me-thacrylate is polymerised in the same way as described in Example 20. After dissolution and reprecipitation, 19 g of a polymer having an intrinsic ~iscosity in tetrahydrofuran of 0.45 are obtained.
A solution of 30 parts by weight of acrylonitrile, 3o 70 parts by weight of dimethyl fo~amide and 0.3 part by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydro.Yyethyl)-amidine is stirred for 6 hours at 80C
in a three--necked flask equipped with a thermometer, reflu~ condenser and nitrogen feedpipe. The highly Le A 19 058 ~3~
~iscous solution formed is precipitated in 1000 parts by weight o~ water and dried in vacuo at 50C.
15 parts o~ a polymer having an intrinsic viscosi-ty ~~:.-~s measured in dimethyl formamide) of 0.58 are obtained.
E~AMP~E~
___ Following the procedure of Example 22, a solution ~i 30..parts by weight o~ vinyl acetate, 70 parts by weight of tert.-butanol, 0.3 part by weight o~ azo-di~
-isobutyric acid-(N,N7-bis-~-hydroxyethyl)-amidine and parts by weight of acetic acid is stirred for 6 hours at 80C. After th~ highly viscous solution ha~ been ~recipitated in 1000 parts by weight of water, 13 parts by weight of a polymer having an intrinsic viscosity ~s measured in dimethyl formamide) of 0.35 are obtained af-ter drying.
~AMPLE 24 500 parts by weight of distilled water are i.ltroduced into a three-necked fla~kO The content~ of the flask are then heated under nitrogen to an internal ~s) tempera.ture of 70C, after which a) lU0 parts by weight of acrylonitrile, and b3 a solution o~ 0.5 part by weight of azo-di-isobutyric acid-(N,N'-bis-2-hydro~yethyl)-amidine in 50 parts by weight of distilled water are uni~ormly added dropwise over a period of 2 hours.
0~ completion of the dropwise addition, the mixture is stirred for 2 hours at 70C. The polyacrylonitrile precipitated is filtered off under suction, washed thoroughly with water and dried at 50Co 75 parts by weight of a pol~mer are obtained E.XAMPLE 25 .
o.6 part by weight of azo-di-isobutyric acid-(N~N'-bis-2-hydroxypropyl)-amidine is used as an - initiator under the same test conditions as in E~ample 2l~.
Le A 19 058 62 parts by weight of a polymer are obtained.
_ Following the procedure of Example 20, a mixture of 22.5 parts of styrene and 7.5 parts of acrylonitrile is polymerised in the presence of 0.15 part o azo-di-isobutyric acid-(N,N'-bis-2-hydroxyethyl)-amidine. Instead of tetrahydrofuran, dimethyl formamide is used as a solvent for the copolymer.
Drying _ vacuo leaves 19 parts o a purified copolymer consisting of 72 % of styrene units and 28 % of acrylonitrile units and hav m g an intrinsic viscosityof 0.86, as measured in dLmethyl formamide.
EX~MPLE 27 A mixture of 45 parts of styrene and 55 parts of _-butyl acrylate, 400 parts of chlorobenzene and 2 parts of azo-di-isobutyric acid-(N,N'-bis-3-hydroxybutyl~-amidine are polymerised in the same way as in Example 22, but for
6 hours at 75 &. me copolymer ormed is precipitated from its chlorobenzene solu-tion with 1500 parts of methanol and dried Ln vacuo at 50C. 65 parts of a copolymer of 49 % of styrene units and 51 % of n-b~ltyl acrylate units with an intrinsic viscosity of 0.72, as measured in di~ethyl formamide, are obtained.
Crosslinking of the copolymer through the OH-groups incorporated 2 parts of the copolymer dissolved in 8 parts of anhydrous chloro-benzene are mixed with 0.05 part of tin (II) octoate and 0.2 part of isophorone diisocyanate. Films cast onto gLass frcm this solution are crosslinked after 24 hours at room temperature and can no longer be dissolved by chlorobenzene.
.
Crosslinking of the copolymer through the OH-groups incorporated 2 parts of the copolymer dissolved in 8 parts of anhydrous chloro-benzene are mixed with 0.05 part of tin (II) octoate and 0.2 part of isophorone diisocyanate. Films cast onto gLass frcm this solution are crosslinked after 24 hours at room temperature and can no longer be dissolved by chlorobenzene.
.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of an aqueous plastics dispersion, which comprises emulsion polymerisation of at least one olefinically unsaturated poly-merisable monomer in the presence of a water-soluble polymerisation initiator comprising an azo,di-isobutyric acid-(N,N'-hydroxyalkyl)-amidine corresponding to the general formula (I):
(I) in which R and R', which may be the same or different, represent linear or branched alkylene radicals containing from 2 to 4 carbon atoms, and X represents hydrogen or R'-OH.
(I) in which R and R', which may be the same or different, represent linear or branched alkylene radicals containing from 2 to 4 carbon atoms, and X represents hydrogen or R'-OH.
2. A process as claimed in Claim 1, wherein the polymerisation initiator is completely or partly used in the form of a salt of the azo-di-isobutyric acid-(N,N'-hydroxyalkyl) amidine corresponding to the formula (I) and a saturated or mono-olefinically unsaturated carboxylic or sulphonic acid.
3. A process as claimed in Claim 2, wherein the mono-olefinically unsatur-ated carboxylic acid is acrylic acid, methacrylic acid, itaconic acid, or itaconic acid semiester or maleic acid semiester with, in each case, 1 to 18 carbon atoms in the alcohol radical.
4. A process as claimed in Claim 1, wherein polymerisation is carried out at a temperature of from 50 to 90°C, and in the absence of applied pressure or under a pressure of up to 200 bars.
5. A process as claimed in Claim 1, wherein the initiator is present in aquantity of from 0.2 to 10 % by weight, based on the total weight of monomer.
6. An aqueous plastics dispersion when produced by a process as claimed in Claim 1.
7. An aqueous coating composition comprising a dispersion as claimed in Claim 6 in combination with a phenoplast or aminoplast.
8. A coating composition produced from a dispersion as claimed in Claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782841033 DE2841033A1 (en) | 1978-09-21 | 1978-09-21 | METHOD FOR PRODUCING AQUEOUS POLYMER DISPERSIONS |
| DEP2841033.5 | 1978-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139031A true CA1139031A (en) | 1983-01-04 |
Family
ID=6050009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000335946A Expired CA1139031A (en) | 1978-09-21 | 1979-09-19 | Process for the production of aqueous polymer dispersions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0009659A1 (en) |
| JP (1) | JPS5543194A (en) |
| CA (1) | CA1139031A (en) |
| DE (1) | DE2841033A1 (en) |
| ES (1) | ES484325A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3005889A1 (en) * | 1980-02-16 | 1981-09-03 | Bayer Ag, 5090 Leverkusen | Emulsion polymerisation with prepolymer contg. azo gps. - as catalyst and emulsifier, giving stable emulsion in water or organic solvent |
| DE3048883A1 (en) * | 1980-12-23 | 1982-07-15 | Boehringer Mannheim Gmbh, 6800 Mannheim | Hydrophilic latex particles prodn. by emulsion polymerisation - without added surfactant, useful as carriers for biological or immunological cpds. |
| EP0145220B1 (en) * | 1983-11-10 | 1988-06-01 | Nitto Boseki Co., Ltd. | Process for producing polymers of monoallylamine |
| JPH075647B2 (en) * | 1986-01-29 | 1995-01-25 | 出光石油化学株式会社 | Method for producing hydroxyl group-containing liquid diene polymer |
| JP2598641B2 (en) * | 1986-08-28 | 1997-04-09 | 和光純薬工業株式会社 | Novel cyclic azoamidine compound and its salt |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2599299A (en) * | 1950-06-23 | 1952-06-03 | Du Pont | Aliphatic azo compounds having guanyl radicals on tertiary carbon attached to azo nitrogen |
| US2599300A (en) * | 1950-06-23 | 1952-06-03 | Du Pont | Polymerization employing amidines having azo groups |
| DE1693164C3 (en) * | 1968-01-30 | 1975-03-27 | Bayer Ag, 5090 Leverkusen | Process for the preparation of azo-di-isobutyric acid amidine |
-
1978
- 1978-09-21 DE DE19782841033 patent/DE2841033A1/en not_active Withdrawn
-
1979
- 1979-09-07 EP EP79103334A patent/EP0009659A1/en not_active Withdrawn
- 1979-09-19 JP JP11945779A patent/JPS5543194A/en active Pending
- 1979-09-19 CA CA000335946A patent/CA1139031A/en not_active Expired
- 1979-09-20 ES ES484325A patent/ES484325A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES484325A1 (en) | 1980-05-16 |
| JPS5543194A (en) | 1980-03-26 |
| EP0009659A1 (en) | 1980-04-16 |
| DE2841033A1 (en) | 1980-04-03 |
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