CA1042582A - Producing self-stabilizing polymer dispersions in hydrocarbon liquids - Google Patents
Producing self-stabilizing polymer dispersions in hydrocarbon liquidsInfo
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- CA1042582A CA1042582A CA191,173A CA191173A CA1042582A CA 1042582 A CA1042582 A CA 1042582A CA 191173 A CA191173 A CA 191173A CA 1042582 A CA1042582 A CA 1042582A
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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Abstract
ABSTRACT OF THE DISCLOSURE
Dispersions of hydroxy group useful in combination with cross-linking agents as a thermosetting coating composition and containing co-polymers in organic liquids, and process of making same are described. The dispersions comprise -(A) 10 - 30 percent by weight of a co-polymerizable polymer which is the reaction product of (1) a low molecular weight co-polymer of 80 - 94 percent by weight p-tertiary butyl styrene, and 4 - 12 percent by weight glycidylmethacrylate, and (2) 2 - 8 percent by weight (meth)acrylic acid or (meth)acrylic acid chloride or a mixture thereof, the sum of (1) and (2) being 100 percent;
and (B) 70 - 90 percent by weight of co-polymerizable ethylenically unsaturated monomers, at least one of them carrying a functional hydroxy group, co-polymerized in an organic liquid which is a true solvent for component A, but the disperse co-polymer of A and B being substantially insoluble therein, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210°C. The dispersions are free from coagulates or seeding, precluding the need for the time-consuming filtration operations and the dispersions can be produced with a solids content of more than 50 percent and exhibit excellent stability and resistance to external influences.
Dispersions of hydroxy group useful in combination with cross-linking agents as a thermosetting coating composition and containing co-polymers in organic liquids, and process of making same are described. The dispersions comprise -(A) 10 - 30 percent by weight of a co-polymerizable polymer which is the reaction product of (1) a low molecular weight co-polymer of 80 - 94 percent by weight p-tertiary butyl styrene, and 4 - 12 percent by weight glycidylmethacrylate, and (2) 2 - 8 percent by weight (meth)acrylic acid or (meth)acrylic acid chloride or a mixture thereof, the sum of (1) and (2) being 100 percent;
and (B) 70 - 90 percent by weight of co-polymerizable ethylenically unsaturated monomers, at least one of them carrying a functional hydroxy group, co-polymerized in an organic liquid which is a true solvent for component A, but the disperse co-polymer of A and B being substantially insoluble therein, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210°C. The dispersions are free from coagulates or seeding, precluding the need for the time-consuming filtration operations and the dispersions can be produced with a solids content of more than 50 percent and exhibit excellent stability and resistance to external influences.
Description
~04Z5~3Z
FIELD OF INVENTION AND BACKGROUND
The invention is directed to a process for producing dispersions of film-forming polymeric materials in an organic liquid, to the obtained dispersions, and compositions contain-ing the dispersions.
It is known to produce dispersions in a non-aqueous medium by polymerizing monomers or mixtures of monomers in inert organic solvents in the presence of amph~pathic macro-molecules. Amphipathic molecules as the term is ased herein 10 include one component which is highly solvated by the organic liquid and another component which associates with the dispersed polymer particles. These amphipathic molecules serve as external stabilizers in non-aqueous dispersions. Dispersions which are stabilized with the aid of amphipathic macromolecules usually require a major proportion of aromatic or ester-like liquids which serve as solvents in the preparation of the amphipathic molecule stabilizers and thus these solvents are introduced into the dispersions which are to be stabilized. If these organic liquids which us~ally are highly toxic are to be 20 left out of the dispersions, the removal must occur pxior to the preparation of the dispersions. Such process is uneconomic with regard to energy and work. A further undesired property of the amphipathic macromolecule stabilizers is the fact that for the preparation of their segments solvatable by aliphatic hydrocarbons, monomers are used which, in many cases, are derivatives of stearic acid or other fatty acids with similar chain length, thus imparting wax-like properties to the stabilizers which adversely influence tha quality of the films ~ -formed from the dispersions.
': : . . : '` ' 104'~58Z
It has now been found that the aforesaid disadvantages can be avoided if ~ ethylenically unsaturated monomers are polymerized in the presence o~ a co-polymerizable monomer consisting mainly of p-tertiary butyl styrene, thereby making use of the fact that p-tertiary butyl styrene is infinitely soluble in ardcompatible with aliphatic hydrocarbons. Moreover, films of polymeric p-tertiary butyl styrene have a high light-transmission and excellent gloss.
Accordingly, it is the object of the present invention to provide a process for producing dispersions in organic liquids of co-polymers lO carrying hydroxy groups, which is characterized in that -(A) 10 - 30 percent by weight, preferably 15 - 25 percent by weight, of a co-polymerizable polymer which is a reaction product of tl) a low molecular weight co-polymer of 80 - 94 percent by weight of p-tertiary butyl styrene and 4 - 12 percent by weight of glycidylmethacrylate and ~2) 2 - 8 percent by weight of (meth)acrylic acid or ~meth)acrylic acid chloride or a mixture thereof, the sum of (1) and ~2) being 100 percent, and (B~ 70 - 90 percent by weight, preferably 75 - 85 percent by weight, of ethylenically unsaturated co-polymerizable monomers, at least one of them carrying a functional hydroxy group, are co-polymerized in an organic liquid in which component A is completely soluble and in which the dispersed co-polymer of A and B is substantially insoluble therein, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210C. This invention also relates to the dispersions so produced.
The dispersions of the invention show many advantages over the dispersions produced on the basis of amphipathic macromolecules. In particular, the dispersions are substantially innocuous with regard to the organic ~ -4-' ' `; ` " ` ' ' .
liquids contained therein, since the preparation of the polymer A as well as the preparation of the dispersion is carried out exclusively in aliphatic hydrocarbons and preferably those having a boiling range of from 145 - 200 C.
Furthermore, dispersions which are stabilised by means of external stabilisers through the action of intermolecu~Lar forces, such as dipole-dipole interaction of hydrogen bonding between the polymer-compatible anchor or part of the amphipathic macromolecuLe and the dispersed particles, are highly sensitive to temperatures. A rise in temperature, e.g. in the preparation of the dispersion, may lead to a reduction in the bonding force between stabiLiser and polymer particle, which in turn reduces the stability of the system and increases the tendency to coagulate.
The dispersions o the invention are true copolymers forming self-stabilised non-~queous polymer dispersions due to the cova~Lently buiLt-in p-tertiary butyl styrene chains solvatable by aliphatic hydrocarbons. The stabilisation is not effected through subsidiary valence forces. The possibility of increasing the reaction temperature not only improves the conversion but also reduces reaction time and enables one to use monomers with lower reactivity.
The preparation of the co-polymerizable polymer A is carried out in two steps. In a first step a low molecuLar weight co-polymer A is produced in white spirit, preferably at temperatures of about 140 C., with the use of high quantities of chain transfer agent -- up to 2 percent of the monomors, from 80 - 94 percent by welght of p-tertiary butyl styrene, and 4 - 12 percent by weight of glycidylmothacrylate. The polymer is modified in a second step~ preferably at temperatures of about 120 C., with 2 - 8 percent by weight of (meth)acrylic acid and/or (meth)acrylic acid chloride in order to introduce polymerizable double bonds. The polymer A is produced as a solution~ preferably at about 50 percent so~Lids.
B -s 16~4'~58Z
The dispersions of the invention are produced according to known methods. For example, 10 - 30 percent by weight, preferably 15 - 25 percent by weight, of the polymer A are blended with 70 - 90 percent by weight~ pre-ferably 75 - 85 percent by weight, of component B, and part of this blend, about 5 - 10 percent by weight, are added to the pre-charged organic liquid.
The reaction vessel is blanketed with inert gas and the batch is heated to reaction temperature. The remainder of the blend, initiator, and optionally chain transfer agent are slowly added continuously in known manner.
Suitable unsaturated monomers which may be co-polymerized with polymer A, i.e.~ the monomers of B, are methyl(meth)acrylate~ ethyl(meth)-acrylate, propyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)-acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, tripropyl-eneglycolmono~meth~acrylate, (meth)acrylic acid, styrene, p-tertiarybutyl-styrene, and vinyltoluene.
The co-polymer dispersions of the invention can be produced without any residue and are absolutely free from coagulates or seeding, meaning that time-consuming filtration operations are unnecessary. The dispersions can be produced with a solids content of more than 50 percent and exhibit excellent stability and resistance to extérnal influences. The dispersions have excell- -- -~
ent coalescence at room temperature. Gombined in known manner with pigments, soluble dye-stuffs, cross-linking agents, plasticizers, and the like, and stoved at higher temperatures for short periods, the dispersions yield coatings with excellent performance~ as is~ e.g., requested by the consumer of finish-ing coats. -The following aliphatic hydrocarbons are used in the examples:
Aniline Content of Boilin~ Point Kauri-Butanol Aromatic Range C. About C. Value, About Hydrocarbons White Spirit A 145-200 56 39 18 White Spirit B 184-207 85 26 0 The invention is illustrated by the following examples. Parts are by weight.
..
;~.
~6g4;zS82 ELAM~E 1 A polymer A with co-polymerizable double bonds on the basis of p-tertiary butyl styrene/glycidyl methacrylate/methacrylic acid is prepared in the following manner: 190 parts p-tertiary butyl styrene, 10 parts glycidylmethacrylate, 120 parts white spirit A, 4 parts di-tertiary-butyl-peroxide, and 4 parts tertiary dodecylmercaptan are charged to a reaction vessel equipped vith stirrer, reflux aondensor, addition funnel, and ther-mometer and heated to 140C. A blend consisting of 380 parts p-tertiary butyl styrene, 20 parts glycidylmethacrylate, 240 parts white spirit A, 8 parts di-tertiary butyl pero~i~ and 8 parts tertiary-dodecylmercaptan is added in drops continuously within a period of two hours; and the batch is stirred for a further two hours at 140C.~ then the temperature is reduced to 120C. and a mixture of 0.2 parts hydroquinone, 1 part dimethylbenzylamine, and 50 parts white spirit A and, within the course of 1 hourj 13.2 parts me.thacrylic acid and 250 parts white spirit A are added. The batch is stirred ~
for a further three hours at 120C. The obtained solution has a solids .:
content of 50 percent. ~ .
. A dispersion is prepared from 14.7 parts of the above solution, 18 parts methy.lmethacrylate, 12 parts styrene, 3.6 parts ethylacrylate, 6 parts -.
hydroxybutylacrylate, 0.36 parts bisazoisobutyronitrile, and 601.3 parts of :~
white spirit B. The blend is charged to a reaction vessel as described above .
and the batch is held for 20 minutes at 90l.C. under the protection of N2-gas.
In the course of one hour, a blend of 230 parts of the solution of polymer A, 244.8 parts methylmethacrylate, 163.2 parts styrene, 56.4 parts ethyl acrylate 84 parts hydroxybutylacrylate, 12 parts acrylic acid, and 5.64 parts azobisisobutyronitrile is added and the temperature of 90C~ is held for another hour. A stable dispersion without residues and seeds is obtained.
The dispersion has a solids content of 48 percent and a viscosity of 13.4 s, Ford cup no. 4 at 20C.
7.85 parts of the polymer solution A of Example 1 together with 6 parts methylmethacrylate, 10 parts ethylacrylate, 0.16 parts azobisisobutyro-.
.
.
1C)4Z582 nitrile, and 284 parts white spirit B are charged to a reaction vessel equipped with stirrer, reflux condensor, and thermometer. The batch is held at 90C. for 20 minutes under the protection of N2-gas. Subsequently a blend of 128.1 parts polymer A solution, 81.6 parts methylmethacrylate, 154.4 parts ethylacrylate, 80 parts tripropyleneglycolmonomethacrylate, 6 parts -acrylic acid, and 3.68 parts azobisisobutyronitrile is added in the course of one hour and a temperature of 90C. is held for ano*her hour. A highly stable dispersion, without any residue or seeding, is obtained having a solids content of 52.9 percent and a viscosity of 140 s, Ford cup no. 4 at 20C.
. :
4.8 parts of the polymer A solution of Example 1 are blended with 6 parts methylmethacrylate, 4 parts p-tertiary butyl styrene, 1.2 parts ethylacrylate, 2 parts hydroxybutylacrylate, 0.1 parts azobisisobutyronitrile and 198.6 parts white spirit A, and the blend is charged to the equipment described in Example 1 and held at 90C. for 20 minutes under the protection of N2-gas. In the course of one hour, a blend of 76.4 parts polymer A
solution, 81 parts methylmethacrylate, 54.4 parts p-tertiary butyl styrene, 18.4 parts ethylacrylate, 28 parts hydroxybutylacrylate, 4 parts acrylic acid, and 1.9 parts azobisisobutyronitrile is added continuously and a temperature of 90C. is held for another hour. A highly stable dispersion without residues and seeding is obtained, having a solids content of 49.8 -~
percent and a viscosity of 47.3 s, Ford cup no. 4 at 20C.
A polymer A on the basis of p-tertiary butyl styrene/glycidylmeth_ acrylate/acrylic acid chloride carrying co-polymerizable double bonds i9 prepared in the following way: 90 parts p-tertiary butyl styrene, 10 parts glycidyl methacrylate, 60 parts white spirit A, 2 parts di-tertiary butyl peroxide, 2 parts tertiary dodecylmercaptan are charged to the equipment described in Example 1 and are heated to 140C. A blend of 180 parts p-tertiary butyl styrene, 20 parts glycidyl methacrylate~ 120 parts whi~e spirit A, 4 parts di-tertiary butyl peroxide, and 4 parts tertiary dodecylmercaptan ,' ' .
16)4;~
is added in drops within the course of two hours and the batch is stirred for a further two hours at 140C. Then the temperature is reduced to 120C., and a blend of 0.2 parts hydroquinone, 1.2 parts dioctylhexylamine and 90 parts white spirit A is added and~ in the course of one hour, a blend of 19.8 parts acrylic acid chloride and 30 parts white spirit A is added. The batch is held for a further three hours at 120C. and stirred. The obtained solution has a solids content of 51 percent.
A dispersion is prepared from 0.7 parts of this solution and 3 parts styrene, 5 parts methylmethacrylate, 0.06 parts azobisisobutyronitrile, and 113 parts white spirit A. The blend is charged to the equipment des-cr~bed in Example 1 and hehd at 90C. for 20 minutes under N2-gas. In the course of one hour, a blend of 22.1 parts of the polymer solution (of paragraph 1), 32 parts styrene, 30 parts methyl~ethacrylate~ 30 parts hydroxy- -butylacrylate, and 0.94 parts azobisisobutyronitrile are added and the -~
temperature of 90C. is held for another hour. A dispersion without residues is obtained having a solids ~ontent of 46 percent and a viscosity of 29.2 s, Ford cup no. 4 at 20C.
50 parts of the dispersion of Example 2 are mixed with 17.5 parts of benzoguanamine resin ~a non-plasticized butanol partially etherified benzoguanamine-formaldehyde condensation product with high reactivity; a viscosity of 6 - 10 P/20C.~ 70 percent solids in butanol) adding 0.16 parts of p-toluene sulfonic acid. The blend is applied (by conventional methods) to glass or steel panels and cured at 130C. for 30 minutes. A hard, clear, and scratch-resistant (thermoset) aoating is obtained, which shows excellent resistance to solvents such as xylol or acetone.
_ 9 _ . .. . .
.
FIELD OF INVENTION AND BACKGROUND
The invention is directed to a process for producing dispersions of film-forming polymeric materials in an organic liquid, to the obtained dispersions, and compositions contain-ing the dispersions.
It is known to produce dispersions in a non-aqueous medium by polymerizing monomers or mixtures of monomers in inert organic solvents in the presence of amph~pathic macro-molecules. Amphipathic molecules as the term is ased herein 10 include one component which is highly solvated by the organic liquid and another component which associates with the dispersed polymer particles. These amphipathic molecules serve as external stabilizers in non-aqueous dispersions. Dispersions which are stabilized with the aid of amphipathic macromolecules usually require a major proportion of aromatic or ester-like liquids which serve as solvents in the preparation of the amphipathic molecule stabilizers and thus these solvents are introduced into the dispersions which are to be stabilized. If these organic liquids which us~ally are highly toxic are to be 20 left out of the dispersions, the removal must occur pxior to the preparation of the dispersions. Such process is uneconomic with regard to energy and work. A further undesired property of the amphipathic macromolecule stabilizers is the fact that for the preparation of their segments solvatable by aliphatic hydrocarbons, monomers are used which, in many cases, are derivatives of stearic acid or other fatty acids with similar chain length, thus imparting wax-like properties to the stabilizers which adversely influence tha quality of the films ~ -formed from the dispersions.
': : . . : '` ' 104'~58Z
It has now been found that the aforesaid disadvantages can be avoided if ~ ethylenically unsaturated monomers are polymerized in the presence o~ a co-polymerizable monomer consisting mainly of p-tertiary butyl styrene, thereby making use of the fact that p-tertiary butyl styrene is infinitely soluble in ardcompatible with aliphatic hydrocarbons. Moreover, films of polymeric p-tertiary butyl styrene have a high light-transmission and excellent gloss.
Accordingly, it is the object of the present invention to provide a process for producing dispersions in organic liquids of co-polymers lO carrying hydroxy groups, which is characterized in that -(A) 10 - 30 percent by weight, preferably 15 - 25 percent by weight, of a co-polymerizable polymer which is a reaction product of tl) a low molecular weight co-polymer of 80 - 94 percent by weight of p-tertiary butyl styrene and 4 - 12 percent by weight of glycidylmethacrylate and ~2) 2 - 8 percent by weight of (meth)acrylic acid or ~meth)acrylic acid chloride or a mixture thereof, the sum of (1) and ~2) being 100 percent, and (B~ 70 - 90 percent by weight, preferably 75 - 85 percent by weight, of ethylenically unsaturated co-polymerizable monomers, at least one of them carrying a functional hydroxy group, are co-polymerized in an organic liquid in which component A is completely soluble and in which the dispersed co-polymer of A and B is substantially insoluble therein, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210C. This invention also relates to the dispersions so produced.
The dispersions of the invention show many advantages over the dispersions produced on the basis of amphipathic macromolecules. In particular, the dispersions are substantially innocuous with regard to the organic ~ -4-' ' `; ` " ` ' ' .
liquids contained therein, since the preparation of the polymer A as well as the preparation of the dispersion is carried out exclusively in aliphatic hydrocarbons and preferably those having a boiling range of from 145 - 200 C.
Furthermore, dispersions which are stabilised by means of external stabilisers through the action of intermolecu~Lar forces, such as dipole-dipole interaction of hydrogen bonding between the polymer-compatible anchor or part of the amphipathic macromolecuLe and the dispersed particles, are highly sensitive to temperatures. A rise in temperature, e.g. in the preparation of the dispersion, may lead to a reduction in the bonding force between stabiLiser and polymer particle, which in turn reduces the stability of the system and increases the tendency to coagulate.
The dispersions o the invention are true copolymers forming self-stabilised non-~queous polymer dispersions due to the cova~Lently buiLt-in p-tertiary butyl styrene chains solvatable by aliphatic hydrocarbons. The stabilisation is not effected through subsidiary valence forces. The possibility of increasing the reaction temperature not only improves the conversion but also reduces reaction time and enables one to use monomers with lower reactivity.
The preparation of the co-polymerizable polymer A is carried out in two steps. In a first step a low molecuLar weight co-polymer A is produced in white spirit, preferably at temperatures of about 140 C., with the use of high quantities of chain transfer agent -- up to 2 percent of the monomors, from 80 - 94 percent by welght of p-tertiary butyl styrene, and 4 - 12 percent by weight of glycidylmothacrylate. The polymer is modified in a second step~ preferably at temperatures of about 120 C., with 2 - 8 percent by weight of (meth)acrylic acid and/or (meth)acrylic acid chloride in order to introduce polymerizable double bonds. The polymer A is produced as a solution~ preferably at about 50 percent so~Lids.
B -s 16~4'~58Z
The dispersions of the invention are produced according to known methods. For example, 10 - 30 percent by weight, preferably 15 - 25 percent by weight, of the polymer A are blended with 70 - 90 percent by weight~ pre-ferably 75 - 85 percent by weight, of component B, and part of this blend, about 5 - 10 percent by weight, are added to the pre-charged organic liquid.
The reaction vessel is blanketed with inert gas and the batch is heated to reaction temperature. The remainder of the blend, initiator, and optionally chain transfer agent are slowly added continuously in known manner.
Suitable unsaturated monomers which may be co-polymerized with polymer A, i.e.~ the monomers of B, are methyl(meth)acrylate~ ethyl(meth)-acrylate, propyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)-acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, tripropyl-eneglycolmono~meth~acrylate, (meth)acrylic acid, styrene, p-tertiarybutyl-styrene, and vinyltoluene.
The co-polymer dispersions of the invention can be produced without any residue and are absolutely free from coagulates or seeding, meaning that time-consuming filtration operations are unnecessary. The dispersions can be produced with a solids content of more than 50 percent and exhibit excellent stability and resistance to extérnal influences. The dispersions have excell- -- -~
ent coalescence at room temperature. Gombined in known manner with pigments, soluble dye-stuffs, cross-linking agents, plasticizers, and the like, and stoved at higher temperatures for short periods, the dispersions yield coatings with excellent performance~ as is~ e.g., requested by the consumer of finish-ing coats. -The following aliphatic hydrocarbons are used in the examples:
Aniline Content of Boilin~ Point Kauri-Butanol Aromatic Range C. About C. Value, About Hydrocarbons White Spirit A 145-200 56 39 18 White Spirit B 184-207 85 26 0 The invention is illustrated by the following examples. Parts are by weight.
..
;~.
~6g4;zS82 ELAM~E 1 A polymer A with co-polymerizable double bonds on the basis of p-tertiary butyl styrene/glycidyl methacrylate/methacrylic acid is prepared in the following manner: 190 parts p-tertiary butyl styrene, 10 parts glycidylmethacrylate, 120 parts white spirit A, 4 parts di-tertiary-butyl-peroxide, and 4 parts tertiary dodecylmercaptan are charged to a reaction vessel equipped vith stirrer, reflux aondensor, addition funnel, and ther-mometer and heated to 140C. A blend consisting of 380 parts p-tertiary butyl styrene, 20 parts glycidylmethacrylate, 240 parts white spirit A, 8 parts di-tertiary butyl pero~i~ and 8 parts tertiary-dodecylmercaptan is added in drops continuously within a period of two hours; and the batch is stirred for a further two hours at 140C.~ then the temperature is reduced to 120C. and a mixture of 0.2 parts hydroquinone, 1 part dimethylbenzylamine, and 50 parts white spirit A and, within the course of 1 hourj 13.2 parts me.thacrylic acid and 250 parts white spirit A are added. The batch is stirred ~
for a further three hours at 120C. The obtained solution has a solids .:
content of 50 percent. ~ .
. A dispersion is prepared from 14.7 parts of the above solution, 18 parts methy.lmethacrylate, 12 parts styrene, 3.6 parts ethylacrylate, 6 parts -.
hydroxybutylacrylate, 0.36 parts bisazoisobutyronitrile, and 601.3 parts of :~
white spirit B. The blend is charged to a reaction vessel as described above .
and the batch is held for 20 minutes at 90l.C. under the protection of N2-gas.
In the course of one hour, a blend of 230 parts of the solution of polymer A, 244.8 parts methylmethacrylate, 163.2 parts styrene, 56.4 parts ethyl acrylate 84 parts hydroxybutylacrylate, 12 parts acrylic acid, and 5.64 parts azobisisobutyronitrile is added and the temperature of 90C~ is held for another hour. A stable dispersion without residues and seeds is obtained.
The dispersion has a solids content of 48 percent and a viscosity of 13.4 s, Ford cup no. 4 at 20C.
7.85 parts of the polymer solution A of Example 1 together with 6 parts methylmethacrylate, 10 parts ethylacrylate, 0.16 parts azobisisobutyro-.
.
.
1C)4Z582 nitrile, and 284 parts white spirit B are charged to a reaction vessel equipped with stirrer, reflux condensor, and thermometer. The batch is held at 90C. for 20 minutes under the protection of N2-gas. Subsequently a blend of 128.1 parts polymer A solution, 81.6 parts methylmethacrylate, 154.4 parts ethylacrylate, 80 parts tripropyleneglycolmonomethacrylate, 6 parts -acrylic acid, and 3.68 parts azobisisobutyronitrile is added in the course of one hour and a temperature of 90C. is held for ano*her hour. A highly stable dispersion, without any residue or seeding, is obtained having a solids content of 52.9 percent and a viscosity of 140 s, Ford cup no. 4 at 20C.
. :
4.8 parts of the polymer A solution of Example 1 are blended with 6 parts methylmethacrylate, 4 parts p-tertiary butyl styrene, 1.2 parts ethylacrylate, 2 parts hydroxybutylacrylate, 0.1 parts azobisisobutyronitrile and 198.6 parts white spirit A, and the blend is charged to the equipment described in Example 1 and held at 90C. for 20 minutes under the protection of N2-gas. In the course of one hour, a blend of 76.4 parts polymer A
solution, 81 parts methylmethacrylate, 54.4 parts p-tertiary butyl styrene, 18.4 parts ethylacrylate, 28 parts hydroxybutylacrylate, 4 parts acrylic acid, and 1.9 parts azobisisobutyronitrile is added continuously and a temperature of 90C. is held for another hour. A highly stable dispersion without residues and seeding is obtained, having a solids content of 49.8 -~
percent and a viscosity of 47.3 s, Ford cup no. 4 at 20C.
A polymer A on the basis of p-tertiary butyl styrene/glycidylmeth_ acrylate/acrylic acid chloride carrying co-polymerizable double bonds i9 prepared in the following way: 90 parts p-tertiary butyl styrene, 10 parts glycidyl methacrylate, 60 parts white spirit A, 2 parts di-tertiary butyl peroxide, 2 parts tertiary dodecylmercaptan are charged to the equipment described in Example 1 and are heated to 140C. A blend of 180 parts p-tertiary butyl styrene, 20 parts glycidyl methacrylate~ 120 parts whi~e spirit A, 4 parts di-tertiary butyl peroxide, and 4 parts tertiary dodecylmercaptan ,' ' .
16)4;~
is added in drops within the course of two hours and the batch is stirred for a further two hours at 140C. Then the temperature is reduced to 120C., and a blend of 0.2 parts hydroquinone, 1.2 parts dioctylhexylamine and 90 parts white spirit A is added and~ in the course of one hour, a blend of 19.8 parts acrylic acid chloride and 30 parts white spirit A is added. The batch is held for a further three hours at 120C. and stirred. The obtained solution has a solids content of 51 percent.
A dispersion is prepared from 0.7 parts of this solution and 3 parts styrene, 5 parts methylmethacrylate, 0.06 parts azobisisobutyronitrile, and 113 parts white spirit A. The blend is charged to the equipment des-cr~bed in Example 1 and hehd at 90C. for 20 minutes under N2-gas. In the course of one hour, a blend of 22.1 parts of the polymer solution (of paragraph 1), 32 parts styrene, 30 parts methyl~ethacrylate~ 30 parts hydroxy- -butylacrylate, and 0.94 parts azobisisobutyronitrile are added and the -~
temperature of 90C. is held for another hour. A dispersion without residues is obtained having a solids ~ontent of 46 percent and a viscosity of 29.2 s, Ford cup no. 4 at 20C.
50 parts of the dispersion of Example 2 are mixed with 17.5 parts of benzoguanamine resin ~a non-plasticized butanol partially etherified benzoguanamine-formaldehyde condensation product with high reactivity; a viscosity of 6 - 10 P/20C.~ 70 percent solids in butanol) adding 0.16 parts of p-toluene sulfonic acid. The blend is applied (by conventional methods) to glass or steel panels and cured at 130C. for 30 minutes. A hard, clear, and scratch-resistant (thermoset) aoating is obtained, which shows excellent resistance to solvents such as xylol or acetone.
_ 9 _ . .. . .
.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Dispersions of hydroxy group containing co-polymers in organic liquids, comprising:
(A) 10 - 30 percent by weight of a co-polymerizable polymer which is the reaction product of (1) a low molecular weight co-polymer of 80 - 94 percent by weight p-tertiary butyl styrene, and 4 - 12 percent by weight glycidylmethacrylate, and (2) 2 - 8 percent by weight (meth)acrylic acid or (meth)acrylic acid chloride or a mixture thereof, the sum of (1) and (2) being 100 percent, and (8) 70 - 90 percent by weight of co-polymerizable ethylenically un-saturated monomers, at least one of them carrying a functional hydroxy group, co-polymerized in an organic liquid, said organic liquid being a true solvent for component A and the dispersed co-polymer of A and B being substantially insoluble therein, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210°C.
(A) 10 - 30 percent by weight of a co-polymerizable polymer which is the reaction product of (1) a low molecular weight co-polymer of 80 - 94 percent by weight p-tertiary butyl styrene, and 4 - 12 percent by weight glycidylmethacrylate, and (2) 2 - 8 percent by weight (meth)acrylic acid or (meth)acrylic acid chloride or a mixture thereof, the sum of (1) and (2) being 100 percent, and (8) 70 - 90 percent by weight of co-polymerizable ethylenically un-saturated monomers, at least one of them carrying a functional hydroxy group, co-polymerized in an organic liquid, said organic liquid being a true solvent for component A and the dispersed co-polymer of A and B being substantially insoluble therein, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210°C.
2. The dispersion of claim 1 containing from 15 to 25 percent by weight of A and 75 to 85 percent by weight of B.
3. The dispersion of claim 2 wherein the ethylenically unsaturated monomers of B are selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, hydroxy-ethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, tripropyleneglycolmono(meth)acrylate, (meth)acrylic acid, styrene, p-tertiary-butylstyrene, and vinyltoluene.
4. A composition of matter comprising in combination the dispersion of claim 1 and a crosslinking agent as a thermosetting coating composition.
5. Process for producing dispersions of hydroxy group containing co-polymers in organic liquids, comprising co-polymerizing (A) 10 - 30 percent by weight of a co-polymerizable polymer being a reaction product of (1) a low molecular weight co-polymer of 80 - 94 percent by weight p-tertiary butyl styrene and 4 - 12 percent by weight glycidylmethacrylate, and (2) 2 - 8 percent by weight (meth)acrylic acid or (meth)acrylic acid chloride or a mixture thereof, the sum of (1) and (2) being 100 percent, and (B) 70 - 90 percent by weight of co-polymerizable ethylenically un-saturated monomers, at least one of them carrying a functional hydroxy group, in an organic liquid, said organic liquid being a true solvent for component A and the dispersed co-polymer of A and B being substantially insoluble there-in, wherein the organic liquid is a straight chain or branched chain aliphatic hydrocarbon, or a mixture thereof, having a boiling range of from 145 to 210°C.
6. The process of claim 5 wherein component A is present at from 15 to 25 percent by weight and component B is present at from 75 to 85 percent by weight.
7. The process of claim 6 wherein the ethylenically unsaturated monomers of B are selected from the group consisting of methyl(meth)-acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)-acrylate, tripropyleneglycolmono(meth)acrylate, (meth)acrylic acid, styrene, p-tertiarybutylstyrene, and vinyltoluene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT90173A AT320279B (en) | 1973-02-01 | 1973-02-01 | Process for the preparation of dispersions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1042582A true CA1042582A (en) | 1978-11-14 |
Family
ID=3502444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA191,173A Expired CA1042582A (en) | 1973-02-01 | 1974-01-29 | Producing self-stabilizing polymer dispersions in hydrocarbon liquids |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS49107391A (en) |
| AT (1) | AT320279B (en) |
| CA (1) | CA1042582A (en) |
| CS (1) | CS175471B2 (en) |
| DE (1) | DE2400923A1 (en) |
| FR (1) | FR2216303B3 (en) |
| GB (1) | GB1440282A (en) |
| IT (1) | IT1006726B (en) |
| PL (1) | PL88578B1 (en) |
| SU (1) | SU629885A3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764447A (en) * | 1985-07-17 | 1988-08-16 | Ricoh Co., Ltd. | Non-aqueous type resin dispersion and electrophotographic developer containing said resin |
| CA1335908C (en) * | 1988-10-07 | 1995-06-13 | Junji Oshima | Core-shell polymer, composition containing the polymers and its molded articles. |
| US5496905A (en) * | 1995-03-10 | 1996-03-05 | The Goodyear Tire & Rubber Company | Paint resin for use in paraffinic solvents |
| DE10010417C1 (en) * | 2000-03-03 | 2001-09-27 | Basf Coatings Ag | Aqueous spray paint, useful e.g. for repairing defects on automobiles, contains water-soluble or -dispersible copolymer of ethylenically unsaturated monomers |
| CN110191930B (en) * | 2017-01-19 | 2022-01-04 | 日产化学株式会社 | Composition for forming underlayer film for forming fine phase separation pattern |
-
1973
- 1973-02-01 AT AT90173A patent/AT320279B/en active
-
1974
- 1974-01-04 IT IT1908774A patent/IT1006726B/en active
- 1974-01-09 DE DE19742400923 patent/DE2400923A1/en active Pending
- 1974-01-28 FR FR7402734A patent/FR2216303B3/fr not_active Expired
- 1974-01-29 CS CS59974A patent/CS175471B2/cs unknown
- 1974-01-29 PL PL16840774A patent/PL88578B1/pl unknown
- 1974-01-29 CA CA191,173A patent/CA1042582A/en not_active Expired
- 1974-01-31 GB GB461374A patent/GB1440282A/en not_active Expired
- 1974-02-01 JP JP1291474A patent/JPS49107391A/ja active Pending
- 1974-02-01 SU SU742000728A patent/SU629885A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| PL88578B1 (en) | 1976-09-30 |
| FR2216303A1 (en) | 1974-08-30 |
| JPS49107391A (en) | 1974-10-11 |
| FR2216303B3 (en) | 1976-11-19 |
| DE2400923A1 (en) | 1974-08-22 |
| SU629885A3 (en) | 1978-10-25 |
| GB1440282A (en) | 1976-06-23 |
| CS175471B2 (en) | 1977-05-31 |
| IT1006726B (en) | 1976-10-20 |
| AT320279B (en) | 1975-02-10 |
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