DISPERSING AGENT

Abstract

The invention relates to compositions containing compounds of formula (I), formula (II), or mixtures thereof, in which n is an integer greater than or equal to 1, R.sup.1, an aliphatic, linear or branched hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom, the structural unit —O—X, or the structural unit —CH.sub.2—O—X, X corresponds to formula (III), in which a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28, m is 1 or 2, R.sup.2 is an aliphatic, linear or branched hydrocarbon group having 1 to 10 carbon atoms, Y is hydrogen, —SO.sub.3M, —SO.sub.2M, —PO.sub.3M.sub.2, or —CH.sub.2COOM, and M is a cation. The compounds of formula (I), of formula (II), or mixtures thereof are preferably suitable to act as a dispersing agent.

##STR00001##

Claims

1. A composition containing compounds of formula (I), formula (II), or mixtures thereof, ##STR00011## wherein n is an integer greater than or equal to 1 R.sup.1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, a hydrogen atom, the structural unit —O—X, or the structural unit —CH.sub.2—O—X, X corresponds to formula (III) ##STR00012## in which a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28, m is 1 or 2, R.sup.2 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, Y is hydrogen, —SO.sub.3M, —SO.sub.2M, —PO.sub.3M.sub.2 or —CH.sub.2COOM, and M is a cation.

2. The composition as claimed in claim 1, wherein in formula Ill, read from left to right, block m is before block c, and wherein blocks a and b are arranged within m in a random or blockwise manner.

3. The composition as claimed in claim 1, wherein a is 3, 4 or 5.

4. The composition as claimed in claim 1, wherein b is an integer from 0 to 2.

5. The composition as claimed in claim 1, wherein m is equal to 1.

6. The composition as claimed in claim 1, wherein Y is H or —PO.sub.3M.sub.2.

7. The composition as claimed in claim 1, wherein the ratio of (a+b):c is 1:4 to 1:6.

8. The composition as claimed in claim 1, wherein a is a number from 2 to 6, b is a number from 0 to 3, c is a number from 20 to 28, m is 1 or 2, and Y is H or —PO.sub.3M.sub.2.

9. The composition as claimed in claim 1, wherein a is a number from 2 to 6, b is zero or 1, m is equal to one, and c is a number from 20 to 28.

10. The composition as claimed in claim 1, wherein R.sup.1 is —CH.sub.2—O—X.

11. The composition as claimed in claim 1, wherein R.sup.2 is —CH.sub.3.

12. The composition as claimed in claim 1, wherein n is 1.

13. A process for preparing compounds of formula (I), formula (II), or mixtures thereof, ##STR00013## wherein n is an integer greater than or equal to 1 R.sup.1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, a hydrogen atom, the structural unit —O—X, or the structural unit —CH.sub.2—O—X, X corresponds to formula (III) ##STR00014## in which a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28, m is 1 or 2, R.sup.2 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, Y is hydrogen, —SO.sub.3M, —SO.sub.2M, —PO.sub.3M.sub.2 or —CH.sub.2COOM, and M is a cation, by 1. providing an alcohol resulting from formula I or formula II by formal replacement of the X radical with H, 2. alkoxylating the alcohol with, per active hydrogen atom, 2 to 6 mol of styrene oxide and optionally with up to 3 mol of a C.sub.3- to C.sub.12-alkylene oxide, wherein the alkoxylation can be effected simultaneously with styrene oxide and the C.sub.3- to C.sub.32-alkylene oxide or sequentially, 3. optionally repeating step 2 once or twice, and 4. alkoxylating the product thus obtained with 20 to 28 mol of ethylene oxide per active hydrogen atom.

14. The process as claimed in claim 13, wherein the alkoylating is conducted using alkali metal, alkaline-earth metal or double metal cyanide catalysts.

15. The process as claimed in claim 13, wherein the alkoylating is conducted at temperatures in the range from 130-140° C. and at a pressure of from 2 to 9 bar.

16. The process as claimed in claim 13, wherein an alkali, alkaline earth or double metal cyanide catalyst is present in the alkoylating step, and wherein the catalyst is neutralized at the end of reaction.

17. The process as claimed in claim 13, further comprising the step of modifying the product obtained by adduct formation with an anionic group Y, wherein Y is selected from the group consisting of —SO.sub.3M, —SO.sub.2M, —PO.sub.3M.sub.2 and —CH.sub.2COOM.

18. The process as claimed in claim 13, further comprising the step after the end of reaction, wherein the product obtained is mixed with an aqueous substance and neutralized with lactic acid.

19. The process as claimed in claim 13, wherein a is a number from 2 to 6, b is zero or 1, m is equal to 1, and c is a number from 20 to 28.

20. The process as claimed in claim 13, wherein Y is PO.sub.3M.sub.2.

21. A dispersing agent for aqueous formulations of crop protection agent, comprising at least one compound of formula (I), formula (II), or mixtures thereof, ##STR00015## wherein n is an integer greater than or equal to 1 R.sup.1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, a hydrogen atom, the structural unit —O—X, or the structural unit —CH.sub.2—O—X, X corresponds to formula (III) ##STR00016## in which a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28, m is 1 or 2, R.sup.2 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, Y is hydrogen, —SO.sub.3M, —SO.sub.2M, —PO.sub.3M.sub.2 or —CH.sub.2COOM, and M is a cation.

Description

EXAMPLES

Synthesis of Examples 1 to 3 and Comparative Examples 1 to 4

Example 1: Pentaerythritol+4 Mol of Propylene Oxide+12 Mol of Styrene Oxide+80 Mol of Ethylene Oxide

[0073] A 1 L glass autoclave was initially charged with the reaction product of pentaerythritol and 4 eq. of propylene oxide (150.0 g, 0.41 mol) together with potassium hydroxide (40% by weight in water; 2.40 g). The mixture was dried at 125° C. under reduced pressure for one hour. Styrene oxide (587.1 g, 4.89 mol) was then added in portions at this temperature. The reaction was monitored by titration of the epoxide number. The intermediate was then cooled down to 100° C. and isolated. The intermediate (250.0 g, 0.14 mol) was then initially charged anew in a 1 L glass autoclave heated to 125° C. 486.7 g (11.05 mol) of ethylene oxide were metered in in portions at this 30 temperature under an inertized operation mode at a total pressure of 2-5 bar. After reacting to constant pressure, the product was cooled down to 80° C., traces of unreacted ethylene oxide were removed by application of reduced pressure for 30 min, and the product was isolated.

Example 2: Glycerol+12 Mol of Styrene Oxide+75 Mol of Ethylene Oxide

[0074] A 1 L autoclave was initially charged with glycerol (200 g, 2.17 mol) and KOH (40% aq., 30.46 g), the mixture was dried at 120° C. for 2 hours and then heated to 130° C. Styrene oxide (521.9 g, 4.34 mol) was added in portions at this temperature. The reaction was monitored by titration of the epoxide number. The intermediate was isolated and a portion (172.0 g, 0.51 mol) was initially charged in a further reaction and converted by the portionwise addition of styrene oxide (735.9 g, 6.12 mol) at 130° C. The reaction was monitored by titration of the epoxide number. The intermediate (200.0 g, 0.13 mol) was initially charged in an autoclave and reacted with ethylene oxide (459.5 g, 10.4 mol) at 135° C. under an inertized operation mode at a total pressure of 2-6 bar. After reacting to constant pressure, the product was cooled down to 80° C., traces of unreacted ethylene oxide were removed by application of reduced pressure for 30 min, and the product was isolated.

Example 3: Glycerol+12 Mol of Styrene Oxide+75 Mol of Ethylene Oxide+Phosphate Sodium Salt

[0075] The precursor was prepared in analogy with “example 2”. A stirring apparatus was initially charged with example 2 (1730.7 g) and this was heated to 60° C. before polyphosphoric acid (117.1 g) was metered in over a period of 2.5 hours. The internal temperature of the exothermal reaction was in the range from 60−70° C. After addition of had ended, the mixture was allowed to continue to react for 1 hour at 70° C. and for a further 5 hours at 100° C. The product was adjusted with sodium hydroxide solution (50% by weight aq.) to a pH of 7.7 and the total water content was adjusted to 20% by weight.

Comparative Example 1: Ethylenediamine+16 Styrene Oxide+100 Ethylene Oxide

[0076] Ethylenediamine (60.1 g) was dissolved in dimethyl tetraglycol (294.5 g) and reacted with styrene oxide (480.6 g). Potassium hydroxide was added (40% by weight aq., 15.0 g) and the water present was removed at 100° C. under reduced pressure. Further styrene oxide (1441.8 g) was then added and the intermediate was isolated after the reaction was complete. In a following reaction, the intermediate (341.6 g) was reacted with ethylene oxide (656.5 g). After complete reaction, the product was adjusted to a water content of 20% and isolated.

Comparative Example 2: Ethylenediamine+4 Propylene Oxide+8 Styrene Oxide+80 Ethylene Oxide

[0077] In analogy to the syntheses described above, the reaction product of ethylenediamine and 4 eq. of propylene oxide (200.0 g, 0.68 mol) was alkalized with potassium hydroxide (40% by weight in water; 5.59 g) and dried and reacted at 130° C. with styrene oxide (587.1 g, 4.89 mol). The intermediate (220.0 g, 0.17 mol) obtained was reacted at 135° C. with ethylene oxide (583.1 g, 13.24 mol). After reacting to constant pressure, the product was cooled down to 80° C., traces of unreacted ethylene oxide were removed by application of reduced pressure for 30 min, and the product was isolated.

Comparative Example 3: Pentaerythritol+4 Propylene Oxide+4 Styrene Oxide+10 Ethylene Oxide

[0078] In analogy to the syntheses described above, the reaction product of pentaerythritol and 4 eq. of propylene oxide (225.0 g, 0.61 mol) was alkalized with potassium hydroxide (40% by weight in water; 3.61 g) and dried and reacted at 130° C. with styrene oxide (293.5 g, 2.44 mol). The intermediate (180.0 g, 0.21 mol) obtained was reacted at 135° C. with ethylene oxide (373.6.7 g, 8.48 mol). After reacting to constant pressure, the product was cooled down to 80° C., traces of unreacted ethylene oxide were removed by application of reduced pressure for 30 min, and the product was isolated.

Comparative Example 4: Pentaerythritol+4 Propylene Oxide+8 Styrene Oxide+140 Ethylene Oxide

[0079] In analogy to the syntheses described above, the reaction product of pentaerythritol and 4 eq. of propylene oxide (225.0 g, 0.61 mol) was alkalized with potassium hydroxide (40% by weight in water; 3.61 g) and dried and reacted at 130° C. with styrene oxide (587.1 g, 4.89 mol). The intermediate (180.0 g, 0.14 mol) obtained was reacted at 135° C. with ethylene oxide (834.9 g, 18.95 mol). After reacting to constant pressure, the product was cooled down to 80° C., traces of unreacted ethylene oxide were removed by application of reduced pressure for 30 min, and the product was isolated.

[0080] Examples 1-3 according to the invention are started from pentaerythritol or glycerol. Example 1 was propoxylated once per alcohol group, before the styrene oxide and ethylene oxide blocks were added. In examples 2-3, glycerol was used as starter without propoxylation, and first styrene oxide was added, and thereafter ethylene oxide was added.

[0081] Comparative example 1 contains ethylenediamine as starter molecule. Diglyme is therefore necessary as polymerization solvent. This has the result that the polymeric dispersing agent thus obtained contains VOCs/SVOCs and hence does not satisfy the requirement.

[0082] In comparative example 2—similarly to in example 1 according to the invention—a single propoxylation was conducted per amine hydrogen. As a result, a starter with a relatively high molecular weight can be produced with which there is then no need for the use of a solvent for the subsequent polymerization. Comparative example 2 is therefore VOC/SVOC-free. Because of the use of ethylenediamine as starter, comparative example 2 is not in accordance with the invention.

[0083] Comparative example 3 was prepared using a polyol starter, pentaerythritol. In comparative example 3, a=1, i.e. the styrene oxide content is lower than that required according to the invention.

[0084] Comparative example 4 was prepared using a polyol starter, pentaerythritol. In comparative example 4, c=35, i.e. the ethylene oxide content is higher than that required according to the invention.

TABLE-US-00001 TABLE 1 Properties of the examples OH number Viscosity at Composition [mg KOH/g] 60° C. [mPas] Example 1 Pentaerythritol + 1.3 236 4 mol propylene oxide + 12 styrene oxide + 80 ethylene oxide Example 2 Glycerol + 12 51 269 styrene oxide + 75 ethylene oxide Example 3 Glycerol + 12 Total 1007 styrene oxide + phosphorus: 75 ethylene 2.25% by oxide + weight phosphate sodium salt Comparative Ethylene- Total 145 example 1 diamine + 16 nitrogen: styrene oxide + 0.44% by 100 ethylene weight oxide Comparative Ethylene- 59 237 example 2 diamine + 4 propylene oxide + 8 styrene oxide + 80 ethylene oxide Comparative Pentaerythritol + 102 154 example 3 4 propylene oxide + 4 styrene oxide + 40 ethylene oxide Comparative Pentaerythritol + 38 324 example 4 4 propylene oxide + 8 styrene oxide + 140 ethylene oxide

[0085] The OH numbers and viscosities reported were determined on 100%-pure substance. The number of oxide units reported is based on the whole molecule. In order to arrive, from the reported numbers, at the values for a, 5 b and c, these should be divided by the number of active hydrogen atoms in the starter molecule, for example 3 for glycerol and 4 for pentaerythritol.

TABLE-US-00002 TABLE 2 Structures of the examples Composition Structure Example 1 Pentaerythritol + 4 mol propylene oxide + 12 mol styrene oxide + 80 mol ethylene oxide [00004] Example 2 Glycerol + 12 mol styrene oxide + 75 mol ethylene oxide [00005] Example 3 Glycerol + 12 mol styrene oxide + 75 mol ethylene oxide + phosphate sodium salt [00006] Compara- tive example 1 Ethylenediamine + 16 mol styrene oxide + 100 mol ethylene oxide [00007] Compara- tive example 2 Ethylenediamine + 4 mol propylene oxide + 8 mol styrene oxide + 80 mol ethylene oxide [00008] Compara- tive example 3 Pentaerythritol + 4 mol propylene oxide + 4 mol styrene oxide + 40 mol ethylene oxide [00009] Compara- tive example 4 Pentaerythritol + 4 mol propylene oxide + 8 mol styrene oxide + 140 mol ethylene oxide [00010]

[0086] In order to assess the suitability of the polymers as dispersing agents for pigments, aqueous pigment pastes were prepared. To this end, the pigment, together with the dispersing agent according to the invention and other additives known from the prior art, was formed into a paste in deionized water and then preliminarily dispersed with a dissolver (for example of CN-F2 type from VMA-Getzmann GmbH) or another suitable apparatus. Fine dispersion was then effected using a bead mill (for example APS 500 from VMA-Getzmann) or another suitable dispersing unit, the grinding being performed using siliquartzite beads or zirconium mixed oxide beads having a size d=1 mm while coaling. The grinding media were then removed from the pigment dispersion and said dispersion was assessed. In particular, the polymers according to the invention were compared with the comparative examples with regard to viscosity, color strength and compatibility.

[0087] To this end, the following four base preparations were selected (all figures in % by mass are based on the total composition=100%).

TABLE-US-00003 TABLE 3 Test compositions I to IV. Item I II III IV Pigment Hostaperm Hansa Hostaperm Bayferrox brand Blue B2G- Brilliant Green Red 130 name EDS Yellow 2 GNX GX70S Pigment P.B. 15:3 P.Y. 74 P.G. 7 P.R. 101 Color Index Pigment A 45 50 45 65 Dispersing B 6 4 6 4 agent Antifoam C 0.3 0.3 0.3 0.3 Humectant D 10 10 10 10 Aqueous E 0.2 0.2 0.2 0.2 biocide Other F — — — Oleic acid 1% Water G to 100 to 100 to 100 to 100

[0088] The pigment preparation was prepared by initially charging components B, C, D, E, F and G and mixing them. The pulverulent component A was then added and preliminarily dispersed with the dissolver. Fine dispersion was effected in a bead mill using zirconium mixed oxide beads having a size d=1 mm while cooling. Grinding times were between 30 and 60 minutes. The grinding medium was then removed and the pigment preparation was isolated. The pigment preparation was analyzed after 24 hours in respect of color strength (tinting in emulsion paint) and viscosity. It was then stored for 28 days at 50° C. and reanalyzed in respect of both properties to give the storage stability.

[0089] The viscosity was analyzed with a cone/plate viscometer (Haake Viscotester 550 model) from Thermofischer GmbH at 20° C. over the shear rate range of 0 to 200 s.sup.−1, the shear rate of 60 s.sup.−1 being used to give the viscosity.

[0090] The storage stability was assessed on the basis of the viscosity. The storage stability after 24 h was compared with the viscosity measured after warm storage at 50° C. for 28 days. A paste was assessed as “very good” in terms of its storage stability when these viscosities do not differ in absolute amount by more than 200 mPas and the paste exhibited no sedimentation or syneresis. The storage stability was labelled as “good” when the viscosity changed by more than the amount of 200 mPas and/or slight sedimentation occurred. Non-storage-stable pastes thickened significantly during storage (rise in viscosity of more than 400 mPas) or became semisolid or thixotropic.

[0091] Color strength was determined in accordance with DIN 55986 by conducting a 2% tinting of an emulsion paint with the paste of interest. The tinted paint was then drawn down in a defined layer thickness onto a paint card and analyzed after drying with a Konica Minolta spectrophotometer.

[0092] Compatibility was determined by means of a rub-out test. To this end, the emulsion paint was applied after mixing with the pigment dispersion to a paint card. The lower part of the paint card was subsequently rubbed with a finger. Incompatibility was present when the rubbed area was more strongly colored than the adjacent, non-aftertreated area (cf. also in this respect DE 2 368 946). The following results were achieved:

TABLE-US-00004 TABLE 4 Performance results for the preparations Preparation Dispersing VOC/ Color Viscosity Storage Example type agent SVOC strength Compatibility (mPas) stability  1 I Example 1 no very good no rub-out 90 very good  2 I Example 2 no very good no rub-out 92 very good  3 I Example 3 no very good no rub-out 95 very good  4 I Comparative yes good no rub-out 83 not storage- example 1 stable  5 I Comparative no very good no rub-out 117 not storage- example 2 stable  6 I Comparative no very good no rub-out 191 paste already example 3 solid after one week  7 I Comparative no very good no rub-out 160 not storage- example 4 stable  9 II Example 1 no very good no rub-out 259 very good  9 II Example 2 no very good no rub-out 102 very good 10 II Example 3 no very good no rub-out 176 very good 11 II Comparative yes very good no rub-out 74 very good example 1 12 II Comparative no good strong rub-out 86 very good example 2 13 II Comparative no good no rub-out 68 not storage- example 3 stable 14 II Comparative no good no rub-out 305 not storage- example 4 stable 15 III Example 1 no very good no rub-out 107 very good 16 III Example 2 no very good no rub-out 105 very good 17 III Example 3 no very good no rub-out 246 very good 18 III Comparative yes very good no rub-out 105 not storage- example 1 stable 19 III Comparative no good strong rub-out 539 very good example 2 20 IV Example 1 no very good no rub-out 728 good 21 IV Comparative yes Creation of a free-flowing paste not possible example 1

[0093] As can be seen in the above examples, better results in terms of color strength, compatibility, viscosity and storage stability are achieved when polyols are used as starter and the amounts of oxirane derivatives in accordance with the invention are used.

[0094] Pigment Blue 15:3, which is used in the preparations of example A, can be satisfactorily dispersed in all aspects with examples 1-3 according to the invention. In contrast, preparations with comparative examples 1 and 2 are not storage-stable, which is identifiable by a significant increase in viscosity during storage and thixotropy in the case of comparative example 1. Comparative examples 3 and 4, with styrene oxide/ethylene oxide content not in accordance with the invention, stand out firstly due to very intense foam formation. In addition, the preparation with comparative example 3 is already semisolid after a week. The preparation with comparative example 4 is not storage-stable, either.

[0095] Pigment Yellow 74, which is used in all preparations of example B, is a pigment which can be dispersed with relative ease and therefore can also be dispersed satisfactorily by many dispersing agent examples. In the case of comparative example 2, a high degree of incompatibility of the paste with the base paint is seen, as a very strong rub-out is observed. Comparative example 1 leads to a pigment preparation containing volatile organic constituents (VOCs/SVOCs). In addition, comparative examples 3 and 4 stand out again due to intense foam formation and a lack of storage stability.

[0096] Pigment Green 7, which is used in the preparations of example B, can be satisfactorily dispersed in all aspects with examples 1-3 according to the invention. In the case of comparative example 1, the lack of storage stability is again an issue, including thixotropy and a viscosity increase within a week of greater than 1000 mPas. In the case of comparative example 2, a high degree of incompatibility arises again, as a very strong rub-out is observed.

[0097] Pigment Red 101 is the sole inorganic pigment of the examples. Example 1 can also disperse this inorganic pigment sufficiently well. In the event of storage, slight sedimentation occurs which can however be readily stirred up again. This property can be compensated again in more developed preparation formulations using rheology additives. It was not possible to create a free-flowing paste with comparative example 1.

[0098] Comparative example 1 was started with ethylenediamine and contains diglyme as solvent, which contributes VOCs/SVOCs. Color strengths of a quality similar to those with examples 1-3 according to the invention can be achieved with this dispersing agent in organic pigments, however, only the paste with the less-demanding Pigment Yellow 74 is storage stable. For inorganic iron oxide red, comparative example 1 is not advisable.

[0099] Comparative example 2 likewise contains ethylenediamine as starter, but also contains one propylene oxide unit per active amine oxygen before the styrene oxide blocks. This synthesis strategy makes it possible to operate without solvent since the single propoxylation increases the molecular weight of the starter. Therefore, the requirements for a VOC/SVOC-free dispersing agent are satisfied. However, comparative example 2 regularly leads to incompatibilities with the base paint in tinting, visible through a strong rub-out in yellow and green.

[0100] In the case of Pigment Blue 15:3. the paste is not storage stable; there is significant formation of sediment which cannot readily be redispersed. Therefore, this example does not satisfy the requirements.

[0101] The amine-started comparative examples cannot fulfill the requirements in all claims and all tested pigment preparations. They do not have the formula (I) or (II) according to the invention as starter.

[0102] Comparative example 3 with a styrene oxide content not in accordance with the invention (a=1) does not satisfy the object either, and neither does comparative example 4 with an excessively high ethylene oxide content (c=35).

[0103] Examples 1-3 according to the invention achieve the technical object set in regards to pigment dispersions, irrespective of whether propoxylation was conducted on the polyol starter (example 1) or not (examples 2-3).

[0104] In summary, it can be stated that the object is achieved only by the polymers according to the invention with polyol starters and correct contents of styrene oxide and ethylene oxide. Only the polymers according to the invention satisfy all required criteria in the resulting pigment preparations.

Crop Protection Formulation Example

[0105]

TABLE-US-00005 Suspension concentrate with 430 g/L tebuconazole Composition SC 1 [%] SC 2 [%] SC 3 [%] Tebuconazole 40.70 40.70 40.70 Example 2 0.60 Comparative 0.60 example 3 Comparative 0.60 example 4 Genapol PF 40 1.25 1.25 1.25 Propylene glycol 5.25 5.25 5.25 Silfoam SE 3060 0.50 0.50 0.50 Thickener 10.00 10.00 10.00 solution with xanthan gum (2% solution in water) Deionized water 41.70 41.70 41.70 Σ 100.00 100.00 100.00 Appearance white solid solid suspension Density [g/ccm] 1.078 n.d. n.d. pH [1%] 6.49 n.d. n.d. Suspensibility 94.26 n.d. n.d. [%] n.d. = not determinable

[0106] In the crop protection formulation with tebuconazole as well, only the formulation with example 2 according to the invention results in a stable suspension, whereas the formulations with the comparative examples are solid.