NZ237146A - Preparation of stabilised polymer dispersion by forming a stabiliser component from unsaturated monomers and co 2+ chain transfer agent followed by the polymerisation of at least one acrylic monomer in the presence of the stabiliser component - Google Patents
Preparation of stabilised polymer dispersion by forming a stabiliser component from unsaturated monomers and co 2+ chain transfer agent followed by the polymerisation of at least one acrylic monomer in the presence of the stabiliser componentInfo
- Publication number
- NZ237146A NZ237146A NZ23714691A NZ23714691A NZ237146A NZ 237146 A NZ237146 A NZ 237146A NZ 23714691 A NZ23714691 A NZ 23714691A NZ 23714691 A NZ23714691 A NZ 23714691A NZ 237146 A NZ237146 A NZ 237146A
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- NZ
- New Zealand
- Prior art keywords
- methacrylate
- chain transfer
- stabilizer
- transfer agent
- cobaltate
- Prior art date
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
New Zealand Paient Spedficaiion for Paient Number £37146
23 7
Priority Date(s)'-
®!c>ecMca:ion Filed: .
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'ubllcatton Date: ..
P.O. Jouma*. No. jgj
DRAWINGS
Patents Form No. 5
NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION
PROCESS FOR PREPARING STABILIZED POLYMER DISPERSION
WE, E.I. DU PONT DE NEMOURS AND COMPANY, a corporation under the laws of the State of Delaware, U.S.A. of 10th & Market Streets, Wilmington, Delaware, U.S.A.
hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
(followed by page la)
23 7 1 4 6 -
la.
m
This invention relates to a process for preparing a stabilized polymer dispersion. It is more particularly directed to a process for preparing a dispersion of a polymer having an acrylic polymer core component and a polymeric stabilizer component, in 10 which the stabilizer component is prepared using a cobalt catalytic chain transfer agent.
The stabilized polymeric dispersions 15 prepared according to this invention are described in a general way in U.S. Patent 4,746,714 to Spinelli, Scopazzi and Antonelli.
While those dispersions function very well for their intended purpose, the method described for 20 their preparation provides no convenient way for incorporating living functional groups, especially hydroxyl groups, on the chains of the stabilizer polymer molecules. These functional groups confer certain advantages when the polymer system is to be 25 cross-linked with melamines or isocyanates.
It has now been found that such groups can be easily incorporated on the stabilizer polymer molecules, in any number, if one uses a cobalt catalytic chain transfer agent in the polymer's 30 preparation.
3 35
la. (followed by page lb)
23 7 1 4
-lb-
This invention provides a process for preparing a stabilized polymer dispersion in which the principal polymer has
(a) a core component composed of acrylic polymers, and
(b) a plurality of stabilizer components which are polymers of ethylenically unsaturated monomers, substantially all of the stabilizer components being grafted to the core component at one of the stabilizer ends, the process comprising
(a) preparing the stabilizer component by polymerizing one or more ethylenically unsaturated monomers, using a catalytic
♦ *+2
chain transfer agent containing Co ,
and then
(b) preparing the core component by polymerizing one or more acrylic monomers while they are in contact with stabilizer components,
steps (a) and (b) being conducted in an organic liquid which is a solvent for the stabilizer components but a non-solvent for the core component.
The principal polymers of according to the invention are 714 previously mentioned. That the dispersions prepared described in U.S. patent 4 74 6
(followed by page 2)
237 1 /, 3
description, and the disclosures of how the polymers are prepared, are incorporated into this specification. The polymers described there have core components of acrylic polymers and substantially linear acrylic polymeric stabilizer components, each having a terminal polymerizable functional group, 5 which are grafted to the core component at one end of the chain.
Illustrative of monomers which can be used to prepare the core components are those shown in the '714 patent, column 3, line 55, to column 4, line 25. 10 Isocyanate, silane and amine functional monomers can also be used. Preferred for use in the process of the invention are methyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, methyl acrylate, styrene and glycidyl methacrylate. 15 The monomers used to prepare the stabilizer component according to the invention can be any of the conventional polymerizable ethylenically unsaturated monomers. Preferred for use are butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 20 hydroxyethyl methacrylate, methyl methacrylate,
glycidyl methacrylate, itaconic acid or anhydride, maleic acid or anhydride, styrene, isocyanatoethyl methacrylate, benzene 1-(1-isocyanato-l-methyl ethyl)-3,4(1-methyl ethenyl), methacrylic acid, 25 acrylic acid, silanes and amines.
The ratio of monomer units in the final polymer is a matter of choice, as will be understood by those skilled in this art.
The catalytic chain transfer agent used in
the process of the invention can be any compound which
+ 2
contains Co . Cobalt chelates are preferred, especially those described in U.S. Patent 4,680,352 to Janowicz and Melby, and U.S. Patent 4,722,984 to
2
3
23 7 1 4
Janowicz. Most preferred are pentacyanocobaltate (II), diaquabis(borondifluorodimethyl-glyoximato)cobaltate (II) and diaquabis(borondifluoro-diphenylglyoximato)cobaltate (II) .
The chain transfer agents are ordinarily used at concentrations of 5-150 ppm based on monomers.
The process is run in two steps, the second of which can be run immediately after the first but which is ordinarily run after a pause for analysis and to permit more efficient use of the reactor.
In step one, a mixture of stabilizer monomers and organic liquid is heated, preferably to reflux temperature for ease of control, and to it is added the catalytic chain transfer agent of choice, additional monomer(s) and solvent, and the usual amount of a conventional polymerization initiator such as azo- or peroxide initiators. The reaction is run, with additions of monomers and initiator as needed, until the desired stabilizer component is obtained (ordinarily having a of 5000-12000).
In step two, an organic liquid which is a solvent for the stabilizer component but a non-solvent for the core component is added to the product of step one. "Solvent" and "non-solvent" are being used in the conventional sense, as will be understood by those skilled in the polymer art. Illustrative of organic liquids which can be used are aromatic- and aliphatic hydrocarbons such as heptane and VM&P naphtha.
Mixtures of liquids can also be used. The stabilizer/liquid ratio is of secondary importance, but is usually in the range 1/2 to 1/4 (weight).
237 14 6
The resulting mixture is again heated, preferably to reflux temperature for better control and to it are added the core monomers and a conventional initiator such as one of those previously mentioned, in the usual amount. Polymerization is continued, with additions of liquid and initiator as 5 needed, until it is complete, as determined by periodic sampling and analysis.
The dispersions prepared according to the process of the invention can be used to modify the rheology and/or the physical properties of 10 conventional coating compositions at concentrations of 1-80%, preferably 10-40%, by weight of the total composition.
Examples
Those skilled in the art will be able to practice this invention more easily after referring to the following illustrative examples.
Those artisans will no doubt be able to compose numerous variations on the themes disclosed, 20 such as changing the amounts of ingredients slightly but insignificantly from those shown, adding innocuous substances, or substituting equivalent or nearly equivalent components for those shown. All such • variations are considered to be within the inventive 25 concept.
In the examples, all parts are by weight unless indicated otherwise.
4
2 3 7 1 4
Example 1 Pert A
To a reaction vessel were charged
Toluene 827.2 parts
n-butyl methacrylate 447.9
2-Ethylhexyl methacrylate 588.9
3-methacryloxypropyl-trimethoxysilane (A-174) 108.1
This mixture was brought to reflux temperature, held there under nitrogen with stirring, and to it was then added, over a ten-minute period, a solution of
1,l'-azobis(cyclohexane-15 carbonitrile) (initiator) 1.14 parts
Diaquabis(borondifluoro-dimethylglyoximato)-cobaltate(II) 0.023
n-butyl methacrylate 80.7
Toluene 42.1
The reaction mixture was then held at reflux temperature, with stirring, and to it was added, over a 60-minute period, a mixture of
n-butyl methacrylate 209.0
2-ethylhexyl methacrylate 271.6
A-174 (described above) 63.6
Initiator 1.95
This was followed immediately by the addition of a solution of
23 7 U
n-butyl methacrylate 209.0 parts
2-ethylhexyl methacrylate 304.9
A-174 (described above) 63.0 Initiator 2.12
Toluene 84.4
over a 180-minute period while maintaining reflux temperature. The reaction mixture was then held at reflux temperature, with stirring, for 30 minutes after which time was added, over a 60-minute period, mixture of
Toluene 105.9 parts
Initiator 0.5
This reaction mixture was held at reflux temperature 15 for 60 minutes, and toluene (246.3 parts) was then added to it and the mixture cooled. The resulting solution, 64.2% solids, contained the stabilizer component 2-EHMA/IBMA/A-174 50/40/10.
Part P
To a reaction vessel were charged
Product of (A) 265.0 parts
Heptane 396.0
This mixture was brought to reflux temperature and to it were then added 0.6 parts of t-butyl peroctoate. The mixture was then held at reflux temperature and to it were immediately and simultaneously added, over a 30 210-minute period,
(1) A solution of
Methyl methacrylate 207.9 parts
Methyl acrylate 103.9
6
237 14 6
Styrene 62.4
A-174 41.6
Heptane 19.3
Product of A 128.8
and
(2) A solution of
Heptane 67.7
t-butyl peroctoate 6.2
The resulting mixture was held at reflux temperature 10 for 45 minutes, and to it was then added, over a 30-minute period, at reflux, a solution of
Heptane 24.7 parts t-butyl peroctoate 4.1
This was again held at reflux temperature for 60 minutes, and 119.7 parts of solvent were boiled off to give a dispersion containing 55% solids.
The composition of the principal polymer in 20 the resulting product was
BMA/2-EHMA/A-174/MMA/MA/STY 14.4/18.8/9.9/31.6/15.8/9.5
Example 2 P9rt A
To a reaction vessel were charged
Toluene 853.5 parts
Isobutyl methacrylate 495.2
2-ethylhexyl methacrylate 434.2
Hydroxyethyl methacrylate 151.5
7
c
2 3 7 1 4
The mixture was brought to reflux temperature (129*C), held there under nitrogen with stirring, and to it was then added, over a 10-minute period, a solution of
Diaquabis(borondifluoro-dimethylglyoximato)-
cobaltate II 0.033 parts
1,1'-azobis(cyclohexane-
carbonitrile) (initiator) 1.0
Hydroxyethyl methacrylate 36.6
Toluene 38.0
The reaction mixture was held at reflux temperature with stirring and to it was added, over a 24 0-minute period, a mixture of
Isobutyl methacrylate 353.1 parts
2-ethylhexyl methacrylate 414.0
Hydroxyethyl methacrylate 213.8
Toluene 76.3
The reaction mixture was then held at reflux temperature with stirring for 30 minutes, after which time was added, over a 60-minute period, a mixture of
Toluene 227.9 parts
Initiator 0.9
The reaction mixture was further held at reflux temperature for 60 minutes and then cooled. The 30 resulting solution, 63.6% solids, contained the stabilizer component 2-EHMA/IBMA/HEMA 40/40/20.
Part B
To a reaction vessel were charged
8
237 14 6
v..
Product of A 639.2 parts Isopropanol 44.0 Petroleum naphtha 62.8
Heptane 790.6 Xylol 99.1
The mixture was brought to reflux temperature (92*C) and to it were added 1.6 parts of t-butyl peroctoate. The reaction mixture was held at reflux temperature and to it were immediately and simultaneously added, over a 210-minute period,
(1) a solution of
Methacrylic acid 42.2 parts Hydroxyethyl-
acrylate 264.7
Methyl methacrylate 370.3
Methyl acrylate 190.6
Styrene 158.9
Glycidyl methacrylate 32.2
Xylol 49.1
Product of A 320.9
and
(2) a solution of
Petroleum naphtha 157.0 parts
Butanol 27.9
t-butyl peroctoate 15.9
The reaction mixture was then held at reflux temperature for 45 minutes and to it was then added,
over a 30-minute period, at reflux, a solution of
Butanol 62.8 parts
t-butyl peroctoate 10.4
9
Claims (7)
1. A process for preparing a stabilized polymer dispersion in which the principal polymer has (a) a core component composed of acrylic polymers, and (b) a plurality of stabilizer components which are polymers of ethylenically unsaturated monomers, 5 substantially all of the stabilizer components being grafted to the core component at one of the stabilizer ends, the process comprising (a) preparing the stabilizer component by polymerizing one or more ethylenically 10 unsaturated monomers, using a catalytic + 2 chain transfer agent containing Co , and then 15 (b) preparing the core component by polymerizing one or more acrylic monomers while they are in contact with stabilizer components, steps (a) and (b) being conducted in an organic liquid 20 which is a solvent for the stabilizer components but a non-solvent for the core component.
2. The process of claim 1 in which the + 2 chain transfer agent is a cobalt chelate.
3. The process of claim 2 in which the 25 chelate is a pentacyanocobaltate(II), diaquabis(borondifluorodimethyl- glyoximato)cobaltate (II) or diaquabis(borondifluorodiphenyl-glyoximato)cobaltate (II).
4. The process of any one of claims 1-3 in 30 which the monomers used in (a) are butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, glycidyl methacrylate, styrene, methacrylic acid, acrylic acid, itaconic acid or anhydride, maleic acid 33 35 11 237146 -12- or anhydride, or an isocyanate, silane or amine functional ethylenically unsaturated monomer.
5. The process of any one of claims 1 to 4 in which the monomers used in (b) are methyl methacrylate, hydroxyethyl methacrylate, methacylic acid, styrene, glycidyl methacrylate or an ethylenically unsaturated monomer.
6. A process according to claim 1 and substantially as described in this specification with reference to example 1 or example 2.
7. A stabilized polymer dispersion whenever produced by a process according to any one of claims 1 to 6. E.I. DU PONT DE NEMOURS AND COMPANY \ r-v By Their Attorneys BALDWIN SON & CAREY
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ23714691A NZ237146A (en) | 1991-02-18 | 1991-02-18 | Preparation of stabilised polymer dispersion by forming a stabiliser component from unsaturated monomers and co 2+ chain transfer agent followed by the polymerisation of at least one acrylic monomer in the presence of the stabiliser component |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ23714691A NZ237146A (en) | 1991-02-18 | 1991-02-18 | Preparation of stabilised polymer dispersion by forming a stabiliser component from unsaturated monomers and co 2+ chain transfer agent followed by the polymerisation of at least one acrylic monomer in the presence of the stabiliser component |
Publications (1)
Publication Number | Publication Date |
---|---|
NZ237146A true NZ237146A (en) | 1992-02-25 |
Family
ID=19923493
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NZ23714691A NZ237146A (en) | 1991-02-18 | 1991-02-18 | Preparation of stabilised polymer dispersion by forming a stabiliser component from unsaturated monomers and co 2+ chain transfer agent followed by the polymerisation of at least one acrylic monomer in the presence of the stabiliser component |
Country Status (1)
Country | Link |
---|---|
NZ (1) | NZ237146A (en) |
-
1991
- 1991-02-18 NZ NZ23714691A patent/NZ237146A/en unknown
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