The compound, its preparation and use

 

(57) Abstract:

The invention relates to a dispersant for dispersing particulate solids in the aquatic environment, which is a phosphate ester, polyalkylene ether block copolymer of the formula RO(C2H4O)m(C3H6O)n-H, where R is a C1-4-alkyl, m and n are independently each can take values from 2 to 60, its use in the composition of water-based paints and printing inks, as well as to a method for obtaining the reaction of polyalkylene ether block copolymer with a phosphating agent. Composition in addition to the dispersant contains a particulate solid phase, and the paint or ink also contain film-forming resin. Disperser provides increased stability of the dispersion and improved properties of the obtained paint film, especially its high Shine. 5 s and 5 C.p. f-crystals, 5 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 are usually preparing, exposing the grinding in the aquatic environment h, the La uniform distribution of finely powdered 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.

According to this invention presents the dispersant is a phosphoric acid ester of poly(C2-3-)allenglish)-mono-C1-4alkyl ether of the formula I

RO(C2H4O)m(C3H6O)n-H,

where R is C1-4-alkyl, and

m and n are independently each can take values from 2 to 60;

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

Preferably, m has at least 3, particularly preferably has at least 5. It is also preferred that m is not exceeded Stateline, order n has at least 3, more preferably has at least 5, particularly preferably has at least 7. It is also preferred that n does not exceed 40, more preferably does not exceed 30, and particularly preferably does not exceed 25.

Preferably, the molecular weight monoalkyl ether of formula I would be less than 12000, more preferably would be less than 8000, even more preferably would be less than 5000, and particularly preferably would be less than 3000. Also preferably, the molecular weight monoalkyl ether of formula I would be at least 400, more preferably would be at least 800, and particularly preferably would be at least 1000.

Preferably, the ratio of m and n would be between 1: 3 and 3 : 1, particularly preferably between 2: 5 and 5 : 2.

Phosphate ester receive when interacting monoalkyl ether of the formula I with a phosphating agent, when the number monoalkyl ester per atom of phosphorus 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, whereas what may be in the form of the free acid or may form a salt with an alkaline metal, ammonia, an 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 ratio monoalkyl ether of the formula I to the phosphorus atom phosphating agent becomes less than 2, and especially less than 1.5.

When phosphate ester further interacts 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 and especially P2O5.

Preferably the alkali metal is lithium, potassium, especially sodium.

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

Monoalkyl ether of the formula I get from any known prior art method, predpochtitel/SUB>O)mH, where R and m are defined above.

Usually, monoalkyl ether of the formula II interacts with propylene oxide in the presence of an alkali metal in an inert atmosphere, such as nitrogen, in the absence of moisture. The preferred alkali metal is lithium, sodium, and potassium. Alkali metal in the form of water-soluble inorganic salts, mainly in the form of hydroxide, before loading of propylene oxide appropriately add to monoalkylation ether of the formula II, water is removed by heating, especially when heated under reduced pressure. Due to the volatility of propylene oxide its interaction with monoalkyl ether of the formula II is carried out in a closed vessel usually at 40 - 140oC. Preferably, the temperature was above 80oC, and particularly preferably above 100oC.

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 is o temperature was less than 120oC, and particularly preferably less than 100oC.

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 under the same conditions that were used to communicate monoalkyl ether with a phosphating agent.

As mentioned 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 b is ol. Typically, 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 relative to the total weight of the composition.

The composition may include a homogeneous mixture of a dispersant and a particulate 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 for stabilization in liquid medium in fine condition. Examples of suitable solids are pigments and fillers for inks, paints and other coatings for surfaces, magnetic materials or alloys, and magnetic oxides for use in the manufacture of magnetic tapes, disks, and memory devices, particles of dirt and soil, biocides, the other ingredients, such as resins, binders, thinning agents, protivovospalitel, plasticizers, 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 a inorganic pigment, a metallic pigment or a metal salt of an organic dye (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, Colnago colors under the names of the Chrome primarosa, lemon, medium, orange, scarlet and 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 (other names 2V Toner or Permanent Red 2B), Pigment Red 53 (other names Lake Red C, or Red Lake (C), Pigment Red 52, Pigment Red 48 (other names 4V Toner, Lithol Rubine, Rubine Toner or Permanent Red 4B), Pigment Red 58, Pigment Red 247, Pigment Yellow 61, Pigment Yellow 62, Pigment Yellow 183, and 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 liquids which positions are 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 at least partially soluble. If you want to obtain a composition in solid form, it is desirable that the liquid medium had that kind of 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, a particulate solid phase and a liquid medium, it Pro - 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 contains not more than 90%, more preferably not more than 80%, and especially preferably not more than 75 wt.% particulate solid phase, starting from the total mass of the composition. The preferred amount of the dispersant with respect to the mass of particulate solid phase is defined as a dry composition.

As mentioned above, the dispersant according to this invention is particularly suitable for the preparation of aqueous bases, in which the particulate solid phase suspended in the liquid in the presence of a dispersant and a film-forming resinous binder.

Thus, another aspect of the present 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 not less than 30, and particularly preferably not less than 50 wt.% by weight of the base.

The amount of resin in the base may vary within wide limits, but preferably is n the number of the resin is less than 50%, and especially preferably not more than 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 capable of acting as a binder in aqueous paints and printing inks. The preferred resin capable of crosslinking when interacting with cross-linking agent, and preferably is 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 monoalkyl ethers of polyalkylene glycols

In the following descriptions, we obtain block copolymers onomatology ether glycol has a short name MeO PEG, and polypropylenglycol is the abbreviated name of the BCP. In parentheses are the approximate values of molecular masses of the polymer chains.

The intermediate product 1-MeO PEG (750) GPR (650).

Charged to the reactor MeO PEG (750) (750 parts, 1 M (Fluka)) together and at 110oC and 20-30 mm RT.article to remove the water. Then add the propylene oxide (750 parts, 12.9 M), the vessel is heated to 110oC under stirring for 8 h to complete the reaction. The remains unreacted propylene oxide is removed at 110oC and 0-30 mm RT.article Obtain a block copolymer (1514 parts) in the form of a red-brown oil, which solidified upon cooling. It contains PEG:BCP in the ratio of approximately 1:5:1.

The intermediate product 2-MeO PEG (750) GPR (1260).

Get the method described for intermediate 1, except that the amount of propylene oxide was increased to 1400 parts. Obtain a block copolymer (1863) in the form of a light brown oil, which contains PEG:BCP in the ratio of approximately 1:1.4.

The intermediate product 3 - MeO PEG (350) GPR (930).

Get a manner analogous to that described for intermediate 1, except that use MeO PEG (350) (350 parts, 1 M (Fluka)). Get the block copolymer in the form of a dark brown oil. The copolymer contains PEG: BCP in a ratio of about 2:1 and has a hydroxyl number of 48 mg KOH/GM (Effective m m 1190).

The intermediate product 4 - MeO PEG (550) GPR (700).

Get way, picalilli (700 parts, 12 M). Get the block copolymer in the form of a dark yellow oil with a ratio of PEG:BCP approximately 1:1 and has a hydroxyl number of 50.6 mg KOH/GM-1(Effective m m 1109).

The intermediate product 5 - MeO PEG (750) GPR (500).

Get the method described for intermediate 2, except that use MeO PEG (750) (750 parts, 1 M). Get the block copolymer in the form of a dark brown oil with a ratio of PEG: BCP approximately 2:1 and has a hydroxyl number of 50.8 mg KOH/GM-1(Effective m m 1104).

Getting dispersant.

Example 1 - MeO PEG (750) GPR (650) (phosphorus 1:1).

The intermediate product 1 (28 parts, 0.02 M) loaded into a nitrogen purged reactor. When 20-25oC add patikis phosphorus (1.42 parts, 0.01 M) and 15 min intensively mix the reagents. Then the temperature was raised to 80oC. After 2 h stirring at 80oC gradually formed a white solid, which under stirring in nitrogen atmosphere at 80oC dissolved for 16 h with the formation of a yellow oil containing some solid phase. The temperature was raised to 90oC, and mix the reagents in an atmosphere of nitrogen for 16 hours until complete dissolution. Get var) GPR (1260) (phosphorus 1:1).

Get a way similar to that described in Example 1, except that instead of intermediate 1 using intermediate 2 (30 parts, 0.015 M) and patikis phosphorus (1.06 parts, 0.0075 M). However, in this example, after addition of phosphorus pentoxide reagent is stirred for a total of 21 hours at 80oC. Disperser 2 obtained as a brownish oil.

Example 3 - MeO PEG (350) GPR (930) (phosphorus 1.5:1).

Charged to the reactor intermediate product 3 (35.67 parts, 0.03 M) and purge with nitrogen. Add patikis phosphorus (1.42 parts, 0.01 M) and the reactants stirred for 1 h at 20-25oC in nitrogen atmosphere. Patikis phosphorus quickly dispersed, and the reactants stirred at 80-90oC in an atmosphere of nitrogen for 16 hours Get disperser 3 in the form of a clear yellow oil.

Example 4 - MeO PEG (550) GPR (700) (phosphorus 1.5:1).

Get the method described in Example 3, except that the intermediate product 3 replace the intermediate product 4 (33.27 parts, 0.03 M). Get disperser 4 in the form of a clear yellow oil.

Example 5 - MeO PEG (750) GPR (500) (phosphorus 1.5:1).

Get the method described in Example 3, except that the intermediate product 3 soroe forms when standing plastic paste.

Example 6 - MeO PEG (750) GPR (650) (phosphorus 1.5:1).

Intermediate 1 (100 parts) 24 h mixed with polyphosphoric acid (7.94 part, the content of P2ABOUT585%) at the 90oC in nitrogen atmosphere. Get a brown oil (104 parts), which upon cooling gives a waxy solid dispersant 6.

Example 7 - MeO PEG (750) GPR (1260) (phosphorus 1.5:1). Intermediate 2 (100 parts) 24 h mixed with polyphosphoric acid (5.54 part, the content of P2O585%) at the 90oC in nitrogen atmosphere. Get a brown oil (103 parts), which upon cooling gives a waxy solid dispersant 7.

Example 8 - MeO PEG (350) GPR (930) (phosphorus 1:1).

Get a manner analogous to that described for dispersant 6, except that the use of intermediate 3 (100 parts) instead of intermediate 1 and lead react with 13.05 parts of polyphosphoric acid. After cooling, get a dispersant 8 (110 parts) in the form of a dark brown viscous oil.

Example 9 - MeO PEG (550) GPR (700) (phosphorus 1:1).

Also obtained by the method similar to that described for dispersant 6, except that the use of intermediate 4 (100 parts) Vlasta) in the form of a dark brown viscous oil.

Example 10 - MeO PEG (750) GPR (500) (phosphorus 1:1).

Also obtained by the method similar to that described for dispersant 6, except that the use of intermediate 5 (100 parts) instead of intermediate 1 and lead react with 13.42 parts pyrophosphoric acid. Get disperser 10 (109 parts) in the form of a dark brown viscous liquid.

Examples 11 through 13

Determination of dispersant in the basics

Basics get the grinding of the ingredients specified in table 1 in a ball mill, high power with 3 mm glass balls (125 pieces) for 30 minutes

After grinding, the resulting basis is transformed into ready-to-use paint by diluting diluting the emulsion shown in table 1.

Test panels are prepared, painting aluminum and coated steel panels using a system having a mechanically moved down wrapped a wire-shaped profile, the company supplied RK Print-Coat Instruments Ltd, Royston, Herts, England. K-shaped profile is calibrated so that he left a wet film thickness of 100 μm. Paint film is dried at room temperature for 30 min, and then incubated for 30 min at 120oC. the Average of the 20othe glow of each SS="ptx2">

Examples 14, 15 and comparative examples A through C

Bases are prepared with dispersant 1 and 2 from Examples 14 and 15 in accordance with the method described in Examples 11 to 13. Both dispersant 1 and 2 have a ratio of the block copolymer: phosphorus of 1:1. They are compared with dispersant A, B and C, which have the ratio of the block copolymer: phosphorus 1: 1, but the copolymer is a block copolymer MeO PEG, i.e., the segments BCPs and PEG are reversed compared with dispersant 1 and 2.

Measuring 20oShine these foundations are given in table 3 and show that such a dispersant, obtained from the block copolymers of the General formula MeO (PEG) (BCPs) exceed the dispersant derived from block copolymers of General formula MeO (BCP) (PEG), especially if the basis is applied to primed steel panels.

Examples 16 to 25.

The basis is obtained by dissolving under heating dispersant (2.55) and Dehydrin and 1295 (0.3 parts) in a mixture of water (9.6 parts), propylene glycol (6,75) and 2-amino-2-methyl-1-propanol (0.23 parts), setting the pH in the area 10. The resulting solution is cooled and poured into apparatus for dispersion. Add Neocal HK (44.8) and Tioxide TR92 (64 parts) together with 1 m the received base is then separated from the glass beads and diluted Neocal Ohm HC taken in the amount indicated in table 4. Dehydrin 1293 is a defoamer manufactured by Henkel GmbH, Neocal HK is an acrylic resin in a mixture of water/propylene glycol, manufactured by Zeneca Resins, and Tioxide TR92 is titanium dioxide, manufactured by ICI PLC.

The above paint was subjected to standing (16 hours) for deaeration, and then were covered with panels of coated steel and aluminum, as described in Examples 11 to 13. Approximate 20ogloss paints are shown in table 5.

1. Dispersant which is a phosphate ester, polyalkylene ether block copolymer of the formula I

RO(C4H4O)m(C3H6O)n- H,

where R is C1-4-alkyl;

m and n are independently each can take values from 2 to 60,

and where the phosphate ester is obtained by reaction of polyalkylene ether block copolymer with a phosphating agent, the ratio of the polyalkylene ether block copolymer and each phosphorus atom phosphating agent is 3 : 1 to 1 : 1.

2. Disperser under item 1, characterized in that R is methyl.

3. Disperser under item 1 or 2, characterized in that aetsa a mixture of mono - and diphosphate.

5. A composition comprising a dispersant according to any one of paragraphs.1 to 4 and the particulate solid phase.

6. The composition according to p. 5, characterized in that it further includes a liquid environment.

7. The composition according to p. 6, characterized in that the liquid medium is water.

8. Water based, containing dispersant according to any one of paragraphs.1 - 4, particulate solid phase and a film-forming resin.

9. Paint containing dispersant according to any one of paragraphs.1 - 4, particulate solid phase and a film-forming resin.

10. Ink containing a dispersant according to any one of paragraphs.1 - 4, particulate solid phase and a film-forming resin.

 

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