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EP1129113A1 - Redox polymerization process - Google Patents

Redox polymerization process

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Publication number
EP1129113A1
EP1129113A1 EP99952574A EP99952574A EP1129113A1 EP 1129113 A1 EP1129113 A1 EP 1129113A1 EP 99952574 A EP99952574 A EP 99952574A EP 99952574 A EP99952574 A EP 99952574A EP 1129113 A1 EP1129113 A1 EP 1129113A1
Authority
EP
European Patent Office
Prior art keywords
tert
butyl
temperature
process according
bis
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.)
Withdrawn
Application number
EP99952574A
Other languages
German (de)
French (fr)
Inventor
Andreas Petrus Van Swieten
Petrus Paulus Waanders
Annemarieke Maltha
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel NV
Original Assignee
Akzo Nobel NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Akzo Nobel NV filed Critical Akzo Nobel NV
Priority to EP99952574A priority Critical patent/EP1129113A1/en
Publication of EP1129113A1 publication Critical patent/EP1129113A1/en
Withdrawn legal-status Critical Current

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation

Definitions

  • the present invention relates to a process for emulsion polymerization, to the polymers obtainable by such a process, and to their uses.
  • An object of the present invention is to provide an alternative polymerization process which aims to improve the process time.
  • the first aspect of the present invention provides a process according to claim 1.
  • the polymerization process according to the present invention provides a free radical initiator moiety by means of a redox reaction instead of by thermal decomposition, the polymerization can be earned out with a so-called "cold start", which involves the process time being reduced and the reactor output per unit time being increased.
  • a redox polymerization is known for tertiary butyl hydroperoxide "Trigonox A- W70".
  • Trigonox A- W70 tertiary butyl hydroperoxide
  • the inventors have shown, however, that a redox polymerization utilizing other organic peroxides provides unexpectedly good results.
  • the inventors have shown that polymerization can start at a lower initial temperature, which means that because of the longer "heating-up" time necessary in thermal polymerization, the polymerization time can be reduced utilizing the process of the current invention.
  • the inventors have furthermore demonstrated that the process according to the present invention enables a polymer with a very low residual monomer level to be obtained, whilst, with respect to thermal polymerization, the amount of initiator used can be reduced.
  • the polymerization initiator is most preferably a substantially non-water-soluble initiator, such as defined in claim 7 or 8, since these non-water-soluble initiators yield an unexpectedly high efficiency in polymerization.
  • the higher efficiency results in shorter polymerization times and in polymer resins with improved properties.
  • the higher efficiency of the organic peroxides is expressed by the low level of residual monomers and by the low molecular weights (Mw/Mn) of the polymers formed.
  • the conductivity of the resins initiated with the organic peroxide/redox system is lower than for corresponding resins that were initiated by persulfates.
  • the reductor of the redox system preferably is chosen from the following group: sodium formaldehyde sulfoxylate (SFS), sodium bisulfite, Ascorbic acid (vitamin C), aldehydes, for example glutaraldehyde, sodium metabisulfite, sodium dithionate, and sugars, wherein the reductor most preferably is sodium formaldehyde sulfoxide.
  • FSS sodium formaldehyde sulfoxylate
  • vitamin C Ascorbic acid
  • aldehydes for example glutaraldehyde, sodium metabisulfite, sodium dithionate, and sugars, wherein the reductor most preferably is sodium formaldehyde sulfoxide.
  • the polymerizable species preferably is chosen from the following group: acrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, methoxyethyl acrylate, dimethyl aminoacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearic methacrylate, dimethyl aminomethacrylate, allyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, glycidyl acrylate, vinyl ester of versatic acid, styrene, para-methyl styrene, vinyl acetate,
  • the polymerization is earned out in a conventional emulsion, for example in a mixture of anionic and non-ionic surfactants such as Witconate (sodium alpha- olefin sulfonate) and Syntopon (ethoxylated nonylphenol); however, other emulsifiers or mixtures are also possible.
  • anionic and non-ionic surfactants such as Witconate (sodium alpha- olefin sulfonate) and Syntopon (ethoxylated nonylphenol); however, other emulsifiers or mixtures are also possible.
  • This emulsifier solution preferably is a mixture of nonionic and anionic emulsifiers and most preferably is selected from the group consisting essentially of:
  • a second aspect of the present invention provides a polymer obtainable according to this process.
  • Examples 1-6 are comparative examples and Examples 7-12 are examples according to the present invention using a redox system.
  • Examples 3, 4, 6, 8-12 were subjected to a temperature profile increasing from an initial temperature to a final temperature, i.e. subjected to a so-called "cold-start", and Example 7 was earned out at constant temperature.
  • the preparation of the seed was carried out as follows: The reactor was filled with buffered (NaAc/HAc) emulsifier solution (Witconate/Syntopon), prepared with oxygen-free deionized water. At the polymerization temperature 10% of the pre-emulsion containing soaps (Witconate and Syntopon), monomers, and, in the case of the redox system according to the present invention, also reductor and catalyst, were added. In addition the solution or pre-emulsion of the initiator was added to achieve control over the accurate dosing of the initiator.
  • composition of the buffered soap solution used was as follows: NaAC.3aq 0.25 g (sodium acetate) HAc 0.11 g (acetic acid)
  • the temperature was kept at 70' °C during the polymerization.
  • the composition of the used pre-emulsior i was:
  • VEOVA vinyl ester of versatic acid 22.5 g (monomer)
  • the initiator solution was composed of 4.18 mmoles ammonium/sodium or potassium persulfate in 25 g H 2 O.
  • the total process time including the time needed for heating up the reactor contents to 70°C before polymerization amounted to 5.5 hours.
  • the temperature was kept at 70°C (Examples 2, 5) and 20°C (Example 7), respectively.
  • the composition of the used pre-emulsions was as follows:
  • VEOVA vinyl ester of 22.5 g (monomer) versatic acid
  • the reductor SFS sodium formaldehyde sulfoxyde: 0.65 g
  • the catalyst FeSO 4 16.7 mg
  • the polymerization temperature was kept at 20°C for the first 30 minutes to prepare a seed. The temperature was then increased by 20°C/hour to 70°C following a temperature profile.
  • starting temperatures and temperature programmes can be used, either for initiating polymerization or for initiating and completing polymerization.
  • the residual monomers were determined by gas chromatography (GC).
  • GC gas chromatography
  • the molecular weight of the prepared polymers was determined by gel permeation chromatography (GPC) with polystyrene for calibration.
  • the conversion/solids content was determined by standard procedure.
  • the viscosity was determined using a Brookfield digital viscometer.
  • the polymerization in all examples was carried out in a 0.25 L glass reactor with a stirrer under nitrogen.
  • a seed was prepared first by adding 10% of the reactive components at polymerization temperature.
  • the reactor was filled with the emulsifier solution (sodium lauryl sulfate in water) prepared with oxygen-free deionized water.
  • emulsifier solution sodium lauryl sulfate in water
  • the solution or pre-emulsion of the initiator was added to achieve control over the accurate dosing of the initiator.
  • composition of the soap solution was as follows: 0.10 g sodium lauryl sulfate (emulsifier) 25.0 ml deionized water
  • reductor SFS sodium formaldehyde sulfoxylate 0.16 g
  • catalyst Fe"SO 4 2.8 mg
  • Tx C tert-butyl peroxybenzoate
  • Tx 22 1 ,1 di(tert-butylperoxy)cyclohexane
  • Tx 117 tert-butylperoxy-2-ethylhexyl carbonate
  • the results show low residual monomer levels for the non-water-soluble organic peroxides (peroxyesters) under redox conditions.
  • the efficiency of the non-water-soluble peroxyesters such as Trigonox C was much higher than that of the water-soluble persulfates and hydroperoxides, the levels of addition could be lowered to 20-40% of the original milli-equivalents of initiator used. Due to lower amounts of initiator and reductor, a higher value for pH and lower values for the conductivity were obtained.
  • the prepared polymer had molecular weights (Mw/Mn) comparable with those of the reference copolymer of VeoVa/VAc.
  • the peroxyesters such as Trigonox 21 gave a high conversion of monomers at ambient temperature.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A process for emulsion polymerization comprising the steps of reacting together a polymerization initiator, a reductor, and a polymerizable species, with the proviso that the polymerization initiator is not a hydroperoxide, characterized in that the polymerization initiator and the reductor are reacted together to provide a free radical moiety of the initiator, whereupon this free radical moiety initiates polymerization of the polymerizable species, this step being carried out at an initial cold start temperature, whereafter the temperature is increased to follow a temperature profile to a final preselected polymerization temperature.

Description

REDOX POLYMERIZATION PROCESS
The present invention relates to a process for emulsion polymerization, to the polymers obtainable by such a process, and to their uses.
The production of water based resins, for example by means of emulsion polymerization techniques, is earned out thermally with inorganic persulfates. A problem with thermal polymerization is the process time, which leads to a less than desirable reactor output.
An object of the present invention is to provide an alternative polymerization process which aims to improve the process time.
The first aspect of the present invention provides a process according to claim 1.
Since the polymerization process according to the present invention provides a free radical initiator moiety by means of a redox reaction instead of by thermal decomposition, the polymerization can be earned out with a so-called "cold start", which involves the process time being reduced and the reactor output per unit time being increased.
A redox polymerization is known for tertiary butyl hydroperoxide "Trigonox A- W70". The inventors have shown, however, that a redox polymerization utilizing other organic peroxides provides unexpectedly good results.
The inventors have shown that polymerization can start at a lower initial temperature, which means that because of the longer "heating-up" time necessary in thermal polymerization, the polymerization time can be reduced utilizing the process of the current invention.
The inventors have furthermore demonstrated that the process according to the present invention enables a polymer with a very low residual monomer level to be obtained, whilst, with respect to thermal polymerization, the amount of initiator used can be reduced.
Good results have been achieved under the conditions as defined in claims 2-6.
The polymerization initiator is most preferably a substantially non-water-soluble initiator, such as defined in claim 7 or 8, since these non-water-soluble initiators yield an unexpectedly high efficiency in polymerization.
This higher efficiency results in shorter polymerization times and in polymer resins with improved properties. The higher efficiency of the organic peroxides is expressed by the low level of residual monomers and by the low molecular weights (Mw/Mn) of the polymers formed.
Furthermore, the conductivity of the resins initiated with the organic peroxide/redox system is lower than for corresponding resins that were initiated by persulfates.
The reductor of the redox system preferably is chosen from the following group: sodium formaldehyde sulfoxylate (SFS), sodium bisulfite, Ascorbic acid (vitamin C), aldehydes, for example glutaraldehyde, sodium metabisulfite, sodium dithionate, and sugars, wherein the reductor most preferably is sodium formaldehyde sulfoxide.
The polymerizable species preferably is chosen from the following group: acrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, methoxyethyl acrylate, dimethyl aminoacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearic methacrylate, dimethyl aminomethacrylate, allyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, glycidyl acrylate, vinyl ester of versatic acid, styrene, para-methyl styrene, vinyl acetate, alpha-methyl styrene, wherein the polymerizable species most preferably comprises vinyl acetate and/or the vinyl ester of versatic acid.
Further preferred process conditions are detailed in claims 11-15.
The polymerization is earned out in a conventional emulsion, for example in a mixture of anionic and non-ionic surfactants such as Witconate (sodium alpha- olefin sulfonate) and Syntopon (ethoxylated nonylphenol); however, other emulsifiers or mixtures are also possible.
This emulsifier solution preferably is a mixture of nonionic and anionic emulsifiers and most preferably is selected from the group consisting essentially of:
- long-chain aliphatic carboxylates (ionic)
- alkylbenzene sulfonates (ionic)
- alkyl sulphates (ionic)
- dialkylsulphosuccinate (ionic) - ethoxylated alcohols (nonionic)
- ethoxylated alkyl phenols (nonionic)
- ethoxylated amine or amides (nonionic).
A second aspect of the present invention provides a polymer obtainable according to this process.
The invention will now be further elucidated by way of the following examples.
Examples 1-6 are comparative examples and Examples 7-12 are examples according to the present invention using a redox system. Examples 3, 4, 6, 8-12 were subjected to a temperature profile increasing from an initial temperature to a final temperature, i.e. subjected to a so-called "cold-start", and Example 7 was earned out at constant temperature.
Procedure of preparation The polymerization in all the examples was carried out in a 0.25 L glass reactor with a stirrer under nitrogen. A seed was prepared first by adding 10% of the reactive components at polymerization temperature.
The preparation of the seed was carried out as follows: The reactor was filled with buffered (NaAc/HAc) emulsifier solution (Witconate/Syntopon), prepared with oxygen-free deionized water. At the polymerization temperature 10% of the pre-emulsion containing soaps (Witconate and Syntopon), monomers, and, in the case of the redox system according to the present invention, also reductor and catalyst, were added. In addition the solution or pre-emulsion of the initiator was added to achieve control over the accurate dosing of the initiator.
After a polymerization time of 30 minutes the remaining monomers, pre-emulsion, and initiator solution were dosed in 2.5 hours. In Examples 3, 4, 6, 8-12 the temperature was increased to the final temperature in the same period, following a temperature profile. The final temperature was maintained for 1 hour.
The composition of the buffered soap solution used was as follows: NaAC.3aq 0.25 g (sodium acetate) HAc 0.11 g (acetic acid)
H2O 30.3 g
Witconate 0.38 g (soap)
Syntopon 0.38 g (soap) Example 1
Thermal system
The temperature was kept at 70' °C during the polymerization. The composition of the used pre-emulsior i was:
Witconate 1.28 g
Syntopon 1.28 g
H2O 34.43 g
Vac (vinyl acetate) 52.5 g (monomer)
VEOVA (vinyl ester of versatic acid) 22.5 g (monomer)
The initiator solution was composed of 4.18 mmoles ammonium/sodium or potassium persulfate in 25 g H2O. The total process time including the time needed for heating up the reactor contents to 70°C before polymerization amounted to 5.5 hours.
Examples 2, 5, 7
The temperature was kept at 70°C (Examples 2, 5) and 20°C (Example 7), respectively. The composition of the used pre-emulsions was as follows:
Witconate 1.28 g
Syntopon 1.28 g
H2O 34.43 g
Peroxide 1.04-4.18 mmoles as mentioned in the examples
Vac (vinyl acetate) 52.5 g (monomer)
VEOVA (vinyl ester of 22.5 g (monomer) versatic acid)
The reductor SFS (sodium formaldehyde sulfoxyde: 0.65 g) and the catalyst (FeSO4 16.7 mg) were dissolved in 25 g H2O. The total process time was 4 hours. Examples 3. 4. 6. 8-12
The polymerization temperature was kept at 20°C for the first 30 minutes to prepare a seed. The temperature was then increased by 20°C/hour to 70°C following a temperature profile.
It is noted that other starting temperatures and temperature programmes can be used, either for initiating polymerization or for initiating and completing polymerization.
In all the examples the residual monomers were determined by gas chromatography (GC). The molecular weight of the prepared polymers was determined by gel permeation chromatography (GPC) with polystyrene for calibration. The conversion/solids content was determined by standard procedure. The viscosity was determined using a Brookfield digital viscometer.
The results are shown in Table 1.
Examples 13-24
Procedure of preparation
The polymerization in all examples was carried out in a 0.25 L glass reactor with a stirrer under nitrogen. A seed was prepared first by adding 10% of the reactive components at polymerization temperature.
The preparation of the seed was carried out as follows:
The reactor was filled with the emulsifier solution (sodium lauryl sulfate in water) prepared with oxygen-free deionized water. At the starting polymerization temperature 10% of the pre-emulsion containing soap, monomers, and in the case of the redox system, also reductor and catalyst, were added. In addition the solution or pre-emulsion of the initiator was added to achieve control over the accurate dosing of the initiator.
After a polymerization time of 30 minutes the remaining monomers, pre-emulsion, and initiator solution were dosed in 2.5 hours. The temperature was increased to the final temperature in the same period, following a temperature profile. The final temperature was maintained for 1 hour.
The composition of the soap solution was as follows: 0.10 g sodium lauryl sulfate (emulsifier) 25.0 ml deionized water
Pre-emulsion: 1.60 g sodium lauryl sulfate 30 ml deionized water 70 g monomer mixture (butylacrylate / styrene / methacrylic acid = 6/4/0.1) including the initiator (1.04 meq), if not water-soluble.
The reductor SFS (sodium formaldehyde sulfoxylate 0.16 g) and the catalyst (Fe"SO42.8 mg) were dissolved in 10 ml water. The molar ratio oxidator: reductor: Fe = 1 : 1 : 0.01
The results are shown in Tables 2 and 3.
Table 1
Table 2 Emulsion:
Theoretical solids content: VeoVa10/VAc-emulsions: 44% Reductant: SFS/Fe(ll) Ox : SFS : Fe = 1 : 1 : 0.01
n.a. = not applicable n.d. = not detected
Table 3 Emulsion:
Theoretical solids content: STY/BA MA-emulsions:46% Reductant: SFS/Fe(ll) Ox : SFS : Fe = 1 : 1 : 0.01
n.a. = not applicable n.d. = not detected
Styrene/butyl acrylate/methacrylic acid : 4/6/0.1
Tx C = tert-butyl peroxybenzoate
Tx 22 = 1 ,1 di(tert-butylperoxy)cyclohexane
Tx 117 = tert-butylperoxy-2-ethylhexyl carbonate
Laurox = di-lauroyl peroxide
Results
As reference the emulsion copolymerization of vinylacetate and VeoVa with potassium persulfate at 70°C was used (thermal conditions).
The results show low residual monomer levels for the non-water-soluble organic peroxides (peroxyesters) under redox conditions. As the efficiency of the non-water-soluble peroxyesters such as Trigonox C was much higher than that of the water-soluble persulfates and hydroperoxides, the levels of addition could be lowered to 20-40% of the original milli-equivalents of initiator used. Due to lower amounts of initiator and reductor, a higher value for pH and lower values for the conductivity were obtained. The prepared polymer had molecular weights (Mw/Mn) comparable with those of the reference copolymer of VeoVa/VAc.
The peroxyesters such as Trigonox 21 gave a high conversion of monomers at ambient temperature.
The invention is not limited to the above description; rather, the requested rights are determined by the following claims.

Claims

1. A process for emulsion polymerization comprising the steps of reacting together a polymerization initiator, a reductor, and a polymerizable species, with the proviso that the polymerization initiator is not a hydroperoxide, characterized in that the polymerization initiator and the reductor are reacted together to provide a free radical moiety of the initiator, whereupon this free radical moiety initiates polymerization of the polymerizable species, this step being carried out at an initial cold start temperature, whereafter the temperature is increased to follow a temperature profile to a final preselected polymerization temperature.
2. Process according to claim 1 carried out at an initial temperature of up to 70°C, for example carried out at an initial temperature of up to 50°C and preferably of up to 35°C.
3. Process according to claim 1 or 2 carried out at an initial temperature lying in the range of +10° to 35°C, preferably in the range of 15° to 25°C.
4. Process according to any one of the preceding claims wherein the initial temperature is maintained for a predetermined length of time, for example up to 2 hours, preferably up to 1 hour, most preferably up to half an hour.
5. Process according to any one of the preceding claims wherein the temperature is increased subsequent to the initial temperature maintenance period to follow a temperature profile to a final polymerization temperature, preferably up to a final polymerization temperature of at the most 90°C, and wherein the final polymerization temperature preferably lies in the range of 50-80°C and most preferably is 70°C or less.
6. Process according to claim 5 wherein the initial temperature is increased incrementally per pre-selected time period, preferably by about 20°C per hour.
7. Process according to claim 6 wherein the initiator is selected from the group consisting essentially of: diisobutanoyl peroxide, cumyl peroxyneodecanoate, 2,4,4-trimethylpentyl-2-peroxyneodecanoate, tert- amyl peroxyneodecanoate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, bis(-ethylhexyl)peroxydicarbonate, tert-butyl peroxyneodecanoate, dibutyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxy- dicarbonate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, bis(3,5,5- trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5"- bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-amyl peroxy-2- ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, 1 ,4-bis(tert-butylperoxycarbo)cyclohexane, tert-butyl peroxyisobutanoate, 1 ,1-bis(tert-butylperoxy)-3,3,5- trimethylcyclohexane, 1 ,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxy-3,5-trimethylhexanoate, 2,2-bis(tert-butylperoxy)butane, tert- butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-bis(tert- butylperoxy)-2,5-dimethylhexane, tert-butyl cumyl peroxide, 2,5-bis(tert- butylperoxy)-2,5-dimethyl-3-hexyne, and di-tert-butyl peroxide.
8. Process according to claim 7 wherein the initiator is substantially non- water-soluble and is selected from the group consisting essentially of:
- alifatic and aromatic peroxyesters, preferably tert-butyl peroxy-2- ethylhexanoate (Trigonox 21), tert-amyl peroxy-2-ethylhexanoate, tert- butyl peroxybenzoate (Trigonox C), tert-amyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-3,5-trimethylhexanoate, tert-butyl peroxyisobutanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxypivalate;
- peroxycarbonates, preferably tert-butyl peroxyisopropyl carbonate (Trigonox BPIC), and tert-butyl peroxy-2-ethyl hexyl carbonate Trigonox 117).
. Process according to any one of the preceding claims wherein the reductor is chosen from the group consisting essentially of: sodium formaldehyde sulfoxylate (SFS), sodium bisulfite, Ascorbic acid (vitamin C), aldehydes, for example glutaraldehyde, sodium metabisulfite, sodium dithionate, and sugars.
10. Process according to any one of the preceding claims wherein the polymerizable species is selected from the group consisting essentially of: acrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, methoxyethyl acrylate, dimethyl aminoacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearic methacrylate, dimethyl aminomethacrylate, allyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2- hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, glycidyl acrylate, vinyl ester of versatic acid, styrene, para- methyl styrene, vinyl acetate, alpha-methyl styrene.
11. Process according to any one of the preceding claims caπied out in the presence of a catalyst, said catalyst preferably being a water-soluble salt derived from a transition metal, and most preferably being selected from the group consisting essentially of Fe2+, Co3+, Cu\ and Ce3+.
12. Process according to any one of the preceding claims wherein the initiator s and the reductor are provided in the following ratios 10:1 to 1:5, preferably
4:1 to 1:2.
13. Process according to any one of the preceding claims wherein the ratio of catalyst: oxidator is about 0-0.1 on a molar basis. 0
14. A polymer obtainable according to the process of any one of the preceding claims.
15. Polymer according to claim 14 having one or more of the following s characteristics:
- a conductivity lower than about 5,
- a low residual monomer level,
- a particle size of less than about 220 nm, preferably less than 200 nm.
0 16. Use of a polymer according to claims 14 and/or 15 in coatings and/or adhesives.
EP99952574A 1998-10-12 1999-10-11 Redox polymerization process Withdrawn EP1129113A1 (en)

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CN103443130A (en) * 2006-07-18 2013-12-11 赛拉尼斯国际公司 Emulsion polymerisation process
CN103443130B (en) * 2006-07-18 2016-01-20 赛拉尼斯国际公司 Emulsion polymerisation process

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