RO108565B1 - Copolyesteric watery dispersion and preparation process thereof - Google Patents

Abstract

The invention relates to a dispersion aqueous, copolyesteric, used as adhesives, coating compositions, plasticizers, treatment for textiles, leather, metal, wood, paper and to a process for obtaining the same. copolyesters consisting of ortho-, meta-, terephthalic units, without sulfoisophthalic group, ortho-, meta-, terephthalic with sulfoisophthalic group, anhydride trimellitic, dicarboxylic and aliphatic acid units a mixture of glycols, bisphenolpropoxylate and glycerine and is obtained in the presence of the catalysts specific esterification and polyesterification, respectively polycondensation, at temperatures ranging from 140 to 275 ° C and at a pressure of 0.1 ... 0.3 mm col.Hg.

Description

The present invention relates to a copolyester aqueous dispersion having fine particle sizes and used as adhesives, coating compositions, plasticizers, treatment agents for textiles, leather, metal, wood, paper, and a process for obtaining a it.

It is known that in these areas, polymer solutions are used in organic solvents. These have the disadvantage of being toxic, flammable, expensive and polluting the environment.

The copolyester aqueous dispersion, according to the invention, removes the disadvantages mentioned in that it consists of a self-emulsifying copolyester, in a concentration between 1 and 99% g, obtained from 40 ... 90% moles (compared to the acid component), a di- or aromatic or aliphatic polycarboxylic without metalsulfonic group, 2 ... 15% moles (relative to the acid component) an aromatic polycarboxylic acid aromatic group with a metalsulfonic group, 20 ... 100% moles (compared to the glycolic component) having an aliphatic diol or polyol 2 ... 200 carbon atoms and 80% moles (relative to the glycolic component) of a bisphenol A adduct with ethylene oxide or propylene oxide, copolyester having the molecular weight Mn between 2000 and 20000 and the melting temperature between 0 and 200 ° C, with / without an organic cosolvent, up to 50% g, miscible with water and having a boiling temperature between 60 and 200 ° C, and water in a proportion of 1 ... 9 9% and optionally a component selected from a group consisting of an amine resin, an epoxy resin and a di- or polyisocyanate compound in a proportion between 1 and 50% g (compared to the aqueous dispersion), obtaining both dispersions with particle size between 1 and 10 μ as well as microemulsions and solutions with particle size <1 μ.

The process of obtaining the copolyester aqueous dispersions according to the invention consists in the esterification, respectively, the re-esterification of a mixture of aromatic or aliphatic di- or polycarboxylic acids without a metal-sulfonic group, an aromatic di- or polycarboxylic acid with a metal-sulphonic group or their ester derivatives, with an aliphatic diol, an aliphatic polyol or a bisphenol A adduct with ethylene oxide or propylene oxide in the presence of the catalyst selected from zinc acetate, calcium acetate or cobalt acetate in the amount of 0.02 ... 0.1% g / 100 g acids, at a temperature between 140 and 220 ° C, then polycondensation of the resulting reaction mixture, in the presence of the polycondensation catalyst chosen from styrene trioxide, zinc oxide or tetrabutyltitanate, in the proportion of 0.02 ... 0.1 g / 100 g reaction mixture, at a temperature between 220 and 275 ° C and pressure reduced gradually from 760 to 0.2 mm Hg, for 3 ... 6 h, making the poly mixture organic solvent-apple, at a temperature between 40 and 130 ° C, for a minimum of one hour and finally dispersing the mixture thus obtained, in water, at a temperature between 40 and 95 ° C and optionally at the aqueous dispersion thus obtained. add a component selected from a group consisting of an amine resin, epoxy resin and a di- or polyisocyanate compound.

The aqueous dispersion, according to the invention, was achieved by introducing hydrophilic comonomers with polar groups, such as metal-sulfonic salts of dicarboxylic acids and / or non-polyglycolic groups.

Water-dispersible copolyesters according to the invention are obtained by the polyesterification or polycondensation fusion reaction of some aromatic and / or aliphatic dicarboxylic acids or esters of the HOOC-R-COOH type wherein R =

- (CHA (n = 4 - 8; X = SO ₃ Na) with a mixture of glycols of the type HO (-RO-) _m H in which m = 1-100, R = (CH2) _p ; p = 2 - 6 or - CR, R ₂ -CH ₂ , R "R ₂ = H, CH ₃ , C ₂ H _s .

Thus, the aromatic acid component may be: terephthalic, isophthalic, ophthalmic or its anhydride, in a concentration of between 40 and 90 mol% (compared to the total acid component). At a concentration of less than 40%, obtained polyester resin has a lower mechanical and hydrolytic resistance, and when the content exceeds 80%, the resin is difficult to disperse in the aqueous system. Aliphatic dicarboxylic acid can be used in an amount of 0-5% moles (compared to the total acid component). When the aliphatic acid content exceeds 50%, the obtained resin has low mechanical and hydrolytic resistance, and the coating film obtained is sticky.

The aliphatic glycols used have 2 to 6 carbon atoms and are part of the series: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanedium, neopentyl glycol, 1,6-hexandiol and others. They are used in an amount of 0 ... 100% (compared to the polyol component). In some cases polyvalent polyols of the glycerine type can be used in trimethylolpropane, pentaerythritol and others, in the amount of 0 ... 10% mol (compared to the total polyol component). In order to improve the hydrophilicity of the polyesters, polyethylene glycols (M = 106 - 4000), polypropylene or polytetramethylene glycols (M = 500 - 5000) can be used, in a concentration of 0 ... 100% g. If the polyalkylene glycols exceed 40% g, the obtained polyester film has low hydrolytic strength.

Aromatic dicarboxylic acid with a sulphonated metal group is a metal salt of an aromatic acid of the type: sulfoterephthalic acid, 5sulfoisophthalic acid, 4-sulfophthalic acid. The sodium salt of these acids can be introduced in the amount of 0 ... 10% mol (compared to the total amount of acids). In the absence of sulfonic metal groups, the polyester resin has lower dispersibility properties in water. As the concentration of sulphonic metal groups increases, the dispersibility of the polyester improves markedly. The presence of an amount of the acidic component with a sulphonic metal group over 10 mol%, results in a coating having a lower hydrolytic resistance, although the dispersibility in water is excellent.

The molar ratio between the acidic and glycolic components is between 1 ... 1, 1 ... 2,25. Self-dispersible copolyesters have softening temperatures between 40 and 200 ° C, preferably 60 ... 180 ° C. When the softening temperature is lower than 40 ° C, the film obtained from the aqueous, copolyester dispersion, has lower water resistance and poor adhesion. If the softening point is higher than 200 ° C, the polyester resin is difficult to disperse in water.

The copolyesters have molecular weights between 2500 and 20000, preferably 3000 ... 15000, if the copolymer of the iester has a molecular weight of less than 2500, the obtained aqueous dispersion has low water resistance, and lower adhesion and mechanical properties (in particular flexibility). At a molecular weight of over 20,000, the polyester resin disperses hard in water, and the dispersions obtained have a high viscosity.

In order to obtain aqueous dispersions, copo-esterics, with fine particle size, can be used in concentration of 0 ... 50% g miscible organic cosolvents with water of the type: aliphatic or alicyclic alcohols, ethers, esters, ketones and others. The boiling point of the co-solvents used is between 60 and 200 ° C. When the organic solvents have a boiling point below 60 ° C, the films obtained by evaporation of water and solvent are uneven. At over 200 ° C, the aqueous dispersion dries hard and the dispersions have high viscosities.

The invention has the following advantages:

- making self-dispersible copolymers, without the use of an additional surfactant;

- avoiding the use of organic solvents - pollutants of the environment, by modifying the chemical structure of polymers, increasing the hydrophilicity of the macromolecular chain.

Further examples of the invention will be presented below.

Physico-chemical and physico-mechanical properties were measured by the following methods:

(1) The molecular weight was measured by determining the terminal groups, according to the equation:

jț / - 2 ^x 5.61 x 1000 '(-COOH) + (- OH) wherein: (-COOH) is the concentration of acid groups, expressed in mgKOH / g; (-OH) is the concentration of hydroxyl groups, expressed in mg KOH / g.

(2) The softening temperature was determined using the ring and ball apparatus, according to N.I.323 / 78.

(3) The melting temperature was determined using a Boetzius type heated table.

(4) The viscosity of the polymer was determined using a 1% concentration polymer solution in phenol: tetrachloroethane 3: 2 (25 ° C) on the Ubbelodhe viscometer.

(5) The particle size of the aqueous dispersion was determined using an optical microscope, type MC 01.

(6) The viscosity of the emulsion was determined with a Rheotest type 2 viscometer.

SUMMARY I

A mixture of dimethyl terephthalate (0.82 mol), dimethyladipate (0.10 mol), sodium dimethylsulfoisophthalate (0.08 mol), ethylene glycol (1.35 mol), 1,2-propanediol (0.9 mol), zinc acetate (0.1 g) and horseradish trioxide (0.1 g), was subjected to the transesterification reaction, at a temperature between 140 and 220 ° C, for 3 hours.

After removal of methanol, resulting as a by-product of the reaction, the reaction mixture is subjected to polycondensation under reduced pressure, gradually up to 0.2 mm Hg, at 240 to 270 ° C, for 3 hours, giving a resin. copolyester with a molecular weight of 10,000 and a softening temperature of 168 ° C.

In the same way, all the copolyesters presented in table 1 can be obtained except the proportions between the reactive substances (Ex.

1 ... 17).

10

SUMMARY _II. ----- If adipic acid, or phthalic anhydride, is used in synthesis, instead of dimethyladipate (respectively dimethylphthalate), the synthesis of 5 diglycolesters is carried out in two stages:

1. The synthesis of diglycololesters from adipic acid (phthalic anhydride) and glycols (ethylene glycol, 1,2-propanediol) takes place at a temperature of 140 ... 220 ° C, at a molar ratio of the acid component and the glycolic component 10 of 1: 2.25 with / without zinc acetate catalyst, in a concentration of 0.2 g / 100 g acids. The end of the reaction is considered when the acidity index of the reaction mixture is 5 ... 15 mg KOH / g.

2. Synthesis of dimethyl terephthalate (0.82 mol), 15 sodium dimethylsulfoisophthalate (0.08 new) with ethylene glycol (1.05 mol) and 1,2-propanediol (0.9 mol), zinc acetate (0.1 g ) and 0.1 g of ammonium trioxide takes place at a temperature of 140. 220 ° C, for 3 hours.

After the methanol is removed, as a by-product of the reaction, diglycol-adipate (0.10 mol) is added and the temperature is raised from 220 to 270 ° C for 3 hours with the pressure decreasing gradually to 0.2 mm Hg. The copolyester resin obtained has characteristics similar to that obtained in synthesis I, respectively the softening temperature 168 ° C and the molecular weight Mn = 9000.

In the same way, except the proportions of participation in the reaction, all the copolyesters presented in table 1 (1 ... 17) can be obtained.

SUMMARY III

A mixture of dimethyl terephthalate (0.67 moles), dimethylphthalate (0.3 moles), sodium dimethylsulfoisophthalate (0.03 moles), ethylene glycol (1.5 moles), bisphenolpropoxylate (0.5 moles), zinc acetate ( 0.1 g) and 0.1 g of horseradish trioxide was subjected to the transesterification reaction, at a temperature between 140 and 220 ° C, for 3 to 4 h. After removal of methanol as a by-product of reaction, the reaction mixture is subjected to the polycondensation reaction at a temperature between 220 ... 270 ° C and a gradually reduced pressure up to 0.2 mm Hg (Ex.18). The obtained copolyester has a softening temperature of 90 ° C and a molecular weight of Mn = 3000.

Similarly, the copolyesters presented in table 2 are obtained, except for the participation proportions of the raw materials.

Table 2

Components (% moles) and properties Number experiment 18 19 20 Polycarboxylic components Terephthalic acid 67 67 72 Phthalic anhydride 30 15 10 5-Sulfoisophthalic acid 3 3 8 Adipic acid 15 10 - Polyol components ethylene 50 50 50 polyethylene - - - Propoxylated bisphenol: 50 50 50 properties Temperature, softening, ° C 90 90 105 Molecular Weight, Mn 9500 11200 10700

SUMMARY IV

A mixture of: dimethyl terephthalate (0.5 moles), ethylene glycol (1,129 moles), glycerine (0.217 moles), polyethylene glycol (0.14 moles), zinc acetate (0.2 g) and stibium trioxide (0.07 g), is subjected to the transesterification reaction, at a temperature between 140 and 220 ° C, until all the methanol resulting from the reaction is distilled. Then, diglyphtolphthalate (0.23 moles) is added to the reaction mixture and the reaction temperature is raised to 240 ° C, and the pressure is gradually reduced to 10 mm Hg. Similarly, the copolyesters presented in table 3 are obtained (Ex. 21.22).

Table 3

Components (% moles) and properties Experiment number 21 22 Polycarboxylic components Terephthalic acid 82 77 Phthalic anhydride 15 2. 3 5-Sulfoisophthalic acid 3 - Adipic acid - - Polyol components ethylene 10 76 Polyethylene glycol (1500) - 9.4 Propoxylated bisphenol 80 - Glycerin 10 14.5 properties Temperature, softening, ° C 65 40 Acidity index, mg KOH / g - 2.9 Molecular Weight, Mn 7700 8400

SUMMARY V

A mixture of adipic acid (1 mol), diethylene glycol (1 mol), polyethylene glycol M 200 (0.5 mol), and zinc acetate 0.146 g is subjected to esterification at 140 ... 220 ° C for 2 ... 3 h, until the acidity index of the mixture drops below 60 mg KOH / g. A mixture of oligomers with about 30% diglycoladipate content is diluted with water to infinity. Similarly, the oligoesters presented in table 4 are obtained (Ex. 23 ... 27).

Table 4

Components (% moles) and properties Experiment number 2. 3 24 25 26 27 Polycarboxylic components Adipic acid 100 100 - - 50 Phthalic anhydride - - 100 100 50 Polyol components 2 - Propandiol 50 - - - - diethylene - 50 - 50 - Polyethylene glycol (200) 50 50 100 50 100 properties Acidity index, mg KOH / g 57.5 38.7 67 5 58 Molecular Weight, Mn 613 839 1100 825 900

Copolyesters, synthesized in Examples 1 ... 27, have been transformed into aqueous solutions and / or dispersions with or without the help of water-miscible organic solvents, namely:

DISPERSION I. Copolyester resin (40 parts) 5 and water (60 parts), were mixed in a dispersion vessel provided with agitator, thermometer, reflux refrigerant and heating jacket, at a temperature of 85 ... 1QO ° C , for 3 h. The white aqueous dispersion obtained, D1 ... D-9 obtained from the copolyesters 3 ... 16 have a particle size smaller than 1 μ. When the aqueous dispersion is kept at a temperature between 0 and 70 ° C, for 6 months no change in appearance and viscosity was observed, the aqueous dispersion having a very good storage stability.

Similarly, the D-2, D-3, D-4, D-5, D-6, D-7, D-8, D-9 dispersions of the copolymers 4, 5, 6, 9, 10 were obtained. , 11, 12, 16, and the dispersion properties obtained are shown in table 5 (a and b).

Oligoesters 22 ... 26 have miscibility with water at infinity, at any temperature, and the properties of the obtained solutions are presented in table 5 (a and b).

ι / i

Ό

IZ)

¢ 4

Ί%

> 2 «2 ti ce o

• c • a

Q

Z xi

C

X

A

Έ cS, O

FB - very good, FS - no changes «> tt, 25

18

DISPERSION II. Copolieetheric resin 2 (30 parts) and cosolvent miscible with water, ethylcellosolve (15 parts) is mixed in a vessel equipped with stirrer, thermometer and reflux refrigerant, at a temperature of 100 '... 135 ° C, for one hour , giving a homogeneous viscous mixture. To the mixture is added, under vigorous stirring, water (55 parts) in small portions, for one hour, resulting in a white aqueous dispersion D-10, which has a particle size smaller than 1 μ and is stable at temperature of 0 ... 10 50 ° C, for 2 months, without changing the appearance and viscosity.

Similarly, the D-ll, D-12, D-13, D-14, D-15, D-16 dispersions of the 8, 14, 15, 17, 18, 19 copolyesters were obtained, and the properties of the 15 dispersions obtained are shown in table 5 (a and b).

The aqueous dispersions of the present invention may be used as such for different purposes or may be mixed with one or more cross-linking agents 20 as amino resins, epoxy and isocyanate compounds.

Amino resins can be urea, melamine or benzoguanamine compounds as such or alkylated with an alcohol having 1 to 6 carbon atoms.

The epoxy compounds are polyglycidyl esters and ethers such as bisphenol A diglycidyl ether or its oligomers, diglycidylortophthalate, diglycidylisophthalate, diglycidylterephthalate.

Epoxy compounds may include aliphatic or aromatic polyvalent diisocyanates, tri or polyisocyanates. 30

Crosslinking agents can be added in different ways: in polyester resin, in aqueous dispersion, in water-miscible organic solvent or in water.

MIXTURE 1. In the D-I dispersion obtained from the water-dispersed copolymer resin 3, hexamethoxymethylmelamine (HMMM) is added in 10 proportion of 100 parts resin: 15 parts HMMM.

The mixture obtained is homogenized and a homogeneous aqueous dispersion Al is obtained. This dispersion (Al) has a particle size smaller than 40 1 μ and is stable at 0 ° C for at least 1 month, without changes in appearance. Aqueous dispersion Al can be used as a protective film after curing at 100 ° C for 30 minutes.

MIXTURE 2. In the D-l dispersion obtained 45 from the copolyester resin 3, dispersed in water, 2,4-toluendiisocyanate is added in the gravimetric ratio 100 parts resin: 4.6 parts 2,4-toluendiisocyanate.

The mixture obtained A2 is homogenized and deposited, in the form of a protective film, on 50 paper, wood or metal support.

MIXTURE 3. In the D-2 copolyester dispersion obtained from copolyester resin 4, an epoxy (bisphenol glycidyl ether A) is added in a ratio of 7: 3 (copolyester parts: epoxy ether) and 0.14 parts zinc chloride ( concentration 2 g / 100 g / 100 g polyester).

The mixture obtained is homogenized and deposited, as a protective film, at 160 ° C for 30 minutes.

The polyester dispersions of the present invention can be used as: adhesives, protective varnishes, treatment agents for textile or paper products, in particular for surface protection agents with water protection; For these purposes, the copolyester dispersions can be used as such, but also in combination with other dispersions or emulsions of aqueous resins (acrylic, urethane, ethylene acetate vinyl, rubber latex, etc.), pigments and other additives and may be deposited on plastic supports, glass, metals and others.

In some cases, the polyester resin can be used in mixture with cross-linking agents of the type: amino, epoxy, isocyanate resins, in melting state, or as a solution in water-organic solvent mixture, miscible with water.

The dispersions described can also be used to obtain laminated products from: metals, plastics, textile products woven and non-woven from natural and synthetic fibers, obtaining products with very good durability and water resistance.

Claims (2)

claims 1. Aqueous dispersion, copolyester, characterized in that it consists of: self-emulsifying copolyester, in a concentration between 1 and 99% g, obtained from 40 ... 90% moles (compared to the acid component) a di- or aromatic or aliphatic polycarboxylic, without metalsulfonic group, 2 ... 15% moles (relative to the acid component) an aromatic di- or polycarboxylic acid with a metalsulfonic group, 20 ... 100% moles (compared to the glycolic component) one diol or aliphatic polyol having 2 ... 200 carbon atoms and 80% moles (relative to the glycolic component) an bisphenol A adduct with ethylene oxide or propylene oxide, copolyester having the molecular weight Mn between 2000 and 20000, the melting temperature between 0 and 200 ° G, with / without an organic cosolvent, up to 50% g, miscible with water and having the boiling temperature between 60 and 200 ° C, water in the proportion of 1 ... 99% g and optionally a component a select onat from a group consisting of an amine resin, an epoxy resin and a polyisocyanate dissolved compound in a proportion between 1 and 50% g (as opposed to aqueous dispersion) and both dispersions with particle size ranging from 1 to 10 μ are obtained. as well as microemulsions and solutions with 5 particle size - <1 μ. 2. A process for obtaining aqueous, copolyester dispersions, characterized in that - the esterification, respectively, the re-esterification of a mixture of aromatic di- or polycarboxylic acids 10 or aliphatic without a metal-sulfonic group, an aromatic or polycarboxylic acid with a metal-sulfonic group, an aromatic di- or polycarboxylic acid with a metalsulfonic group or their ester derivatives with an aliphatic diol, a polyolaliphatic or a bisphenol 15A adduct with ethylene oxide or propylene oxide, in the presence of the catalyst selected from zinc acetate, calcium acetate or cobalt acetate in ratio of 0.02 ... 0.1 g / 100 g acids, at a temperature between 140 and 220 ° C, then - polycondensation of the resulting reaction mixture, in the presence of the polycondensation catalyst, chosen from styrene trioxide, zinc oxide or tetrabutyltitanate, in the proportion of 0.02 ... 0.1 g / 100 g reaction mixture, at a temperature between 220 and 275 ° C and pressure is gradually reduced from 760 to 0.2 mm Hg, for 3 ... 6 h, - the realization of the organic polymer-solvent mixture, at a temperature between 40 and 130 ° C, a minimum time of one hour and finally - dispersion of the mixture thus obtained, with water, at a temperature between 40 and 95 ° C and -optionally, to the aqueous dispersion thus obtained, a component selected from a group consisting of an amine resin, epoxy resin and a polyisocyanate disc compound can be added. .