The compound, its preparation and use

 

(57) Abstract:

Describes a dispersant which is a phosphate ester block copolymer of the formula I RO(C2H4O)m(PES)n-H, where R is a C1-4-alkyl; PES - is a simple polyester with repeating group - (CH2)4CO-, -OCH(CH3)(CH2)2CO - or-O(CH2)5CO; m can take values from 4 to 60; n can take values from 2 to 30, and the molecular weight of RO(C2H4O)mmore than the molecular weight (PES)n. describes its preparation and use. The technical result - the creation of improved dispersant capable of dispersing in the environment of large quantities of particulate solid phase and exhibiting high dispersion stability and excellent properties of the obtained paint film, especially the final high Shine. 5 S. and 6 C.p. f-crystals, 6 PL.

The invention relates to a compound for dispersing particulate solids in the aquatic environment, the method thereof and compositions containing the specified connection and a particulate solid phase, including paint and ink.

The basis for water-based paints usually prepared by the AI as resin, and dispersant, for a uniform distribution of finely ground solid phase in the environment. However, adding such a framework in the paint disperser may adversely affect the characteristics of the paint film formation and/or the strength of her films. Some dispersers also adversely affect the gloss of the obtained paint film. Therefore, there is a need for an improved dispersant capable of dispersing in the environment of large quantities of particulate solid phase and exhibiting high dispersion stability and excellent properties of the obtained paint film, especially the final high luster.

In the application for the patent Canada N 2022957 described dispersers, which are phosphate esters of block copolymers containing poly(alkylene) segments, and the segments of the polyester chain, in particular phosphate ester block copolymer, which is onomatology ether of polyethylene glycol with m 750 m, polymerized with valerolactone, which also gives polyester with m 750 m. Recently it was found that phosphate esters, block copolymers of this type exhibit excellent properties dispersant for water-based in that case what about the present invention presents the dispersant is a phosphoric acid ester block copolymer of the formula I.

RO(C2H4O)m(PES)n-H,

where R is C1-4-alkyl;

PES is a polyester derived from cyclic lactone;

m can take values from 5 to 60;

n can take values from 2 to 30, and

the molecular mass of RO(C2H4O)mmore than the molecular weight (PES)n.

R may be normal or branched, but preferably is normal, especially the stands.

Cyclic lactone is preferably valerolactone, particularly preferably-caprolactone. In that case, if PES is a polyester derived from valerolactone, structural unit has the formula-O-(CH2)4CO - or-O-CH(CH3)-(CH2)2CO-if PES is a polyester obtained from caprolactone, structural unit has the formula-O-(CH2)5CO.

It is preferable that m does not exceed 40, and particularly preferably does not exceed 25.

It is also preferred that n does not exceed 20, and particularly preferably does not exceed 10.

Preferably, the ratio of m:n would be at least 3:1, more preferably at least 4:1, and especially prepotentials - do not exceed 4000, even more preferably does not exceed 3500, and particularly preferably does not exceed 3000.

Phosphate ester receive when interacting monoalkyl ether of the formula I with a phosphating agent, when the number monoalkyl ester per atom of phosphate phosphate agent is from 3:1 to 1:1, especially from 2:1 to 1:1.

Particularly preferably, the number monoalkyl ester per atom of phosphorus phosphate agent would be less than 2, for example about 1.5; 1, the dispersant is a mixture of mono - and diphosphonates ethers.

Phosphate ester may be in the form of the free acid or may form a salt with alkali metal, ammonia, amine, alkanolamine or Quaternary ammonium base.

Phosphate ester also may further interact with the aliphatic alcohol or alkanolamine. Preferred aliphatic alcohols are C1-6- and especially - C1-4- alcohols. If phosphate ester further interacts with the aliphatic alcohol, then formed an additional ester group, and the number monoalkyl ether of the formula I on each phosphorus atom fosfatina is the duty to regulate with alkanolamines, alkanolamine can form an ether and/or amide groups and/or amine salt. It is assumed that the reaction product is mainly amine salt.

Preferred phosphating agents are POCl3, polyphosphoric acid or especially P2O5.

Preferred alkali metals are lithium, potassium, especially sodium.

Examples of alkanolamines are ethanolamine, diethanolamine, 2-dimethylaminoethanol 2-amino-2-methyl-1-propanol.

The block copolymer of the formula I get from any known prior art method, preferably in the interaction monoalkyl ether of polyethylene glycol of the formula 2 with a cyclic lactone such as valerolactone or caprolactone.

RO-(C2H4O)mH,

where R and m are defined above.

The reaction is carried out preferably in an inert atmosphere, such as nitrogen, in the absence of moisture, and preferably catalyze the metal salt, which is soluble in the reaction mass. The preferred catalyst is a salt of titanium, in particular the alkoxide such as Tetra(n-butyl) titanium. The reaction is carried out at temperatures above 100oC, preferably at a temperature in the UP>oC, and particularly preferably not higher than 200oC.

The reaction between monoalkyl ether of the formula I and phosphating agent is also preferably carried out in an inert atmosphere, such as nitrogen, in the absence of moisture. The reaction can also be carried out in an inert solvent, but it is more convenient to carry out the interaction monoalkyl ether phosphate agent in the absence of solvent. Preferably, the temperature was above 60oC, and particularly preferably above 80oC. To prevent charring of the dispersant preferably, the temperature was not above 120oC, and particularly preferably not higher than 100oC.

Particularly preferably, not spending allocation, directly converting the block copolymer in the phosphate ester by reacting with a phosphating agent. Preferred phosphating agent in the synthesis in one device is polyphosphoric acid.

If dispersant contains additional ether, amide groups and/or amine salt, obtained by the reaction of phosphate ester with an aliphatic alcohol or alkanolamine, alcohol or alkanolamine can interact with the phosphate ester in the same cazalas above, the dispersant according to this invention are applied to a homogeneous distribution of the particles of the solid phase in a liquid medium, primarily in the aquatic environment.

Thus, the other side of the present invention is a composition comprising the above-described dispersant and a particulate solid phase.

In addition, the composition further includes a liquid, especially one in which the dispersant is at least partially soluble, and more preferably water or an organic liquid miscible with water, including mixtures thereof. Examples of suitable liquids are alcohols, such as C1-10-aliphatic alcohols, glycols, such as C2-6-alkalophile, esters, alcohols, such as methoxy, ethoxy-, propoxy - and butoxyethanol and methoxy, ethoxy-, propoxyphenol and glycol ethers such as diethylene glycol and propylene glycol. Usually the liquid is chosen so that to satisfy the requirements of the target application of the composition, particularly compatibility with any environment, which composition will be diluted. Preferably, the liquid includes at least 25%, more preferably at least 50% and particularly preferably at least 75 wt.% water as far as the C of the solid phase, but preferably includes a layer of a dispersant for the fine particulate solid phase. The particulates of the solid phase preferably have an average diameter of less than 15 microns, more preferably less than 10 μm, particularly preferably less than 5 microns, and most preferably less than 3 microns.

The particulate solid phase can be any substance that is required to be stabilized in a liquid medium in a finely dispersed state. Examples of suitable solids are pigments and fillers for inks, paints and other coatings for surfaces, magnetic metals or alloys, or alloys of magnetic oxides for the production of magnetic tapes, disks, and memory devices, particles of dirt and soil, biocides, agrochemicals and pharmaceuticals. The composition in dry form or in the form of a dispersion in a liquid medium may contain other ingredients, such as resins, binders, thinning agents, protivovospalitel, plastificator, wetting, coagulants, co-solvents, thickeners and preservatives. These ingredients may be soluble, partially soluble, insoluble or dispergirovannykh in a liquid medium.

In that case, if the solid phase is a pigment, it is preferable that it is I who(sometimes referred to as lacquer or toner). He may belong to any known class of pigments described, for example, in the Third edition of the Colour Index (1971) and in its subsequent revised and expanded editions in the section titled "Pigments".

Examples of inorganic pigments are titanium dioxide (including forms of anatase and rutile ultrafine titanium dioxide with a high absorption in the UV region), zinc oxide, Prussian blue, cadmium sulfide, iron oxides (including transparent iron oxides, Ultramarines, mica (including pearl pigments obtained by treating the surface of mica, for example, a thin titanium dioxide and chromium pigments, including chromates, molybdates and mixtures of chromates and sulfates of lead, zinc, barium, calcium and mixtures of their modifications, which industrial produced in the form of pigments from greenish - yellow to red colors under the names of the chrome primrose, lemon, middle, orange, scarlet or red.

Examples of metallic pigments are cheshuirovannyj aluminum, copper powder and Casuarina copper.

Examples of metal salts of organic dyes pigments are metal salts of azo compounds, such as item CI Pigment Red 48 (also known as Lithol Rubine, Rubine Toner or Permanent Red 4B), CI Pigment Red 58, CI Pigment Red 247, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 183 and CI Pigment Yellow 191.

Examples of fillers are calcium carbonate, hydrated alumina, talc, quartz, silica (precipitated, fumed or synthetic), silicates of metals, sulphates of barium and calcium, kaolin, oxides of antimony, slate powder, wollastonite or chopped fiberglass.

The composition may be obtained by any method known from the prior art. So, it can be prepared by mixing a dispersant and a particulate solid phase, preferably with subsequent grinding of the composition to obtain the desired particle size of the solid phase. However, the dispersant may preferably be added to the particulate solid phase in the presence of liquid at the end of cooking or at the final stages of obtaining a particulate solid phase. However, the composition is usually obtained by mixing the dispersant, particulate solid phase and a liquid medium, and then grind or crush the composition to obtain the desired size of the particulate solid phase. Liquid medium can serve as water or an organic liquid in which the dispersant is preferably at least part of akuu volatility, that could be removed with the particulate solid phase by simple methods of separation, for example by evaporation. However, it is preferable that the composition included the liquid medium.

In that case, if the dry composition consists mostly of a dispersant and a particulate solid phase, it is preferable that it contains at least 0.2 percent, more preferably at least 0.5%, and particularly preferably at least 1 wt.% disperser, counting from the mass of particulate solid phase. Preferably, the dry composition contains no more than 100%, preferably not more than 50%, more preferably not more than 20%, and especially preferably not more than 10 wt.% disperser, counting from the mass of particulate solid phase. If the composition contains a dispersant, the particulates of the solid phase and the liquid medium, it is preferable that it contains at least 5%, more preferably at least 20%, especially preferably at least 40% and most preferably at least 50% of the particulate solid phase, starting from the total mass of the composition. Preferably, the composition does not contain more than 90%, more preferably not more than 80%, and especially preferably not more than 75 wt.% particles of tumacacori solid phase is defined as a dry composition.

As mentioned above, the dispersant according to this invention are used, in particular, to prepare aqueous bases, in which the particulate solid phase suspended in the liquid in the presence of a dispersant, and plenkoobrazuyushchie resinous binder.

Thus, the other party of this invention is a water-base, including particulate solid phase, a dispersant and a film-forming resin.

Typically, the core contains from 20 to 70 wt.% particulate solid phase by weight of the total base. It is preferable that the content of the particulate solid phase was at least 30, particularly preferably at least 50 wt.% by weight of the base.

The amount of resin in the base varies within wide limits, but preferably is not less than 10% and particularly preferably at least 20 wt.% from the solid phase/liquid phase basis. Preferably, the amount of resin does not exceed 50%, and particularly preferably does not exceed 40 wt.% from the solid phase/liquid phase basis.

The amount of dispersant in the basis depends on the amount of particulate solid phase, but is preferably from 0.5 to 5 wt.% by weight of the base.

The resin may be any film-forming resin, aniu when interacting with cross-linking agent, and which is preferably acrylic or acrylate copolymer containing ethylene unsaturated group.

The invention is further illustrated by the following examples in which all parts and percentages are mass, unless otherwise specified.

Intermediate block copolymers.

The following descriptions of the intermediate block copolymers nanometrology ether of polyethylene glycol are abbreviated name MeO PEG, and the polymer obtained from caprolactone, has the abbreviation "Pat." Numbers in parentheses are the approximate values of molecular masses of elementary polymer chains.

The intermediate product 1 - MeO PEG (750) cap (456).

At a temperature of 160-180oC in nitrogen atmosphere for 6 hours, stirred mixture MeO PEG (750) (80 parts, 0,107 M (Fluka)), -caprolactone (48,68 part of 0.43 M (Interox)) and tetrabutyl titanate (0.4 parts (Aldrich)). Receive the product (110 parts) as a light brown oil which upon cooling forms a plastic wax.

The intermediate product 2 - MeO PEG (750) cap (228).

Get the method described for intermediate 1, except that used half load-caprolactone. the p (798).

Get the method described for intermediate 1, except that instead of the quantities specified for intermediate 1, using MeO PEG (750) (50 parts, of 0.066 M) and-caprolacton (53,25 part, 0,467 M). Receive the product (100 parts) as a brown viscous oil, which upon cooling forms a waxy solid.

The intermediate product 4 - MeO PEG (750) cap (1026).

The mixture MeO PEG (750) (40 parts 0,053 M) and-caprolactone (54,72 part, to 0.480 M) was stirred at 100oC in nitrogen atmosphere. Add tetrabutyl the titanate (0.4 parts), and stirred for 6 hours reagents at 170-180oC in nitrogen atmosphere. Receive the product (90 parts) as a brown oil, which upon cooling forms a solid wax.

The intermediate product 5 - MeO PEG (750) -valerolactone (750).

The mixture MeO PEG (750) (40 parts 0,053 M) and-valerolactone (40 parts, 0.4 M (Aldrich)) was heated to 150oC. Add dibutyltindilaurate (0.5 parts (Aldrich)), and 6 hours stand the reagents at 180-185oC in nitrogen atmosphere. After cooling, get the product (75 parts) in the form of wax.

Getting dispersant phosphate ester.

Example 1 - MeO PEG (750) cap (456) (phosphorus 1,5:1).

Interim PR is phosphorus (0,47 part, 0,0033 M) and 1 hour mix reagents at 50oC in nitrogen atmosphere. After this reaction are another 16 hours at 80-90oC in nitrogen atmosphere. Get dispersant 1 in the form of a yellowish oil, which upon cooling forms a plastic waxy solid.

Example 2 - MeO PEG (750) cap (228) (phosphorus 1,5:1).

Dispersant 2 get a way similar to that described in Example 1, except that instead of intermediate 1 using an equivalent quantity of the intermediate product 2. Dispersant 2 get in the form of a yellowish oil, which upon cooling forms a plastic waxy solid.

Example 3 - MeO PEG (750) cap (798) (phosphorus 1,5:1).

Get a way similar to that described in Example 1, except that instead of intermediate 1 using intermediate 3 (7,74 part, 0.005 M) and patikis phosphorus (0,24 part, 0,0017 M). Disperser 3 get in the form of a yellowish oil, which upon cooling forms a plastic wax.

Example 4 - MeO PEG (750) cap (1026) (phosphorus 1,5:1).

Get a way similar to that described in example 1, except that instead of the intermediate product 1 use promezhutochnoyee when cooled forms a plastic wax.

Example 5 - MeO PEG (2000) cap (456) (phosphorus 1,5:1).

MeO PEG (2000) (50 parts, 0.025 M (Fluka)), -caprolacton (11,41 part, 0.1 M (Interox)) and tetrabutyltin (0.4 parts) is stirred for 6 hours at 180-185oC in nitrogen atmosphere. Reagents cooled to 80oC and added polyphosphoric acid (2,78). Then stirred for further 24 hours at 90-95oC in nitrogen atmosphere. Get disperser 5 (60 parts) in the form of a slightly coloured oil, which upon cooling forms a gel.

Example 6 - MeO PEG (2000) cap (798) (phosphorus 1,5:1).

Get a way similar to that described in example 5, except that the number of caprolactone increase to 19,97 part. Disperser 6 (65 parts) obtained as a yellowish viscous oil, which upon cooling forms a gel.

Example 7 - MeO PEG (2000) cap (1026) (phosphorus 1,5:1).

Get a way similar to that described in example 5, except that the number of caprolactone increase to 25,67 part. Disperser 7 (71 part) are obtained in the form of a yellowish oil, which upon cooling solidifies with the formation of a waxy solid.

Example 8 - MeO PEG (750) -valerolactone (750) (phosphorus 1,5:1).

Intermediate 5 (40 parts) 4 hours negator 8 (40 parts) as a brown solid.

Examples 9 to 11 and comparative examples A to D.

Bases corresponding to the compositions shown in table 1, get, adding a dispersant to the mixture of water and resin and setting the pH to about 10 by adding ammonia followed by heating in a boiling water bath to dissolve the dispersant. After cooling, the solution of the dispersant is placed in the tank of the apparatus for dispersing and stirring was added titanium dioxide. Make a 1 mm glass balls (180 pieces), and the basis of the ground at a speed of 3000 for 30 minutes without starting the water in the cooling jacket. After this Foundation is cooled and separated from the balls before adding to the dilution of the composition.

After standing for 16 hours at 15-20oC for deaeration of the ink applied on the ground steel and aluminum panels using K-shaped profile N 8 connected to the automatic painting device (Model CSC 202, giving a wet film thickness of 100 μm. Of the paint film is dried in air for 90 minutes, and then incubated for 30 minutes at 120oC. 20othe brilliance of each panel is determined by averaging 5 measurements made on the surface of the panel. The results are shown in table 2.

Dispersing agents 3 and 4 are not on the corresponding compositions, in table 3, is prepared by a method similar to that described in examples 9 through 11. Data received 20othe brilliance of these bases are given in table 4.

The basics are manufactured using dispersant 5, 6 and 7, give a very good dispersion, free from lumps of the solid phase.

Examples 15 to 21.

The basis is obtained by dissolving adding dispersant (2,55 part), Dehydrin and 1293 (0.3 part) and AMR 95 (0,23 part) to a mixture of water (up to 9.6 parts) and propylene glycol (6,75). The pH value is set at 10 and the mixture is heated to dissolve the components. Then the mixture is cooled and poured into the tank of the apparatus for dispersion. Add Neocal XK90 (44,8) and Tioxide TR92 (64 parts), then make a 1 mm glass balls (180 pieces). Grind basis at a speed of 3000 for 30 minutes without external cooling. The resulting framework is then separated from the glass balls and diluted to obtain the final colorful part number Neocal and XK90, as indicated in the following table 5.

Dehydrin 1293 is a defoamer manufactured Henken GmbH, AMR 95 is a 2-amino-2-methyl-1-propanol, Neocal XK90 is an acrylic resin in a mixture of water with propylene is otopleniya framework is used dispersant 8, it is not possible to obtain satisfactory dispersion in the case, if the grinding is performed in the presence of Neocal and XK90.

The above paint was subjected to standing (16 hours) for deaeration, and then they were covered with panels of coated steel and aluminum using the automatic painting device model CSC 202, equipped with a K-shaped profile N 8. The film paints were dried in air for 90 min and then solidified for 30 min at 120oC. Specific 20ogloss finished colourful films are shown in table 6.

1. Dispersant which is a phosphate ester block copolymer of the formula 1

RO(C2H4O)m(PES)n-H

where R is a C1-4-alkyl;

PES is polyester with repeating group-O(CH2)4CO-, -OCH(CH3)(CH2)2CO-, or-O(CH2)5CO-;

m can take values from 5 to 60:

n can take values from 2 to 30,

moreover, the molecular mass of RO(C2H4O)mmore than the molecular weight (PES)nand

where the phosphate ester is obtained by reaction of the block copolymer of formula 1 with a phosphating agent, where the ratio of block copolymer to confess the fact, what R is the stands.

3. Dispersant according to any one of p. 1 or 2, characterized in that the PES is a complex polyester with repeating group-O(CH2)5CO.

4. Dispersant according to any one of paragraphs.1 to 3, characterized in that the ratio m : n is not less than 3 : 1.

5. Dispersant according to any one of paragraphs.1 to 4, characterized in that it is a mixture of mono - and di - phosphate.

6. Composition comprising a dispersant according to any one of paragraphs.1 to 5 and particulate solid phase.

7. The composition according to p. 6, characterized in that it further includes a liquid environment.

8. The composition according to p. 7, characterized in that the liquid medium is water.

9. Water base, characterized in that it includes a disperser according to any one of paragraphs.1 to 5, the particulates of the solid phase and the film-forming resin.

10. The paint that includes a disperser according to any one of paragraphs.1 to 5, the particulates of the solid phase and the film-forming resin.

11. Ink containing a dispersant according to any one of paragraphs.1 to 5, the particulates of the solid phase and the film-forming resin.

 

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