CA1121531A - Acrylonitrile copolymer dispersions - Google Patents
Acrylonitrile copolymer dispersionsInfo
- Publication number
- CA1121531A CA1121531A CA000326699A CA326699A CA1121531A CA 1121531 A CA1121531 A CA 1121531A CA 000326699 A CA000326699 A CA 000326699A CA 326699 A CA326699 A CA 326699A CA 1121531 A CA1121531 A CA 1121531A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- acrylonitrile
- emulsifier
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
Abstract
(11) (A) No. 1,121,531 (45) ISSUED 820406 (52) CLASS 400-48 (51) INT. CL.3BOlF 17/42, (19) (CA) CANADIAN PATENT (12) (54) ACRYLONITRILE COPOLYMER DISPERSIONS
(72) Lindner, Christian;
Ott, Karl-Heinz;
Humme, Gert, Germany (Federal Republic of) (73) Granted to Bayer Aktiengesellschaft Germany (Federal Republic of) (21) APPLICATION No. 326,699 (22) FILED 790501 (30) PRIORITY DATE Germany (Federal Republic of) (P 28 19 380.8) 780503 No. OF CLAIMS 2 - NO DRAWING
(72) Lindner, Christian;
Ott, Karl-Heinz;
Humme, Gert, Germany (Federal Republic of) (73) Granted to Bayer Aktiengesellschaft Germany (Federal Republic of) (21) APPLICATION No. 326,699 (22) FILED 790501 (30) PRIORITY DATE Germany (Federal Republic of) (P 28 19 380.8) 780503 No. OF CLAIMS 2 - NO DRAWING
Description
l~ZlS~
This invention relates to polymer dispersions of copolymers of acrylonitrlle with other vinyl monomers having a low residual monomerlc acrylonitrile content and to a process for their production.
It is known that radically initiated, aqueous polymer dispersions contain fractions of unreacted monomer. These residual contents generally have to be removed before the emulsion (dispersion) accumulating during emulsion polymerisation is further processed, for example by subjecting the emulsion (dispersion) to a degassing process or by chemically destroying the residual contents of monomers. It is desirable to reduce the residual monomer content to such an extent that, for example, the necessary degassing process can be shortened or dispensed with. The advantage of improving the process in this way is that it simplifies the production of the polymers from emulsions (dispersions) and reduces possible atmospheric pollution by free monomers.
The object of the present invention is to produce aqueous acrylonitrile copolymer dispersions having residual contents of monomeric acrylonltrile of 500 ppm and, in special cases, ~ 100 ppm.
According to the lnvention, this object is achieved by polymerising acrylonitrile and at least one other vinyl monomer under emulsion polymerisation conditions and under special process conditions in the presence of selected anionic emulsifiers up to a substantially complete conversion of the monomers to form 30 to 45 % by weight aqueous copolymer dispersions having an average particle diameter of - 90 nm, as determined by the light scattering method.
The emulsifiers used in the process according to the invention, i.e. alkylaryl polyethylene glycol Le A 18 85~
,. - ~
3~
ether sulphates and alkylaryl sulphonate polyalkylene glycol ether sulphates ~alkali metal or ammonium salts), and their emulsifying properties are known from United States Patents Nos. 2,203,883 and 2,106,716. In addition, it is known from United States Patent No. 3,592,879 (column 5, line 68) that acryloni-trile-styrene copolymers can be produced by emulsion polymerisation using C10-C20-alkylaryl sulphates as emulsifier.
The present invention provides a process for the production of 30 to 45 % by weight aqueous acrylonitrile copolymer dispersions having an average particle diameter of < 90 nm, as determined by the light scattering method, and a residual monomer content of acrylonitrile of < 500 ppm by the emulsion poly-merisation of from 5 to 50 parts by weight of acrylonitrile and from 50 to 95 parts by weight of at least one other vinyl monomer (the sum of the parts by weight being 100) at temperatures of from 40 to 85C in the presence of at least one water-soluble radical former or redox system and in the presence of at least one anionic emulsifier and, optionally, the usual auxiliaries up to a substan-tially complete conversion of the monomers, characterised in that at least one emulsifier corresponding to the formula (I):
Rl ~ O(CH2-CH2-0)_-S03Me (I) (S03Me)n in which ~1 represents a branched or t E~
s~
straight-chain alkyl radical containing from 5 to 12 carbon atoms, n = 0 or 1, m = 2 to 12, and Me represents an alkali metal or ammonium, ls used in a total quantity of from 1 to 4 parts by welght, based on 100 parts by weight of monomer, from 60 to 95 ~ by weight of the quantity of emulsifler and from q to 20 ~ by weiclht of the total quantlty Of monomers being inittally introduced in most of the w~ter (in 50 to 90 % by wt. of the total amount of w~ter used in the process), polymeri~ation being initiated with an aqueoUs solution of the r~dical former or ~he redox system~, and from 5 to 40 % by weight of the emulsifier and the balance of the monomers subsequently being added.
In formula (I) above, Me preferably represents Na. In addition, compounds of formula (I) in which n = 0 are preferred.
The monomers used are mixtures of from 5 to 50 parts by weight, preferably from 20 to 40 parts by weight, of acrylonitrile and from 95 to 50 parts by weight, preferably from 80 to 60 parts by weight, of at least one vinyl monomer which can be copolymerised with acrylonitrile, for example aromatic vinyl compounds, preferably styrene or ~-methyl styrene, and (meth)acrylic acid esters of which the alcohol components contain from 1 to 12 carbon atoms, preferably methyl methacrylate and n-butyl acrylate.
Suitable radical formers for the emulsion polymerisation reaction are the usual water-soluble initiators used in the usual quantities (from 0.1 to 5 ~ by weight, based on monomer) at temperatures of from 40C to 80C, such as for example alkali metal persulphates, ammonium persulphate, water-soluble Le A 18 859 peroxides, percarboxylic acid esters, a~o ccmpounds and also the usual redox systems, such as for example mixtures of persulphates and pyrosulphites or per-sulphates and oxalic acid. The radical formers are preferably used as 0.5 to 10 % by wt. aqueous solutions.
If desired, the emulsion polymerisation reaction may ~e carried out in the presence of so-called molecular weight regulators (usual auxiliaries), such as aIkyl mercaptans, for exampler used in quantities of from about 0.1 to 1.0 by weight, based on monomer. Polymerisation is preferably OE ried out at pH-values in the range of from 3 to 9 and more particularly at pH-values in the range of frcm 4 to 8.
In one preferred en}cdlm,nt of the polymerisation process according to the invention, a mixture consisting of water, optionally acids or alkalis, com~
plex formers for heavy metal ions (usual auxiliaries), such as nitriloaoetic acid, alkyl mercaptan, some of the mcnomers and most of the emulsifier is heated to the reqlired reaction temperature and, after polymerisation has been initiated with one of the usual initiators, mixtures of mLncmers and mercaptan on t~e one hand and water and emulsifier on the other hand are added to this mixture. me quantities by weight of monamer ~ixture in the polymerisation mix-ture æe selected in such a way that polymer dispersions having a polymer con-tent of fram 30 to 45 % by weight are obtained an completion of polymerisation.From 4 to 20 ~ by weight of the total manomer mixture for polymerisation are introduced initially.
me process according to the invention gives dispersions of acrylo-nitrile copolymers which have average p æticle diameters of < 90 nm and an extremely low residual oontent or monameric acrylonitrile. In 53:1 the case of dispersions of acrylonitrile/styrene copolymers, the residual monomeric acrylonltrile content amounts to less than 100 ppm and, in the case of acrylonitrile~-methyl styrene dispersions, to less than 500 ppm. As can be seen from the Comparison Examples, the residual contents of acrylonitrile are considerably greater where other standard emulsifiers are used in the same procedure.
The acrylonitrile copolymer dispersions obtained by the process according to the invention may be coagulated by the usual methods and the copolymers obtained may be processed to form high-impact plastics mQuldinss, optionally after admixture with suitable rubbers and grafted rubbers.
The following experimental results illustrate the effect of reducing the residual acrylonitrile content by the measures according to the invention and the use of the special emulsifiers corresponding to formula ~I) above in accordance with the invention.
The particle size of the latex particles was determined by the light scattering method (c M.
Hoffmann, H. Kromer and R. Kuhn: Polymeranalytik II, Georg Thieme Verlag, Stuttgart, 1977, pages 267 to 268). The residual acrylonitrile contents were determined by quantitative gas chromatography in Carbowachs 20 M_saure(Tr~demark)(prOducts of the Merck Company) and PND-detectors (PND = phosphorus-nitrogen detector).
EX~PLE 1 85.3 parts by weight of water, 2.0 parts by weight of emulsifier according to 1.1.1, x parts by weight of 1 N sodium hydroxide, 1O8 parts by weight of acrylonitrile, 4.8 parts by weight of ..
~lZ~53~
styrene and 0.0002 part by weight of tert.-dodecyl mercaptan are initially introduced for polymerisation.
Polymerisation is initiated at a reaction temperature of 63 to 65C by the addition of a solution of 16 parts by weight of water and 0.32 parts by weight of potassium persulphate.
The following solutions are then uniformly introduced simultaneously, but separately, over a period of 4 hours~
Solution 1) 72.0 parts bv weight of styrene 28 parts b-y weight of acrylonitrile 0.27 part by weight of tert.-dodecyl mercaptan Solution 2~ 26.7 parts by weight of water y parts by weight of 1 N sodium hydroxide 0.56 part by weight of emulsifier according to 1.1.1.
This is followed by stirring for 4 hours at 63 to 65C. Polymer disperslons are obtained, their properties being shown in the following Table.
Le A ~
3:1 -- 8 -- ~
O J- O I`
~ 8 ~ ,, ~, .,, ~, _I _ N r~l. la 41 r) r/l D~ N
. ~ O O ~1 Q~.,l ~ ~1 ~ ~,X
~1 ~ a~ a~
~i --I N 1 ~1 ~ ~ a~ a~
~J e. ~ ~ N
Q~ ~ ~ ~ I
N ~ l 0 a~ a I P.~ a ~ Q
Ul Ul .,1 1 ~Z g ~ ,1 ~ O ~
~ ~.,1 ~ ~ ~
~ O X ~ U~ ~ ~
,¢ Z: ~ _l ,i o o o al o E~ ,~.C Z u~
1' 1' A r~ r~ ~
~C c~ o ~ O
Y ~ ~ e, ~, ~, Le A 18 859 .
l:~Z1~3~
~ 9 _ 141 parts by weight of water, 2.8 parts by weight of emulsifier according to 2.1, 0.06 part by weight of the sodium salt of ethylene diamine tetraacetic acid, 5.5 parts by weight of acrylonitrile, 12,2 parts by weight of a-methyl styrene and 0.08 part by weight of tert.-dodecyl mercaptan are initially introduced for polymerisation.
Polymerisation is initiated at a reaction temperature of 70C by the addition of a solution of 15.6 parts by weight of water and 0.35 part by weight of potassium persulphate.
The following solutions are then unifor~ly introduced simultaneously, but separately, over a period of 4 hours:
Solution 1) 69 parts by weight of a-methyl styrene 31 parts by weight of acrylonitrile 0.54 part by weight of tert.-dodecyl mercaptan Solution 2) 29 parts by weight of water 0.67 part by weight of emulsifier according to 2.1.
This i5 followed by stirring for 4 hours at 70C.
Polymer dispersions are obtained, their residual acrylonitrile contents being shown in the following Table:
This invention relates to polymer dispersions of copolymers of acrylonitrlle with other vinyl monomers having a low residual monomerlc acrylonitrile content and to a process for their production.
It is known that radically initiated, aqueous polymer dispersions contain fractions of unreacted monomer. These residual contents generally have to be removed before the emulsion (dispersion) accumulating during emulsion polymerisation is further processed, for example by subjecting the emulsion (dispersion) to a degassing process or by chemically destroying the residual contents of monomers. It is desirable to reduce the residual monomer content to such an extent that, for example, the necessary degassing process can be shortened or dispensed with. The advantage of improving the process in this way is that it simplifies the production of the polymers from emulsions (dispersions) and reduces possible atmospheric pollution by free monomers.
The object of the present invention is to produce aqueous acrylonitrile copolymer dispersions having residual contents of monomeric acrylonltrile of 500 ppm and, in special cases, ~ 100 ppm.
According to the lnvention, this object is achieved by polymerising acrylonitrile and at least one other vinyl monomer under emulsion polymerisation conditions and under special process conditions in the presence of selected anionic emulsifiers up to a substantially complete conversion of the monomers to form 30 to 45 % by weight aqueous copolymer dispersions having an average particle diameter of - 90 nm, as determined by the light scattering method.
The emulsifiers used in the process according to the invention, i.e. alkylaryl polyethylene glycol Le A 18 85~
,. - ~
3~
ether sulphates and alkylaryl sulphonate polyalkylene glycol ether sulphates ~alkali metal or ammonium salts), and their emulsifying properties are known from United States Patents Nos. 2,203,883 and 2,106,716. In addition, it is known from United States Patent No. 3,592,879 (column 5, line 68) that acryloni-trile-styrene copolymers can be produced by emulsion polymerisation using C10-C20-alkylaryl sulphates as emulsifier.
The present invention provides a process for the production of 30 to 45 % by weight aqueous acrylonitrile copolymer dispersions having an average particle diameter of < 90 nm, as determined by the light scattering method, and a residual monomer content of acrylonitrile of < 500 ppm by the emulsion poly-merisation of from 5 to 50 parts by weight of acrylonitrile and from 50 to 95 parts by weight of at least one other vinyl monomer (the sum of the parts by weight being 100) at temperatures of from 40 to 85C in the presence of at least one water-soluble radical former or redox system and in the presence of at least one anionic emulsifier and, optionally, the usual auxiliaries up to a substan-tially complete conversion of the monomers, characterised in that at least one emulsifier corresponding to the formula (I):
Rl ~ O(CH2-CH2-0)_-S03Me (I) (S03Me)n in which ~1 represents a branched or t E~
s~
straight-chain alkyl radical containing from 5 to 12 carbon atoms, n = 0 or 1, m = 2 to 12, and Me represents an alkali metal or ammonium, ls used in a total quantity of from 1 to 4 parts by welght, based on 100 parts by weight of monomer, from 60 to 95 ~ by weight of the quantity of emulsifler and from q to 20 ~ by weiclht of the total quantlty Of monomers being inittally introduced in most of the w~ter (in 50 to 90 % by wt. of the total amount of w~ter used in the process), polymeri~ation being initiated with an aqueoUs solution of the r~dical former or ~he redox system~, and from 5 to 40 % by weight of the emulsifier and the balance of the monomers subsequently being added.
In formula (I) above, Me preferably represents Na. In addition, compounds of formula (I) in which n = 0 are preferred.
The monomers used are mixtures of from 5 to 50 parts by weight, preferably from 20 to 40 parts by weight, of acrylonitrile and from 95 to 50 parts by weight, preferably from 80 to 60 parts by weight, of at least one vinyl monomer which can be copolymerised with acrylonitrile, for example aromatic vinyl compounds, preferably styrene or ~-methyl styrene, and (meth)acrylic acid esters of which the alcohol components contain from 1 to 12 carbon atoms, preferably methyl methacrylate and n-butyl acrylate.
Suitable radical formers for the emulsion polymerisation reaction are the usual water-soluble initiators used in the usual quantities (from 0.1 to 5 ~ by weight, based on monomer) at temperatures of from 40C to 80C, such as for example alkali metal persulphates, ammonium persulphate, water-soluble Le A 18 859 peroxides, percarboxylic acid esters, a~o ccmpounds and also the usual redox systems, such as for example mixtures of persulphates and pyrosulphites or per-sulphates and oxalic acid. The radical formers are preferably used as 0.5 to 10 % by wt. aqueous solutions.
If desired, the emulsion polymerisation reaction may ~e carried out in the presence of so-called molecular weight regulators (usual auxiliaries), such as aIkyl mercaptans, for exampler used in quantities of from about 0.1 to 1.0 by weight, based on monomer. Polymerisation is preferably OE ried out at pH-values in the range of from 3 to 9 and more particularly at pH-values in the range of frcm 4 to 8.
In one preferred en}cdlm,nt of the polymerisation process according to the invention, a mixture consisting of water, optionally acids or alkalis, com~
plex formers for heavy metal ions (usual auxiliaries), such as nitriloaoetic acid, alkyl mercaptan, some of the mcnomers and most of the emulsifier is heated to the reqlired reaction temperature and, after polymerisation has been initiated with one of the usual initiators, mixtures of mLncmers and mercaptan on t~e one hand and water and emulsifier on the other hand are added to this mixture. me quantities by weight of monamer ~ixture in the polymerisation mix-ture æe selected in such a way that polymer dispersions having a polymer con-tent of fram 30 to 45 % by weight are obtained an completion of polymerisation.From 4 to 20 ~ by weight of the total manomer mixture for polymerisation are introduced initially.
me process according to the invention gives dispersions of acrylo-nitrile copolymers which have average p æticle diameters of < 90 nm and an extremely low residual oontent or monameric acrylonitrile. In 53:1 the case of dispersions of acrylonitrile/styrene copolymers, the residual monomeric acrylonltrile content amounts to less than 100 ppm and, in the case of acrylonitrile~-methyl styrene dispersions, to less than 500 ppm. As can be seen from the Comparison Examples, the residual contents of acrylonitrile are considerably greater where other standard emulsifiers are used in the same procedure.
The acrylonitrile copolymer dispersions obtained by the process according to the invention may be coagulated by the usual methods and the copolymers obtained may be processed to form high-impact plastics mQuldinss, optionally after admixture with suitable rubbers and grafted rubbers.
The following experimental results illustrate the effect of reducing the residual acrylonitrile content by the measures according to the invention and the use of the special emulsifiers corresponding to formula ~I) above in accordance with the invention.
The particle size of the latex particles was determined by the light scattering method (c M.
Hoffmann, H. Kromer and R. Kuhn: Polymeranalytik II, Georg Thieme Verlag, Stuttgart, 1977, pages 267 to 268). The residual acrylonitrile contents were determined by quantitative gas chromatography in Carbowachs 20 M_saure(Tr~demark)(prOducts of the Merck Company) and PND-detectors (PND = phosphorus-nitrogen detector).
EX~PLE 1 85.3 parts by weight of water, 2.0 parts by weight of emulsifier according to 1.1.1, x parts by weight of 1 N sodium hydroxide, 1O8 parts by weight of acrylonitrile, 4.8 parts by weight of ..
~lZ~53~
styrene and 0.0002 part by weight of tert.-dodecyl mercaptan are initially introduced for polymerisation.
Polymerisation is initiated at a reaction temperature of 63 to 65C by the addition of a solution of 16 parts by weight of water and 0.32 parts by weight of potassium persulphate.
The following solutions are then uniformly introduced simultaneously, but separately, over a period of 4 hours~
Solution 1) 72.0 parts bv weight of styrene 28 parts b-y weight of acrylonitrile 0.27 part by weight of tert.-dodecyl mercaptan Solution 2~ 26.7 parts by weight of water y parts by weight of 1 N sodium hydroxide 0.56 part by weight of emulsifier according to 1.1.1.
This is followed by stirring for 4 hours at 63 to 65C. Polymer disperslons are obtained, their properties being shown in the following Table.
Le A ~
3:1 -- 8 -- ~
O J- O I`
~ 8 ~ ,, ~, .,, ~, _I _ N r~l. la 41 r) r/l D~ N
. ~ O O ~1 Q~.,l ~ ~1 ~ ~,X
~1 ~ a~ a~
~i --I N 1 ~1 ~ ~ a~ a~
~J e. ~ ~ N
Q~ ~ ~ ~ I
N ~ l 0 a~ a I P.~ a ~ Q
Ul Ul .,1 1 ~Z g ~ ,1 ~ O ~
~ ~.,1 ~ ~ ~
~ O X ~ U~ ~ ~
,¢ Z: ~ _l ,i o o o al o E~ ,~.C Z u~
1' 1' A r~ r~ ~
~C c~ o ~ O
Y ~ ~ e, ~, ~, Le A 18 859 .
l:~Z1~3~
~ 9 _ 141 parts by weight of water, 2.8 parts by weight of emulsifier according to 2.1, 0.06 part by weight of the sodium salt of ethylene diamine tetraacetic acid, 5.5 parts by weight of acrylonitrile, 12,2 parts by weight of a-methyl styrene and 0.08 part by weight of tert.-dodecyl mercaptan are initially introduced for polymerisation.
Polymerisation is initiated at a reaction temperature of 70C by the addition of a solution of 15.6 parts by weight of water and 0.35 part by weight of potassium persulphate.
The following solutions are then unifor~ly introduced simultaneously, but separately, over a period of 4 hours:
Solution 1) 69 parts by weight of a-methyl styrene 31 parts by weight of acrylonitrile 0.54 part by weight of tert.-dodecyl mercaptan Solution 2) 29 parts by weight of water 0.67 part by weight of emulsifier according to 2.1.
This i5 followed by stirring for 4 hours at 70C.
Polymer dispersions are obtained, their residual acrylonitrile contents being shown in the following Table:
2.1.) Emulsifier *) Latex Residual acrylo-particle nitrile content (ppM) size (nm) C (Comp.) 55 2045 *) For the definition of the emulsifiers, see 1.1.1.).
, ..
llZ1531 As can be seen from the preceding Examples, therefore, the residual cont2nts of acrylonitr~le ln the polymer dispersion on completion of the emulsion polymerisation of acrylonitrile wlth aromatic vinyl compounds, for example, are surprisingly much lower where the emulsifiers of formula (I) are used than where other standard polymerisation emulsifiers (such as for example A and C in 1.1.1.) are used.
90 parts by weight of water, 2.5 parts by weight of emulsifier according to 3.1, 1.8 parts by weight of acrylo~itrile, 4.8 parts by weight of styrene, 0.6 part by weight of methyl methacrylate and 0.00025 part by weight of tert.-dodecyl mercaptan are initially introduced for polymerisation.
Polymerisation is initiated at a reaction temperature of 63 to 65C by the addition of a solution of 15 parts by weight of water and 0.3 part by weight of potassium persulphate.
The following solutions are then uniformly added over a period of 4.5 hours:
Solution 1~ 9 parts by weight of methyl methacrylate 65 parts by weight of styrene 26 parts by weight of acrylonitrile 0.2 part by weight of n-butyl mercaptan Solution 2) 26 parts by weight of water 0.3 part by weight of emulsifier.
This is followed by stirring for 4 hours at 63 to 65C. Polymer dispersions are obtainedl their properties being shown in the following Table:
Le~A 18 8,~2 9 ~Z153~L
.1.1.) Emulsifier ~) Latex Residual acrylo-particle nitrile content =
C (Compari~on) 65 3010 ~ (Invention) 67 480 *) For the definition of t:~e emulsiflers, see 1.1.1.).
Le A 18 85~
, ..
llZ1531 As can be seen from the preceding Examples, therefore, the residual cont2nts of acrylonitr~le ln the polymer dispersion on completion of the emulsion polymerisation of acrylonitrile wlth aromatic vinyl compounds, for example, are surprisingly much lower where the emulsifiers of formula (I) are used than where other standard polymerisation emulsifiers (such as for example A and C in 1.1.1.) are used.
90 parts by weight of water, 2.5 parts by weight of emulsifier according to 3.1, 1.8 parts by weight of acrylo~itrile, 4.8 parts by weight of styrene, 0.6 part by weight of methyl methacrylate and 0.00025 part by weight of tert.-dodecyl mercaptan are initially introduced for polymerisation.
Polymerisation is initiated at a reaction temperature of 63 to 65C by the addition of a solution of 15 parts by weight of water and 0.3 part by weight of potassium persulphate.
The following solutions are then uniformly added over a period of 4.5 hours:
Solution 1~ 9 parts by weight of methyl methacrylate 65 parts by weight of styrene 26 parts by weight of acrylonitrile 0.2 part by weight of n-butyl mercaptan Solution 2) 26 parts by weight of water 0.3 part by weight of emulsifier.
This is followed by stirring for 4 hours at 63 to 65C. Polymer dispersions are obtainedl their properties being shown in the following Table:
Le~A 18 8,~2 9 ~Z153~L
.1.1.) Emulsifier ~) Latex Residual acrylo-particle nitrile content =
C (Compari~on) 65 3010 ~ (Invention) 67 480 *) For the definition of t:~e emulsiflers, see 1.1.1.).
Le A 18 85~
Claims (2)
- - 12 -l. A process for the production of 30 to 45 %
by weight aqueous acrylonitrile copolymer dispersions having an average particle diameter of ? 90 nm, as determined by the light scattering method, and a residual monomer content of acrylonitrile ? 500 ppm which comprises emulsion polymerisation of from 5 to 50 parts by weight of acrylonitrile and from 50 to 95 parts by weight of at least one other vinyl monomer (the sum of the parts by weight being 100) up to a substantially complete conversion at temperatures of from 40 to 80°C in the presence of at least one water-soluble radical former or redox system and, optionally, the usual auxiliaries, and in the presence of at least one anionic emulsifier corresponding to the Formula (I):
(I) in which R1 represents a branched or straight-chain alkyl radical containing from 5 to 12 carbon atoms, n = 0 or 1, m = 2 to 12, and Me represents an alkali metal or ammonium, said emulsifier is used in a total quantity of from 1 to 4 parts by weight, based on 100 parts by weight of monomers, Le A 18 859 from 60 to 95 % by weight of the quantity of emulsifier and from 4 to 20 % by weight of the total quantity of monomers being initially introduced in most of the water, polymerisation being initiated with an aqueous solution of the radical former or the redox system, and from 5 to 40 % by weight of the emulsifier in the rest of the water and the balance of the monomers subsequently being added. - 2. A process as claimed in Claim 1, characterised in that the vinyl monomer used is styrene, .alpha.-methyl styrene, methyl methacrylate or n-butyl acrylate or a mixture thereof.
Le A 18 859
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2819380.8 | 1978-05-03 | ||
| DE19782819380 DE2819380A1 (en) | 1978-05-03 | 1978-05-03 | ACRYLIC NITRILE COPOLYMERIZED DISPERSIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121531A true CA1121531A (en) | 1982-04-06 |
Family
ID=6038568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000326699A Expired CA1121531A (en) | 1978-05-03 | 1979-05-01 | Acrylonitrile copolymer dispersions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0005221B1 (en) |
| JP (1) | JPS54144492A (en) |
| CA (1) | CA1121531A (en) |
| DE (2) | DE2819380A1 (en) |
| ES (1) | ES480155A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1157598A (en) * | 1979-10-03 | 1983-11-22 | Paritosh M. Chakrabarti | Polyethyleneoxy sulfonate surfactants |
| DE3134222A1 (en) * | 1981-08-29 | 1983-03-10 | Röhm GmbH, 6100 Darmstadt | METHOD FOR PRODUCING ACRYLIC PLASTIC DISPERSIONS |
| JPH0544922Y2 (en) * | 1988-11-16 | 1993-11-16 | ||
| DE4136657A1 (en) * | 1991-11-07 | 1993-05-13 | Basf Ag | EMULSION POLYMERISATE WITH LOW RESIDUAL MONOMER CONTENT |
| EP3995547B1 (en) | 2019-07-02 | 2024-02-07 | Konica Minolta, Inc. | Thermally curable ink-jet ink |
| JPWO2021090872A1 (en) | 2019-11-08 | 2021-05-14 | ||
| EP4215551A4 (en) | 2020-09-18 | 2024-03-13 | Konica Minolta Inc | Curable composition, ink for solder resist, and printed circuit board |
| JP2022070019A (en) | 2020-10-26 | 2022-05-12 | コニカミノルタ株式会社 | Inkjet textile printing ink and image forming method |
| WO2022102058A1 (en) | 2020-11-12 | 2022-05-19 | コニカミノルタ株式会社 | Inkjet recording method and inkjet recording device |
| JP2023000162A (en) | 2021-06-17 | 2023-01-04 | コニカミノルタ株式会社 | Ink for printing |
| JP2023136700A (en) | 2022-03-17 | 2023-09-29 | コニカミノルタ株式会社 | Inkjet ink composition, recorded matter, inkjet recording method and inkjet recording system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3595823A (en) * | 1969-07-18 | 1971-07-27 | Westvaco Corp | Stable aqueous emulsions of styrene-acrylonitrile-acrylic therpolymers |
-
1978
- 1978-05-03 DE DE19782819380 patent/DE2819380A1/en not_active Withdrawn
-
1979
- 1979-04-20 DE DE7979101202T patent/DE2960974D1/en not_active Expired
- 1979-04-20 EP EP79101202A patent/EP0005221B1/en not_active Expired
- 1979-05-01 CA CA000326699A patent/CA1121531A/en not_active Expired
- 1979-05-01 JP JP5259479A patent/JPS54144492A/en active Granted
- 1979-05-02 ES ES480155A patent/ES480155A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2819380A1 (en) | 1979-11-08 |
| DE2960974D1 (en) | 1981-12-24 |
| JPS6261048B2 (en) | 1987-12-19 |
| JPS54144492A (en) | 1979-11-10 |
| EP0005221B1 (en) | 1981-10-14 |
| ES480155A1 (en) | 1980-04-01 |
| EP0005221A3 (en) | 1979-11-28 |
| EP0005221A2 (en) | 1979-11-14 |
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