PT91185B - Process for the preparation of a coating composition and of polyanhydrides - Google Patents

Abstract

A novel polyanhydride having at least two cyclic carboxylic acid anhydride groups per molecule also contains pendent amine groups, the proportion of amine groups to cyclic carboxylic acid anhydride groups being no more than 4:1 and the content of free carboxylic acid groups, if any are present, being less than 200 mole per cent based on the amine groups. A coating composition comprises (A) a hydroxy component having at least two free hydroxy groups per molecule and (B) an anhydride component having at least two cyclic carboxylic acid anhydride groups per molecule, at least one of (A) and (B) being a film-forming polymer. The anhydride component (B) contains a catalytically effective amount of pendent amine groups for accelerating the curing reaction between the hydroxy groups of (A) and the anhydride groups of (B) and is preferably one of the novel polyanhydrides.

Description

DESCRIPTION

The present invention relates to a process for the preparation of coating compositions and a process for the preparation of new polyanhydrides for use in these compositions.

US Patent 4452948 describes a two-component coating composition comprising a hydroxy component and an anhydride component, wherein the hydroxy component is a colored polymer. at least two free hydroxy groups per molecule and also has amino groups in its molecule to accelerate the curing reaction between the two hydroxy groups and the anhydride groups, and the anhydride component and a polymer with at least two anhydride groups. cyclic carboxylic acid per molecule. In a less preferred modification the amino groups are present in a separate amino compound instead of being in the hydroxy component molecule. The coating compositions of the Patent

US 4452948 have the advantage that they are curable at room temperature without the use of toxic isocyanates and have been successfully used with car finishing coatings, particularly in refinishing, and as a yacht paint.

European Patent Application 134691 describes a three-component coating composition comprising a compound with at least two hydroxy groups,

TF is a compound with at least two anhydride groups and a compound with at least two apoxide groups.

European Patent Application 259172 describes a coating composition comprising an anhydride polymer and a polymer containing hydroxyalkylamino, hydroxyalkoxyalkylamino, hydroxy substituted hydroxy, polyacryloxy, hydroxy-substituted polyacrylate, chemic acid or oxide. One of the polymers comprises a flexible polymer chain, and has its functional groups present as terminal groups at the end of the flexible polymer chain.

US Patent 3984382 describes a modified cationic vinyl polymer suitable for electrocoating and prepared by reacting a copolymer of maleic anhydride, styrene and alkyl acrylate and / or a di-functional amine until it has no residual anhydride rings, product with a monoepoxy compound.

with a modified polymer amino alcohol and reacting the

US Patent 3,449,250 and 3329658 describe an additive that communicates mineral oil stability and detergency. The additive comprises a maleic anhydride copolymer and an alpha-olefin which has been partially esterified with an aliphatic alcohol to prepare the oil-soluble copolymer and in which almost all the remaining carboxyl groups are imidized.

German Patent 1595333 describes water-soluble polyelectrolytes useful as flocculating agents and retention aids in papermaking and which are prepared by reacting a copolymer of an ethylenically unsaturated carboxyl anhydride with a polyamine containing only a primary or secondary amino group, and making if the reaction product is reacted with an epihalohydrin and / or a diepoxide.

A process for the preparation of a coating composition according to the invention and characterized by mixing a hydroxy component (A) having at least two free hydroxy groups per molecule with an anhydride component (B) having at least two groups

of cyclic carboxylic acid anhydride per molecule and containing as a pendent groups in their molecules an effectively effective amount of amino groups to accelerate the curing reaction between the hydroxy groups of (A) and the anhydride groups of (B), being at least one of (A) and (B) a film-forming polymer.

Preferably, the anhydride component (B) is a polyanhydride with at least two cyclic carboxylic acid anhydride groups per molecule, and containing pendent amino groups, the ratio of amino groups to cyclic carboxylic acid anhydride groups not exceeding 4 : 1 and the content of the free carboxylic acid groups, if present, inside 200 mole percent based on the amino groups.

The invention also provides processes for the preparation of such functional amino polyanides.

The ratio of amino groups to cyclic carboxylic acid anhydride groups in the polyanhydride is preferably (0.01: 1) and no more than 1.5: 1, more preferably 0.01: 1 to 1: 1. The content of free carboxyl groups is preferably less than 100 mole percent based on amino groups, more preferably, free carboxyl groups are essentially absent or are present in amounts less than 20 mole percent based on amino groups.

The coating compositions prepared according to the invention have advantages over those described in US Patent 4452948 and European Patent Application 259172. Polyanhydrides can be used in coating compositions with a wide variety of polymers with hydroxy functions, including commercial unmodified polymers. The coating compositions also have superior stability against photo-degradation when compared to many of the coating compositions of European Patent Application 259172. The coating compositions avoid the possibilities of environmental damage and adhesion of cured composition that exist when used. a compound with a free amino group as a catalyst.

The amino groups present in the polyanhydride are preferably tertiary amino groups, which are the most effective in catalyzing the reaction between the hydroxy and anhydride groups without giving rise to side reactions.

One type is a polymer containing preferred substituted imido groups and groups of cyclic polyanhydride and carboxylic anhydride with N- (diamethylaminoamino).

Such a polyanhydride can be prepared according to the invention by reacting a polymer containing cyclic carboxylic acid anhydride groups with a less than stoichiometric amount of a polyamine containing a primary amino group and at least one tertiary amino group. Said polymer containing cyclic carboxylic acid anhydride groups is preferably derived from an olefinically unsaturated cyclic carboxylic acid anhydride.

polymer containing cyclic anhydride groups can for example be a copolymer of an olefinically unsaturated cyclic carboxylic acid anhydride such as maleic, itaconic, citraconic or vinylic succinic or vinyl trimellate anhydride with one or more unsaturated olefinic co-monomers as for example an alpha -olefin, for example ethylene or propylene, or a vinyl comonomer, for example styrene or substituted styrene, vinyl acetate or vinyl chloride, or an ester of acrylic or methacrylic acid, for example butyl acrylate, style acrylate, methacrylate methyl or butyl methacrylate. Preferred copolymers contain 10-40 percent, more preferably 20 - 35 percent, by weight of maleic or itaconic anhydride groups and have a molecular weight of 1 500 - 30 000, for example 4 000 - 12 000. If the composition of coating is to be used as a final decorative coating layer it may be preferable to use a vinyl comonomer in a molar ratio of at least 1: 1 to the anhydride monomer, as described in US Patent 4798745.

polymer containing cyclic anhydride groups may alternatively be an anhydride additive of a diene polymer such as maleinised polybutadiene or a maleinised butadiene copolymer, for example a

butadiene / styrene copolymer. The maleinised diene polymer is preferably hydrogenated to remove residual unsaturation. Maleic terpene anhydride copolymer resins are another alternative. An anhydride additive of an unsaturated fatty acid ester, for example a copolymer of allyl styrene alcohol esterified with an unsaturated and maleised fatty acid, may also be the solution to be used. The polymer containing anhydride groups can alternatively be prepared by reacting a polymer containing thiol groups with an olefinically unsaturated cyclic carboxylic acid anhydride such as maleic anhydride or itaconic anhydride. The polymer containing thiol groups is preferably labeled with thiol; it may for example be a multi-pair telequelic polymer formed by the reaction of a hydroxy-bound copolymer corresponding to mercaptoaceptic acid.

Alternative anhydride-containing polymers can be prepared from hydroxy-containing polymers, for example hydroxyethyl acrylate or hydroxyethyl methacrylate copolymers or styrene / allyl alcohol copolymers, by reaction with a tricarboxylic compound capable of introducing anhydride groups, for example, as described in European Patent Application 259172. An additional alternative type of polymer containing anhydride groups is an adduct of trimellitic anhydride and a polyol, as described in European Patent Application 134691.

The polyamine which is reacted with the polymer containing anhydride groups and preferably a primary / tertiary diamine, for example, N, N-dimethylpropane-1,

3-diamine ((CH ^ ^ NCf ^ Cf- ^ Cf ^ Ní ^), N, N-dimethylethylenediamine,

4-amino-1- (dimethylamino) -pentane, N, N-diethylpropane-1,3-diamine, 2-amion-pyridine, 3-amino-pyridine, 4-amino-pyridine or

N- (3-aminopropyl) -morpholine primary amino group reacts with the anhydride group to form an imido group that has an amino group in a pendant organic group attached to the nitrogen atom of the imido group. The substituted imido groups obtained have the general formula.

X in which each Z represents a polymer residue and X and an organic group containing a tertiary amino group and is attached to the imido nitrogen atom by a carbon-nitrogen bond. The group X may for example be an aminoalkyl group of the form -A-NR ₂ , where -A- is a straight or branched chain alkylene group preferably having 2 to 8 carbon atoms; and each group R and an alkyl group preferably having 1 to 4 carbon atoms is a heterocyclic ring containing a tertiary nitrogen atom such as 4-pyridyl; or an alkyl group substituted by a heterocyclic ring containing a tertiary nitrogen atom such as the pyridine or morpholine ring. For example, using N, N-dimethi1-propane1,3-diamine

-h ₂ o

-z + (ch ₃ ) ₂ nch ₂ ch ₂ ch ₂ nh ₂ zΟΑΚΛ)

CH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ in which each Z represents a polymer residue.

The reaction between the polymer containing anhydrous groups and the diamine can, for example, be carried out by heating under reflux in an organic solvent that has a boiling point well above that of water (for example 120 - 180 ^and C) or that forms an azeotrope with water, the water being distilled off during the reaction. Examples of solvents are esters such as butyl acetate or methoxypropyl acetate, ketones such as methyl isobutyl ketone or aromatic hydrocarbons such as xylene. The anhydride and the amine initially react to form

an acid amide and may have a limited (only 1 ubly 1, particularly in hydrocarbon-type solvents. It may be preferable to add the diamine gradually during the reaction. Alternatively, the reaction can be carried out using a two-phase reaction in which the acid amide can be prepared at an early stage and heated in a solvent, with water removal, or with a dehydrating agent such as acetic anhydride or a carboiimide such as dicylhexyl carboiimide.

The proportion of polyamine reacted with the polymer containing anhydride groups is generally not more than 0.8 mole of polymin per mole of anhydride groups in the polymer and is preferably not more than 0.5 moles / mole so that the resulting polyanhydride contains at least as many groups anhydride as N- substituted imido groups (amino acid 1: 11). Preferably, the molar ratio of diamino to anhydride groups is 0. - 0.5: 1, more preferably 0.1 - 0.33: 1.

An alternative form of polyanhydride can be prepared according to the invention from a polymer of an unsaturated tricarboxylic acid such as aconitic acid or an anhydride thereof by reaction with an amino alcohol, preferably a tertiary amino alcohol such as Ν , Ν-dimethyl ethanolamine. The reaction is carried out under conditions suitable for removing water, for example under reflux in an organic solvent with a boiling point higher than that of water and / or azeotroping with water, using for example butyl acetate as a solvent.

CH ₂ COOH

H ₂ 0

COOH COOH

COOH C C = O

CH ₂ COOCH ₂ CH ₂ N (CH ₃ ) ₂ (CH _{3) 2} NCH ₂ CH ₂ OH CH ₂ COOCH ₂ CH ₂ N (CH ₃ ) 2

-c - z

O = C C = 0 -H „0

COOH COOH

This product containing anhydride groups and pendent amino alkyl ester groups may have a higher reactivity with hydroxy groups.

A polymer containing anhydride groups and pendent amino groups cannot in general be obtained by copolymerizing an unsaturated cyclic carboxylic acid anhydride such as maleic anhydride or itaconic anhydride and an unsaturated amine such as diakylamino-alkyl acrylate or methacrylate. This polymerization forms a

polyacid would you like one dark complex of transfer loading as described per Taylor and Woodward in J. Polymer Science, Part A., Vol: 1, pp 1473-1482 (1963) . A polymer containing

anhydride groups and can however be a preferred azeotropic bond and pendent amino groups prepared according to the invention by copolymerizing an alefinically unsaturated dicarboxylic acid and an olefinically unsaturated amine, preferably a tertiary amine such as alkyl dialkylamino acrylate or methacrylate, in specific conditions to remove water, for example at a temperature above 100 C ² and / or olefinically insatuo desti0 dicarboxylic acid itaconic acid, which may be dissolved in a polar organic solvent such as tetrahydrofuran. The unsaturated dicarboxylic acid solution is preferably

added to the polymerization reactor separately from the amine monomer, which can be for example diethyl acrylate or methacrylate. The amine monomer can be dissolved in an organic solvent such as a hydrocarbon, ester or ketone, preferably aromatics together with one or more unsaturated olefinically comonomers. The solvent for the unsaturated dicarboxylic acid can be removed by distillation during ipooimerization; the copolymer is more soluble in organic solvents than momomer acid.

An additional alternative type of polyanhydride and a graft copolymer of a polymer containing cyclic carboxylic acid anhydride groups and a polymer containing amino groups. Such a graft copolymer can be prepared according to the invention if one of the polymers contains an olefinic unsaturation (resulting for example from the polymerization of a diene) and the graft is carried out using a catalyst with free radicals such as peroxide. The polymer containing the unsaturation is suitably a maleinised diene polymer, preferably maleinised polybutadiene containing residual unsaturation.

component with hydroxy functional groups (A) reacting with the component with anhydrous functions containing amino (B) and preferably a film-forming polymer and can be chosen to give the desired properties __. na_c as opposed to _cur.a .gives. For example, it can be an addition glass with pendant hydroxy groups such as an acrylic copolymer containing 5-80% by weight, preferably 10—50% by weight, of a hydroxy containing ester of an olefinically unsaturated carboxylic acid, for a for example a hydroxyalkyl acrylate or methacrylate such as for example hydroxyethyl acrylate, hydroethyl methacrylate, hydroxypropyl methacrylate or hydroxypropyl acrylate. The hydroxy-containing ester may further contain ester bonds or ether bonds, for example 2- (beta-hydroethoxy) ethyl acrylate or methacrylate or a hydroxyethyl acrylate or methacrylate adduct with caprolactone. Examples of olefinically unsaturated monomers that can be copolymerized with the hydroxy-containing ester are acrylic esters such as acrylate

ethyl late and hexyl acrylate and vinyl compounds such as styrene, vinyl acetate and vinyl chloride. The hydroxy component (A) can be a copolymer containing a polyester segment, for example a graft copolymer of acrylic monomers on an unsaturated polyester. The acrylic monomers are preferably chosen from those mentioned above and include a hydroxy-containing monomer such as, for example, hydroxyacrylate acrylate or methacrylate. The polyester segment is preferably a low molecular weight polyester (less than 1,000) derived from a polyol such as ethylene glycol, propylene glycol or trimethyl 1 propane and an acid or anhydride such as, for example, italic acid, isophthalic acid or adipic acid with a small amount of an unsaturated acid or anhydride such as maleic anhydride. The polyester can form, for example, up to 50% by weight, preferably - 25% by weight, of the graft copolymer. Coatings prepared using an acrylic component with hydroxy functions or a component with hydroxy functions of an acrylic polyester graft copolymer have an excellent viscosity and appearance after spray application.

An alternative process for preparing an addition copolymer with pendent hydroxy groups for use as a hydroxy component (A) and preparing a copolymer with starch groups, for example acrylamide or methacrylamide units, and forming N-methylol groups in the amide by reaction with formaldehyde.

component with hydroxy functions (A) may alternatively be a telequelic polymer with hydroxy groups at each end of a polymer chain, such as a polyether, an aliphatic polyester, silicone, diene polymer, hydrogenated diene polymer, polyurethane, polyisobutylene or polyacrylate. The use of this polymer t e 1 and q_ueJL ± -o ^ _p can give coatings cured with_a_also high resistance to impact and abrasion. Such a telequelic polymer preferably contains more than two hydroxy groups per molecule for example it can be a polyester or polyether with three or four bonds terminated each by a hydroxy group.

of polyester. The alkyl polyol polyester containing

An example of such a commercially available hydroxy-terminated polyester is a polycapro lactone tetraol with a molecular weight of about 1,000. Alternative hydroxy functional polyesters can be prepared from polyols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1 , 2-butanediol,, 4-butanediol, 1,6-hexanediol, 1,4-cyclohexane-dimethyl1, diethylene glycol, dipropylene glycol or neopentyl glycol with dicarbοχi1ico components such as phthalic anhydride, isophthalic acid, maleic anhydride and / or adipic, azelaic or sebacic and a trifunctional compound such as trimethyl propane, trimethyl, glycerol or anhydride and trimellitic, using an excess of polyols to obtain a hydroxy-terminated polymer. A lactone such as caprolactone or hydroxy acid, such as hydroxycaproic acid or dimethylol propionic acid, can be included in the formation reaction with hydroxy functions. It can be a fatty acid radical. Another suitable polyester with hydroxy functions can be prepared by reacting an epoxide such as ethylene oxide or an ether or a glycidyl ester with a dicarboxylic acid. Several hydroxy-terminated polyesters are sold commercially, for example under the Registered Trademarks Teracol and Terathane, typically having molecular weights in the range of 600-2,400. These are generally obtained by reacting a polyol such as glycerol, trimethylolpropane or a higher polyol with propylene oxide and / or ethylene oxide or with tetrahydrofuran. Hydroxy-terminated addition polymers, for example polybutadienes or hydroxy-terminated butadiene / acrylonitrile can also be used Hydroxy-terminated polyurethanes can alternatively be used, obtained for example from a polyisocyanate and an excess of a polyol component which it may comprise a polyether polyol and a low molecular weight polyol.

Polymers with alternative hydroxy functions suitable for use as a hydroxy component (A) include starch-containing polyols prepared by reacting a polycarboxylic acid or anhydride with a polyol and a diamino or amino alcohol, epoxy polyols prepared by reacting the glycidyl ethers of polyphenols such as bisphenol A diglycidyl ether with a bisphenol or an aliphatic diol, polyvinyl alcohol, an allyl alcohol polymer such as a styrene / allyl alcohol copolymer, optionally containing allyl ether units, cellulose, or a derivative cellulose, or a polyurethane with hydroxy functions.

component with hydroxy functions (A) may alternatively be a non-polymeric polyol or may include a non-polymeric polyol such as ethylene glycol, 1,4-butane diol, neopentyl glycol, 1,4-cyclohexane-dimethanol, 2,2-dimethyl 2,2-dimethyl-3-hydroxypropyl-3-hydroxypropionate, diethylene glycol or an alkoxylated bisphenol A

The coating composition is generally a two-component composition in which the hydroxy component (A) and the polyanhydride (B) are stored separately and are mixed shortly before use. The coating can be applied to a substrate by spraying, for example spraying without conventional air or by spraying with two component feed in which the polymer (A) and (B) are not mixed until the spray head, either by roller or by brush. The coating composition can generally have a canned life of at least fifteen minutes when and to be applied by a double feed gun or at least one hour after mixing when applied by other techniques. The coating composition is preferably a curing composition at room temperature capable of curing at room temperature, for example 10 - 40® C, on the substrate to form a solvent-resistant and adherent hard film so that it can be overcoated in one period. 24 hour period. Maximum hardness, solvent resistance and impact resistance are generally established for a few days at room temperature, for example 5-20 days. Curing can be carried out at a temperature above room temperature, for example in the range 40-180® C, particularly 100 - 150 ^Q C for shorter periods if more convenient, for example when applied under industrial conditions.

The proportion of anhydride groups in the anhydride component (B) in relation to hydroxy groups in the composition12

hydroxy component (A) is preferably 0.5: 1-2: 1.

the anhydride component and the hydroxy component are each preferably dissolved in a solvent, such as a hydrocarbon and / or a polar organic solvent, for example xylene or toluene or trimethylbenzene or mixtures with an ester such as butyl acetate or acetate of ethoxyethyl or methoxypropyl acetate or with a ketone such as methyl isobutyl ketone or methyl isoamino ketone. For most uses, the polymers (A) and (B) are preferably both compatible in solution and in the absence of solvent in order to obtain a transparent composition.

For some uses where the toughness of the coating is more important than the appearance the polymers may be less compatible so that there is some phase separation as the coating dries, obtaining regions of a mixture rich in one polymer in a rich matrix in the other polymer. This fact can increase the resistance to the impact, although with a less complete cure since the components of hydroxy and anhydride are are stoichiometrically balanced in each phase.

The coating composition generally contains additives such as pigments or fillers, for example opaque or translucent pigments or metallic spot type pigments, fillers and fillers, plasticizers, antioxidants, UV stabilizers, surfactants or viscosity control agents including additives to improve trixotropy or resistance to bending or pigment orientation. These additives can be included in one or both components of the paint, although it is preferred to include any pigments or fillers that may contain significant amounts of water absorbed with the hydroxy component (A) to avoid reaction with the anhydride.

The coating compositions obtained according to the invention can be applied to a wide variety of substrates, particularly rigid substrates such as metal, wood, glass or plastic. Compositions can be applied to most primers

sold commercially. They can be applied by spraying, which is the most generally preferred form, by brush or roller, or by dipping or depositing. The coating compositions of the invention are very useful as finishing paints and are particularly useful as paint. _Pa_ra__ auitomó v ei.s., _ In clu in-_ do paint for vehicle refinishing. They can be applied as transparent coating systems on the basis of which a pigmented coating is covered with a transparent layer. The coating compositions can be used either as a base layer or as a transparent layer in these coating systems or preferably in both forms. They can also be applied as transparent coatings on known base coatings such as polyurethane, acrylic or polyester coatings.

The coating compositions obtained according to the invention may alternatively be obtained in the form of powder coating in some cases, provided that both the hydroxy components (A) and the anhydride component (B) are solid at temperatures up to 50 ^B C and provided that at least one of (A) and (B) is a synthetic resin with a glass transaction temperature in the range 0 - 120 ^s C, preferably 40 - 90 ^s C. For use in a powder paint the anhydride component ( B) preferably does not contain an olefinically unsaturated double bond in the alpha-beta or beta position, gamma with respect to any anhydride groups, and if the anhydride component (B) is an addition polymer or anhydride groups are preferably separated of the addition polymer chain by at least one intervening carbon atom. It can be derived from a polyanhydride of this type described in European Patent Application 209377, for example by reaction with a primary / tertiary diamine.

The polyanhydrides prepared according to the invention can be used as crosslinking agents for polymers containing hydroxy groups in uses other than coatings. For example, they can be used as crosslinking agents for cellulose. Cellulose may be, for example, in the form of pulp or in the form of fibers such as regenerated cellulose or cotton fibers.

It can be reacted with the polyanhydride by heating a suspension of the cellulosic material in a solution of the polyanhydride in an organic solvent. Alternatively, wood or a wood product can be reinforced by impregnation with a solution of the polyanhydride, or a cellulosic textile material that can be hardened with a solution of the polyanhydride.

The invention is illustrated by the following Examples, where parts and percentages are by weight. Examples 1-3, 7, 10, 12, 14 and 17 are examples of the preparation of polyanhydrides with amino functions according to the invention. Examples 4-6, 8, 9, 11, 13, 15, 16 and 18 are examples of coating compositions according to the invention.

Example 1 (a) Preparation of the Itaconic Anhydride Copolymer

The butyl acetate solvent (142 g) was placed in a 5 liter vessel equipped with gas. The addition funnel contained itaconic anhydride (150.0 g), methyl methacrylate (75.0 g) and styrene (275.0 g). 2,2-azobismethylbutyronitrile (25.0 g) was added to the above-mentioned mixture and the whole was dissolved in butyl acetate (500 g). The solvent was heated in the reaction vessel under reflux under a nitrogen atmosphere and the contents of the funnel were slowly added with stirring over a period of 3 hours. After the addition was complete, stirring and heating was continued for another 1.5 hours to complete the polymerization. The resulting polymer, POLYMER A, had an average molecular weight Mn of 8000 with respect to polystyrene, determined by gel permeation chromatography, and an equivalent anhydride weight of 389.

(b) Preparation of Polyanhydride with Amino Functions

Polymer A (92.0 g) was placed in a 500 ml vessel equipped with a mechanical stirrer, addition funnel, Dean and StarR mousetrap and gas inlet, and the addition funnel was filled with N, N-dimethylpropane- 1,3-diamine (12.1 g). The contents of the vessel were heated under reflux in a nitrogen atmosphere and the contents of the funnel were added dropwise with stirring for 2 hours, during which time the reaction water was removed azotropically. Heating was continued for another 0.5 hours. In total,

and the hustle and bustle during up 2.1 g in Water. 0 a value of Mn of 8 500 gel action and a weight equivalent in anhydride ² ( ^a ) Preparation

Example 2

A maleic anhydride copolymer was prepared according to the procedure of Example 1 (a) but replacing an equal weight of maleic anhydride with itaconic anhydride. The resulting polymer, POLYMER D, had an MN value of 8,200 determined by gel permeation chromatography and an equivalent anhydride weight of 368.

(b) Preparation of the Polyanhydride with Amino Functions

In the same manner as described in Example 1 (b), Polymer D (75.0 g) was reacted in the butyl acetate solvent (75.0 g) with N, N-dimethylaminopropylamine (10.2 g).

The resulting polymer, POLYMER E, had an Mn value of 8,700 determined by gel permeation chromatography, an amine equivalent weight of 1010 and the equivalent anhydride weight of 979.

Example 3 (a) Preparation of a Polymer with Anhydride Functions

They were heated together in xylene (100 g) under reflux for 4 hours dipentaerythritol (1 mol,

254 g), epsilon-caprolactone (6 moles, 684 g), and dibutyl tin dilaurate (1.0 g). Mercaptoacetic acid (6 moles, 552 g) is added, and the reflux was continued with a water trap until 108 g of water were collected. Deisopropenyl acetate (100 g) was added, and full reflux was continued for hour to remove residual hydroxy groups.

The solvent and the ester were removed.

reacted in vacuo to obtain 1380 g of a reasonably fluid light yellow oil. If Adiconaram-maleic anhydride (588 g, 6 moles) and triethylamine catalyst (0.6 g) and the mixture kept at temperatures below 30 ⁵ C with stirring for 4 hours.

(b) Preparation of Polyanhydride with Amino Functions

Xylene (1,500 g) was added to the above reaction product, followed by 4-aminopyridine (2 mol, 188 g) over a period of 2 hours. The temperature of the mixture was increased to reflux and water (36 g) was collected over a period of 7 hours. Volumes were removed in vacuo to obtain 2120 g of polyanhydride, POLYMER F, as yellow oil, with an equivalent anhydride weight of 530.

Examples 4-6

Pentaerythritol (79.9 g) was suspended in the xylene solvent (1 400 g) containing dibutyl tin dilaurate (0.75 g) and placed in a 5 liter flask equipped with a mechanical stirrer, reflux condenser, addition funnel and gas inlet, and the addition funnel was loaded with dry epsiloncaprolactone (665.7 g). The contents of the vessel were stirred under reflux in a nitrogen atmosphere and the contents of the addition funnel were added to it slowly over 1 hour. Heating and stirring was continued for a further 2 hours and the solvents were removed in vacuo. The resulting polymeric tetraol, POLYMER C, had an Mn value of 1272 and an hydroxyl equivalent weight of 318.

Example 4

Polymer B (Example 1) (2.67 parts) was mixed in butyl acetate solvent (4.01 parts) as Polymer C (1.00 parts) in butyl acetate (1.00 parts) and poured in a glass. Cured at room temperature to obtain a hard, resistant, glossy film after 16 hours. After 7 days at room temperature, the film had good resistance to methyl ethyl ketone (MEC).

Example 5

A mixture of polymer E (Example 2) (3.08 parts) without butyl acetate solvent (4.62 parts) and polymer C (1.00 parts) in butyl acetate solvent (1.00 parts and cured at room temperature.

room temperature the film had a good

After 7 days the resistance to MEC.

Example 6 (5.30 pieces)

Polymer F (Example 3) was mixed with Polymer C (3.18 parts) in butyl acetate solution and poured into a beaker. The coating composition was cured at room temperature to obtain a hard but highly flexible coating.

Comparison Example

An itaconic anhydride copolymer was prepared in the manner referred to in Example 1 (a) but with a composition of 13% 13% itaconic anhydride monomer 20% methyl methacrylate to 67% styrene. Polymer B.

It was mixed with polymer C with hydroxy functions and coated on a glass panel as described in Example 4. After 7 days at room temperature the coating was soft and dissolved briefly in solvents such as xylene or Mec .

Example 7

A pre-mixture of itaconic anhydride (300 g), styrene (570 g), methyl methacrylate (130 g), Vazo 67 (Trade Mark) which is a free radical initiator (50 g) and a mixture of solvents of xylene (300 g) and N-methyl pyrrolidone (100 g) and a mixture under reflux of xylene (450 g) and N-methyl pyrrolidone (150 g) was added over 4 hours. The mixture was kept under reflux for cooling to obtain a solution with a solids content of 46.6%, a value of

Mn of 3800 and an average molecular weight (MW) of 7700 (in relation to polystyrene).

another hour and polyanide with

Preparation of the polyanhydride with amine functions

N, N-dimethylpropane-1,3-diamine (9.2 g, equivalent to one third of the available anhydride groups) was added dropwise over 15 minutes to a refluxing solution of the anhydride polymer (215 g) in a vessel equipped with water separator. Distillation was continued under reflux for a further 7 hours. Time after which 1.7 g of water were collected. The product had a solids content of 50.0% and an equivalent weight of anhydride of 1204.

Example 8

Preparation of acrylic polyol

Hydroxyethyl acrylate (193.5 g), methyl methacrylate (403.5 g), styrene (403.5 g) and Vazo 67 initiate (40) were pre-mixed and added dropwise to butyl acetate under reflux (1 000 g) for 3 hours. Reflux was continued for one hour to obtain a polymer solution with a solids content of 50%, a Mn value of 5,200, Pm of 10,300 (with respect to polystyrene) and an equivalent hydroxyl weight of 600.

Coating Compositions

24.1 g polyanhydride with amino functions of Example 7 and acrylic polyol action prepared above and film in a glass were mixed to obtain a thickness of the solution of

12.0 g of the solution was deposited as a dry micrometer film. Cure was effected by heating the coating at 150 C for ² 3 minutes of the cured composition tested was soaked in meti1eti1cetona (ECM) primarily by double afectuado passages 200 with the ECM.

Resistance to solvents passing through a fabric the coating was not

Example 9

Preparation of polyester polyol

They were heated under reflux trimethiololpropane (1 mol, 134 g), caprolactone (6 mol, 684 g) and xylene

(407 g) in the presence of tetrabutyl titanate (0.4 g) for 4 hours. The xylene was then removed by vacuum distillation to obtain a polymer with a solids content of 97%, an Mn value of 814 and an equivalent hydroxyl weight of 271.

Coating Composition

24.1 g of the polyanhydride solution with amino functions of Example 7 and 2.8 g of the polyester polyol prepared above were mixed, deposited as a film and cured by heating as described in Example 8. The resistance to solvents of the cured composition was 150 double passages with MEC.

Example 10

Preparation of polymeric anhydride

Aconitic acid (223 g), styrene (800 g) and Vazo 67 (50 g) were dissolved in tetrahydrofuran (780 g) and added dropwise to butyl acetate under reflux over a period of three hours. The azeotropic reflux was continued for another eight hours, the tetrahydrofuran and water were removed through a filling column, replacing the butyl acetate as necessary to prevent the development of a high viscosity.

The product obtained was a polymer with a solids content of 50%, an Mn value of 3,400 and a Pm value of 8,500 (in relation to polystyrene). It had strong anhydride peaks in its infrared spectrum and its acid value after precipitation and methanolysis was 43.6, indicating a substantial incorporation of aconitic residues.

its equivalent weight of calculated anhydride was 780.

Preparation of the polyanhydride with amino functions

Dimethylethanolamine (11.4 g) was added dropwise to the reflux polymeric anhydride solution prepared above (200 g) over a period of 15 minutes. The azeotropic reflux was continued until 2.3 ml were removed

TST · **

of water and no hydroxyl signal is visible in the infrared spectrum (8 hours). The resulting polymer had a solids content of 73. Its equivalent weight of amine after precipitation was 783, and its equivalent weight of anhydride was 851.

Example 11

11.7 g of the polyanhydride solution with amino functions of Example 10 and 2.8 g of the polyester polyol of Example 9 were mixed and deposited as a film in a glass with a dry film thickness of 60 microns. The film was allowed to cure at room temperature (about 20 ^s C). The resistance to coating solvents was tested after 7 days and found to be 95 double passages with MEC.

Example 12

Preparation of the polyanhydride with amino functions

Diethylaminoethyl methacrylate (100 g), styrene (630 g), neopentyl glycol dimethacrylate (70 g), and Vazo 67 (50 g) in xylene (400 g) were dissolved and used as reagent 1.

Itaconic acid (232 g) was dissolved in tetrahydrofuran (1000 g) as reagent 2.

Reagents 1 and 2 were separately added dropwise to reflux xylene (466 g) and N-methylpyrrolidone (200 g) over a period of three hours while simultaneously removing tetrahydrofuran by distillation through a fill column. The azetropic distillation was continued for another eight hours, replacing the solvent mixture with butyl acetate as needed, until the infrared spectrum revealed strong anhydride bands and very weak signals due to free carboxylic acid.

The resulting polymer solution was adjusted to a solids content of 50%. The polymer had an equivalent weight of amine of 1850 and an equivalent weight of anhydride of 560.

Example 13

11.2 g of the polymer with amino functions of Example 12 and 2.8 g of the polyester polyol of Example 9 were mixed, deposited as a film and allowed to cure at room temperature as described in Example 11. The solvent resistance the coating after 7 days was 100 double passages with MEC.

Example 14

Preparation of polymeric anhydride

Treated with hydrogen at a pressure of 80 atmospheres and at a temperature of 100 ^s C in a ratifying autoclave a maleised polybutadiene with anhydrous functions equivalent weight of anhydride calculated from Revertex as Lithene PM25MA) (200 g),

Metallic palladium (0.4 g). It was cooled or unloaded to obtain one of the palladium by filtration, with an equivalent weight of patented anhydride with a 490 (sold by xylene (400 g) and container, ventilated and solution, after recovery of solids content 33%,

490 and without essentially unsaturation.

Preparation of the polyanide with amino minute functions

N, N-dimethylpropane-1,3-diamine (1.37 g over 15% equivalent to 10% of the available anhydride) was added dropwise to a hydrogenated polyanide solution prepared above (200 g). The mixture was azeotroped for eight hours and part of the solvent was removed by vacuum distillation to obtain a polymer with a solids content of 50%, an equivalent weight of 5000 amine and an equivalent weight of anhydride of 555.

Example 15

Preparation of acrylic polyol

Hydroethyl methacrylate (130.0 g), methyl methacrylate (435 g), styrene (435

g) and Vazo 67 (50 g) and was added dropwise to butyl acetate under reflux (1000 g) over three hours. Continued- 22 -

reflux for one hour to obtain a polymer solution with a solids content of 54%, a Mn value of 4,800, a Pm value of 9,000 (with respect to polystyrene) and an equivalent weight of hydroxyl of 1,000.

11.1 g of the polyanhydride solution with amino functions of Example 14 and 18.5 g of the acrylic polyol solution prepared above were mixed, deposited as a film and cured with heat as described in Example 8. Resistance to solvents of the cured coating composition was greater than 200 double passages with MEC.

Example 16

11.1 g of the polyanhydride solution with amino functions of Example 14 and 12.0 g of the acrylic polyol solution of Example 8 were mixed, deposited as a film and treated with heat as described in Example 8. solvents of the cured coating composition was greater than 200 double passages with MEC.

Example 17

Preparation of the polyanhydride with amino functions

Style acrylate (47.1 g), diethylamino ethyl methacrylate (52.9 g) and Vazo (5.0 g) were mixed and introduced into butyl acetate at reflux (100 g) in a three hour period. The resulting polymer had an equivalent amine weight of 349. Then Lithene PM 25 MA (125.9 g) was added and added dropwise in benzoyl peroxide (11.3 g) over four hours . The mixture was refluxed for another four hours to obtain a graft copolymer, cooled and discharged. It had a solids content of 70%, an equivalent weight of amine of 789 and an equivalent weight of anhydride of 879. Although the graft was probably not complete, it was sufficient to ensure compatibility.

Example 18 graft polymer from Example 17

(12.6 g) was mixed with the acrylic polyol solution of Example 15 (18.5 g) and deposited on steel panels. Heat curing (20 minutes at 150 ^s C) produced a hard film, resistant to 70 double passages with MEC. This coating can be used as a greenhouse primer.

Claims (1)

- I ^a Process for the preparation of a polyanhydride with amino functions, characterized in that a polyanhydride containing groups of cyclic carboxylic acid anhydride is reacted with a less than stoichiometric amount of a polyamine containing a primary amino group and at least one amino group tertiary to obtain a polyanhydride containing amino groups pending in its molecule, the ratio of amino groups to cyclic carboxylic acid anhydride groups not exceeding 4: 1 and the content of free carboxylic acid groups, if present, less than 200 mole percent based on amino groups. 2. ^A process according to claim 1 characterized in that said polymer containing groups of cyclic carboxylic acid anhydride is derived from an olefinically unsaturated cyclic carboxylic acid anhydride. 3. ^A process according to claim 1 characterized in that said polymer containing groups of cyclic carboxylic acid anhydride is a copolymer of an olefinically unsaturated cyclic carboxylic acid anhydride with one more unsaturated olefinicarbonate comonomers. 24. The method of claim 1 wherein said polymer containing cyclic carboxylic acid anhydride groups is an addition product of an unsaturated cyclic carboxylic acid anhydride and a diene polymer. - 5 ^a Process for the preparation of a polyanhydride with amino functions, characterized by reacting an olefinically unsaturated tricarboxylic acid polymer or an anhydride thereof with an amino alcohol under conditions suitable to remove water, to obtain a polyanhydride containing amino groups pending in its molecule, the ratio of amino groups to cyclic carboxylic acid anhydride groups not exceeding 4: 1 and the content of free carboxylic acid groups, if present, less than 200 mole percent based on amino groups . - 6 ^a Process for the preparation of a polyanhydride with amino functions, characterized by copolymerizing an olefinically unsaturated dicarboxylic acid and an olefinically unsaturated tertiary amine under conditions suitable for removing water, to obtain a polyanhydride containing amino groups pending in its molecule, the ratio of amino groups to cyclic carboxylic acid anhydride groups not exceeding 4: 1 and the content of free carboxylic acid groups, if present, being less than 200 mole percent based on amino groups. - 7 ^a Process for the preparation of a polyanhydride with amino functions, characterized by reacting a polymer containing groups of cyclic carboxylic acid anhydride and a polymer containing amino groups, one of the said polymers containing an olefinic unsaturation, in the presence of a catalyst with free radicals to obtain a graft polymer. - 8 ^a Process in accordance with the claims 5.6 or 7 characterized by the groups amino be groups amino terciaric IS. - 9 ^a - Process in wake up with any of claims 1 to 8 featured for if make 'the reagents in appropriate proportions to obtain a polyanhydride containing amino groups and cyclic carboxylic anhydride groups in a ratio of 0.1: 1 to 1: 1. - 10 ^a Process for the preparation of a coating composition characterized by mixing an anhydride component (B) containing at least two groups of cyclic carboxylic acid anhydride per molecule and containing as a pendent group in its molecule a catalytically effective amount of groups amino to accelerate the curing reaction between the hydroxy groups in (A) and the anhydride groups in (B), at least one of (A) or (B) being a film-forming polymer. 11. ^A process according to claim 10 characterized in that the anhydride component (B) has been obtained by means of a process according to any one of claims 1 to 9. - 12 A process according ^to claim 10 or 11 characterized in that the hydroxy component (A) is an addition copolymer having hydroxyl groups pendentes.- 13 ^to process according to claims 10 or 11 characterized in that the hydroxy component ( A) be a telequelic polymer having hydroxy groups at each end of a polymer chain. 14a Process for the preparation of a coated substrate, in which a hydroxy component (A) having at least two free hydroxy groups per molecule and an anhydride component (B) having at least two cyclic carboxylic acid anhydride groups are applied to the substrate. per molecule which are reacted on the substrate to form a cured composition, characterized in that the anhydride component (B) contains pendent amino groups to catalyze the reaction of the hydroxy groups of component (A) with the anhydride groups of component ( B). 15. ^A process according to claim 14 characterized by tertiary amino groups. 16. ^A process according to claim 14 wherein the ratio of amino groups to cyclic carboxylic acid anhydride groups is 0.1: 1 to 1: 1. The applicant claims the priority of the patent application in Great Britain submitted on 18