Alkoxylates of S-vinylthioalkanols

Abstract

Unsaturated compounds of formula (I): ##STR00001##
wherein: R.sup.1, R.sup.2, and R.sup.3 are each independently H or CH.sub.3; R.sup.4 is a linear or branched C.sub.1-C.sub.30-alkylene; R.sup.5 and R.sup.6 are each independently H, C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.15-cycloalkyl, aryl, CH.sub.2OC.sub.1-C.sub.20-alkyl, or CH.sub.2OC.sub.2-C.sub.20-alkenyl, where R.sup.5 and R.sup.6 may together form a C.sub.3-C.sub.6-alkylene; R.sup.7 is independently H,C.sub.1-C.sub.4-alkyl, or ##STR00002##
where R.sup.8 is C.sub.1-C.sub.22-alkyl or C.sub.2-C.sub.22-alkenyl; and n is an integer from 2 to 200. Mixtures and polymers including the unsaturated compounds of formula (I). A method for preparing polymers by free-radical polymerization of monomers including the unsaturated compounds of formula (I). A process for preparing polymers including polymer-analogous reactions. And polymers including compounds (I) as cement additives, grinding aids, hydraulic binder additives, concrete plasticizers, reactive plasticizers for preparing plastics, rubber, or latex, associative thickeners and antioxidants, or for preparing polyether siloxanes.

Claims

1. An unsaturated compound of formula (I) ##STR00022## wherein R.sup.1, R.sup.2, and R.sup.3 are the same or different and are each independently H or CH.sub.3, R.sup.4 is a linear or branched C.sub.1-C.sub.30-alkylene, R.sup.5 and R.sup.6 are the same or different and are each independently selected from the group consisting of H, C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.15-cycloalkyl, aryl, CH.sub.2OCH.sub.1-C.sub.20-alkyl, and CH.sub.2OC.sub.2-C.sub.20-alkenyl, where R.sup.5 and R.sup.6 may together form a C.sub.3-C.sub.6-alkylene, R.sup.7 is the same or different and is independently H, C.sub.1-C.sub.4-alkyl, or ##STR00023## R.sup.8 is C.sub.1-C.sub.22-alkyl or C.sub.2-C.sub.22-alkenyl, and n is an integer from 21 to 200.

2. The unsaturated compound according to claim 1, wherein, in formula (I): R.sup.4 is a C.sub.2-C.sub.4-alkylene group, R.sup.5 and R.sup.6 are the same or different and are each independently selected from the group consisting of H, CH.sub.3, CH.sub.2CH.sub.3, C.sub.3-C.sub.11-alkyl, C.sub.12-C.sub.22-alkyl, phenyl, CH.sub.2OC.sub.1-C.sub.10-alkyl, and CH.sub.2OC.sub.2-C.sub.10-alkenyl, R.sup.7 is or C.sub.1-C.sub.4-alkyl, and n is 21 to 140.

3. The unsaturated compound according to claim 1, wherein the compound of formula (I) is an unsaturated compound of formula (Ia): ##STR00024## wherein: R.sup.3 is 1or methyl, R.sup.4 is a linear or branched C.sub.2-C.sub.10-alkylene group, R.sup.5 and R.sup.6 are each independently H, methyl, or ethyl, with the proviso that the sum total of carbon atoms in the R.sup.5 and R.sup.6 residues per alkoxy group is in each case 0 to 2, and n is 21 to 160.

4. The unsaturated compound according to claim 1, wherein the compound of formula (I) is an unsaturated compound of formula (Ib): ##STR00025## wherein n is 21 to 140.

5. The unsaturated compound according to claim 4, wherein, in formula (Ib), n is 21 to 30.

6. A mixture comprising the unsaturated compounds of formula (I) according to claim 1.

7. A polymer comprising the unsaturated compounds of formula (I) according to claim 1 as monomers.

8. A polymer comprising the unsaturated compounds of formula (Ia) according to claim 3 as monomers.

9. A polymer comprising the unsaturated compounds of formula (Ib) according to claim 4 as monomers.

10. The polymer according to claim 7, wherein at least one further monomer different from the unsaturated compounds of formula (I)is present in the polymer.

11. The polymer according to claim 10, wherein the at least one further monomer is at least one monoethylenically unsaturated monomer.

12. The polymer according to claim 11, wherein the monoethylenically unsaturated monomers are monomers comprising acid groups, where the acid groups may also be completely or partly neutralized.

13. The polymer according to claim 12, wherein the acid groups are selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups.

14. The polymer according to claim 13, wherein the polymer comprises at least one monomer having carboxylic acid groups selected from the group consisting of acrylic acid, methacrylic acid, (meth)acrylic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylene malonic acid and salts thereof.

15. The polymer according to claim 13, wherein the polymer comprises at least one monomer having phosphoric acid groups or phosphonic acid groups selected from the group consisting of vinylphosphonic acid, an ester of hydroxyethyl (meth)acrylate with (poly)phosphoric acid, an ester of hydroxypropyl (meth)acrylate with (poly)phosphoric acid, an ester of hvdroxybutyl (meth)acrylate with (poly)phosphoric acid, monovinyl phosphate, allylphosphonic acid, monoallyl phosphate, 3-butenylphosphonic acid, mono-3-butenyl phosphate, mono(4-vinyloxybutyl) phosphate, mono(2-hydroxy-3-vinyloxypropyl) phosphate, mono(1-phosphonoxymethyl-2-vinyloxyethyl)phosphate, mono(3-allyloxy-2-hydroxypropyl) phosphate, mono [2-(allyloxy-1-phosphonoxymethylethyl)]phosphate, 2-hydroxy-4-vinyloxymethyl-1,3,2-dioxaphosphole, 2-hydroxy-4-allyloxymethyl-1,3,2-dioxaphosphole and salts thereof.

16. The polymer according to claim 13, wherein the polymer comprises at least one monomer having sulfonic acid groups selected from the group consisting of vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidomethyldodecylsulfonic acid, 2-(meth)acryloxyethanesulfonic acid, 3-(meth)acryloxypropanesulfonic acid, allyloxybenzenesulfonic acid, vinylbenzenesulfonic acid, vinyltoluenesulfonic acid, allylsulfonic acid, methallylsulfonic acid and salts thereof.

17. The polymer according to claim 11, wherein the at least one monoethylenically unsaturated monomer present is at least one selected from the group consisting of styrene, butadiene, methyl methacrylate, (meth)acrylate, ethyl acrylate, dibutyl maleate, methyl alpha-cyanoacrylate, acrylonitrile, acrylic acid, methacrylic acid, maleic acid (anhydride), itaconic acid, vinvlphosphonic acid, N-vinylpyrrolidone, N,N-dimethyl-N,N-diallylammonium chloride, acrylamide, vinylimidazole, vinyl alcohol, vinyl acetate, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, (iso)prenyl alkoxylate, (meth)allyl alkoxylate, and hydroxybutyl vinyl ether alkoxylate.

18. The polymer according to claim 17, wherein the at least one monoethylenically unsaturated monomer present is at least one selected from the group consisting of acrylic acid, methacrylic acid, (meth)acrylate, maleic acid (anhydride), (iso)prenyl alkoxylate, (meth)allyl alkoxylate, and hydroxybutyl vinyl ether alkoxylate.

19. The polymer according to claim 18, wherein the polymer consists of the unsaturated compounds of formula (I) and at least one monoethylenically unsaturated monomer selected from the group consisting of acid, methacrylic acid, (meth) acrylate, maleic acid (anhydride, (iso)prenyl alkoxylate, (meth)allyl alkoxylate, and hydroxybutyl vinyl ether alkoxylate as monomers.

20. The polymer according to claim 17, wherein the polymer consists of the unsaturated compounds of formula (I) and at least one monoethylenically unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, and maleic acid (anhydride) as monomers.

21. The polymer according to claim 20, wherein the polymer consists of the unsaturated compounds of formula (I), acrylic acid, methacrylic acid, and maleic acid (anhydride) as monomers.

22. The polymer according to claim 7, wherein from 5 to 99.9% by weight of the unsaturated compounds of formula (I) are present in the polymer, based on the total amount of monomers.

23. The polymer according to claim 11, comprising, in each case based on a total amount of monomers: from 5 to 99.9% by weight of the unsaturated compounds of formula (I); and from 95 to 0.1% by weight of the at least one monoethylenically unsaturated monomer.

24. The polymer according to claim 18, comprising, in each case based on a total amount of monomers: from 5 to 99.9% by weight of the unsaturated compounds of formula (I); and from 95 to 0.1% by weight of the at least one monoethylenically unsaturated monomer.

25. The polymer according to claim 7, wherein the number-average molecular weight M.sub.n , of the polymers is 1,000 g/mol to 1,000,000 g/mol.

26. The polymer according to claim 7, wherein the number-average molecular weight M.sub.n of the polymers is 5000 g/mol to 100,000 g/mol.

27. A method for preparing the polymer according to claim 7, wherein the unsaturated compounds of formula (I) and optionally at least one further monomer are subjected to free-radical polymerization.

28. The method according to claim 27, wherein the method is a copolymerization in which the unsaturated compounds of formula (I) and at least one further monoethylenically unsaturated monomer are subjected to free-radical polymerization.

29. The method according to claim 28, wherein the further monoethylenically unsaturated monomers are monomers comprising acid groups, ere he acid groups may also be completely or partly neutralized.

30. The method according to claim 29, wherein the acid groups are selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric acid groups.

31. The method according to claim 27, wherein the unsaturated compounds of formula (I) are unsaturated compounds of formula (Ia): ##STR00026## wherein: R.sup.3 is H or methyl, R.sup.4 is a linear or branched C.sub.2-C.sub.10-alkylene group, R.sup.5 and R.sup.6 are each independently H, methyl, or ethyl, with the proviso that the sum total of carbon atoms in the R.sup.5 and R.sup.6 residues per alkoxy group is in each case 0 to 2, and n is 21 to 160.

32. The method according to claim 27, wherein the unsaturated compounds of formula (I) are unsaturated compounds (Ib): ##STR00027## wherein n is 21 to 140.

33. The method according to claim 27, wherein the free-radical polymerization is carried out in aqueous solution.

34. The method according to claim 33, wherein the pH in the course of the polymerization is 1 to 6.

35. The method according to claim 33, wherein the pH in the course of the polymerization is 1 to 3.

36. The method according to claim 28, wherein the free-radical polymerization is carried out b initially charging a portion of the unsaturated compounds of formula (I), (Ia) or (Ib), a portion of the further monomers and also a portion of a polymerization initiator in a reactor, and gradually metering into the polymerization reactor the remaining amounts of the unsaturated compounds of formula (I), (Ia) or (Ib), the further monomers and also the polymerization initiator: ##STR00028## wherein: R.sup.3 is H or methyl, R.sup.4 is a linear or branched C.sub.2-C.sub.10-alkylene group, R.sup.5 and R.sup.6 are each independently H, methyl, or ethyl, with the proviso that the sum total of carbon atoms in the R.sup.5 and R.sup.6 residues per alkoxy group is in each case 0 to 2, and n is 21 to 160; ##STR00029## wherein n is 21 to 140.

37. The method according to claim 36, wherein the amount of monomers initially charged does not exceed 25% by weight of the total amount of the monomers.

38. A cement additive, grinding aid in the production of cement, concrete plasticizer, additive to hydraulic binders, reactive plasticizer for preparing plastics, rubber or latex, associative thickener and/or antioxidant, comprising the polymer according to claim 7.

39. A mixture comprising the polymer according to claim 7.

Description

EXAMPLES

(1) VME: vinylmercaptoethanol H.sub.2CCHSCH.sub.2CH.sub.2OH HBVE: hydroxybutyl vinyl ether H.sub.2CCHOCH.sub.2CH.sub.2CH.sub.2CH.sub.2OH
Methods of Measurement:
OH Number:

(2) The OH number (OHN) is a measure of the alcohol groups present in a sample. The determination is carried out by esterifying the alcohol groups with an excess of acetic anhydride. Following hydrolysis of the unreacted acetic anhydride, the residual free acetic acid is titrated with KOH. The OH number data are expressed in units of mg KOH/g of sample. The OH number therefore corresponds to the amount of KOH in mg, which is equivalent to the amount of acetic acid linked to the acetylation of 1 g of substance.

(3) PEG Content:

(4) The polyethylene glycol content is defined as the proportion of PEG in nonionic surfactants and EO adducts which may be determined by thin-layer chromatography. This is stated as g per 100 grams. Polyethylene glycol is separated from oxyethylate in a substance spot by thin-layer chromatography using a ready-to-use HPTLC plate and is quantified by remission location curve measurement after derivatization with Dragendorff's reagent. The evaluation is conducted after calibration with a PEG standard (PEG 1000).

(5) GPC Measurement

(6) (For all Experiments Except 5a to 5 g and Comparative Experiments 5a to 5c):

(7) Columns:

(8) The following columns from PSS Mainz were connected in series: PSS Suprema pre-column PSS Suprema 30 , 10 8300 mm PSS Suprema 1000 , 10 8300 mm PSS Suprema 3000 , 10 8300 mm
and maintained at 35 C.

(9) Column Material:

(10) Modified acrylate copolymer network.

(11) Eluent:

(12) Phosphate buffer pH 9.7 0.0239 mol/L disodium hydrogen phosphate (dihydrate), pH 9.7, adjusted with NaOH 2 mol/L, 0.5 g/L sodium azide.

(13) The samples are diluted with the eluent.

(14) Instruments/Software:

(15) Agilent 1100 system with ChemStation, evaluation using PSS WinGPC Unity.

(16) Conditions:

(17) Sample Dilution:

(18) 1.5 mL eluent+10 L acetone (internal standard)+20 L sample (up to max. 50% solution, less at higher concentration), Injection: 50 L, with needle wash, Flow rate: 0.8 mL/min, Run time: 60 min, Detector: RID (Agilent G1362A), 35 C. Calibration:

(19) Calibration standards from PSS: Polyethylene glycol (PEG), polyethylene oxide (PEO) for high molar masses. Internal standard for compensation of flow rate variations: acetone.

(20) GPC Methods for Experiments 5a to 5 g and Comparative Experiments 5a to 5c (See Table 4):

(21) column combinations: OHpak SB-G, OHpeak SB 804 HQ and OHpak SB 802.5 HQ from Shodex, Japan; eluent: 80% by volume aqueous solution of HCO.sub.2NH.sub.4 (0.05 mol/I) and 20% by volume acetonitrile; injection volume 100 l; flow rate 0.5 ml/min). The calibration in order to determine the average molar mass took place using linear polyethylene glycol standards. The polymer peak is normalized to a relative height of 1 as a measure of the conversion and the peak height of the unreacted macromonomer/PEG-containing oligomer is used as a measure of the residual monomer content.

Example 1

Preparation of Alkoxylates of S-vinylthioalkanols

Example 1a

(22) ##STR00011##

(23) A 2 L autoclave was charged with 104 g (1.00 mol) of vinylmercaptoethanol and 2.18 g (19.4 mmol KOH) of an aqueous potassium hydroxide solution (50% by weight) at 70 C. and the water was removed at <20 mbar over a period of 2 h. The autoclave was then flushed with nitrogen and the temperature increased to 130 C. 440 g (10.0 mol) of ethylene oxide were added over a period of 4 h. The reaction mixture obtained was then stirred for 10 h at 130 C. and, after cooling to 100 C., was freed from volatile constituents under reduced pressure.

(24) 572 g of a brown liquid were obtained.

(25) OHN=102.5 mg KOH/g (theory 103.0 mg KOH/g)

Example 1b

(26) ##STR00012##

(27) A 2 L autoclave was charged with 164 g (0.30 mol) of vinylmercaptoethanol*10EO (example 1a) and 686 mg (6.11 mmol KOH) of an aqueous potassium hydroxide solution (50% by weight) at 100 C. and the water was removed at <20 mbar over a period of 2 h. The autoclave was then flushed with nitrogen and the temperature increased to 130 C. 172 g (3.90 mol) of ethylene oxide were added over a period of 1.5 h. The reaction mixture obtained was then stirred for 8 h at 130 C. and, after cooling to 100 C., was freed from volatile constituents under reduced pressure.

(28) 337 g of a brown solid were obtained.

(29) OHN=55.6 mg KOH/g (theory 50.2 mg KOH/g); PEG content=10.5% by weight.

Example 1c

(30) ##STR00013##

(31) A 2 L autoclave was charged with 52.1 g (0.50 mol) of vinylmercaptoethanol and 410 mg (1.87 mmol KOMe) of a methanolic potassium methoxide solution (32% by weight in methanol) at 65 C. and the methanol was removed at <20 mbar over a period of 2 h. The autoclave was then flushed with nitrogen and the temperature increased to 120 C. 528 g (12.0 mol) of ethylene oxide were added over a period of 4 h. The reaction mixture obtained was then stirred for 10 h at 120 C. and, after cooling to 100 C., was freed from volatile constituents under reduced pressure.

(32) 606 g of a brown solid were obtained.

(33) OHN=47.5 mg KOH/g (theory 48.8 mg KOH/g), PEG content: <1% by weight

Example 1d

(34) ##STR00014##

(35) A 2 L autoclave was charged with 104 g (1.00 mol) of vinylmercaptoethanol and 289 mg (90%, 4.50 mmol KOH) of KOH flakes in 416 g of toluene at 60 C. and flushed with nitrogen. The temperature was then increased to 120 C. 1057 g (24.0 mol) of ethylene oxide were added over a period of 13 h. The reaction mixture obtained was then stirred for 10 h at 120 C. and, after cooling to 105 C., was freed from volatile constituents under reduced pressure.

(36) 1181 g of a light brown solid were obtained.

(37) OHN=50.6 mg KOH/g (theory 48.8 mg KOH/g), PEG content: <1% by weight

Example 1e

(38) ##STR00015##

(39) A 2 L autoclave was charged with 104 g (1.00 mol) of vinylmercaptoethanol and 641 mg (2.97 mmol KOMe) of a methanolic potassium methoxide solution (32% by weight in methanol) at 60 C. and the methanol was removed at <20 mbar over a period of 2 h. The autoclave was then flushed with nitrogen and the temperature increased to 130 C. 581 g (10.0 mol) of propylene oxide were added over a period of 10 h. The reaction mixture obtained was then stirred for 10 h at 130 C. and, after cooling to 100 C., was freed from volatile constituents under reduced pressure.

(40) 629 g of a dark brown solid were obtained.

(41) OHN=88.0 mg KOH/g (theory 81.9 mg KOH/g)

Example 1f

(42) ##STR00016##

(43) A 2 L autoclave was charged with 188 g (275 mmol) of vinylmercaptoethanol*10PO (example 1e) and 1.85 g (16.6 mmol KOH) of an aqueous potassium hydroxide solution (50% by weight) at 100 C. and the water was removed at <20 mbar over a period of 2 h. The autoclave was then flushed with nitrogen and the temperature increased to 120 C. 396 g (9.00 mol) of ethylene oxide were added over a period of 6 h. The reaction mixture obtained was then stirred for 5 h at 120 C. and, after cooling to 90 C., was freed from volatile constituents under reduced pressure.

(44) 597 g of a light brown solid were obtained.

(45) OHN=31.8 mg KOH/g (theory 28.8)

Example 1g

(46) ##STR00017##

(47) A 2 L autoclave was charged with 68.4 g (0.10 mmol) of vinylmercaptoethanol*10PO (example 1e) and 0.62 g (5.52 mmol KOH) of an aqueous potassium hydroxide solution (50% by weight) at 100 C. and the water was removed at <20 mbar over a period of 2 h. The autoclave was then flushed with nitrogen and the temperature increased to 120 C. 550 g (12.5 mol) of ethylene oxide were added over a period of 6 h. The reaction mixture obtained was then stirred for 5 h at 120 C. and, after cooling to 90 C., was freed from volatile constituents under reduced pressure.

(48) 610 g of a brown solid were obtained.

(49) OHN=12.2 mg KOH/g (theory 9.2), PEG content: 1.4% by weight

Example 1h

(50) ##STR00018##

(51) A 2 L autoclave was charged with 46.7 g (448 mmol) of vinylmercaptoethanol and 120 mg (1.71 mmol) of potassium methoxide in 100 mL of toluene at 60 C. and flushed with nitrogen. The temperature was then increased to 120 C. 1321 g (30.0 mol) of ethylene oxide were added over a period of 20 h. The reaction mixture obtained was then stirred for 10 h at 120 C. and, after cooling to 100 C., was freed from volatile constituents under reduced pressure.

(52) 1396 g of a light brown solid were obtained.

(53) OHN=21.2 mg KOH/g (theory 18.4 mg KOH/g), PEG content: 1.4% by weight

Example 1i

(54) ##STR00019##

(55) A 2 L autoclave was charged with 23.4 g (224 mmol) of vinylmercaptoethanol and 120 mg (1.71 mmol) of potassium methoxide in 50 mL of toluene at 60 C. and flushed with nitrogen. The temperature was then increased to 120 C. 1332 g (30.2 mol) of ethylene oxide were added over a period of 36 h. The reaction mixture obtained was then stirred for 12 h at 120 C. and, after cooling to 100 C., was freed from volatile constituents under reduced pressure.

(56) 1388 g of a light brown solid were obtained.

(57) OHN=12.1 mg KOH/g (theory 9.3 mg KOH/g), PEG content: 2.0% by weight

Comparative Example 1j

(58) Preparation of HBVE-24 EO

(59) The procedure was as in Example 1c, only a corresponding amount of HBVE was used in place of VME.

Comparative Example 1k

(60) Preparation of HBVE-67 EO

(61) The procedure was as in Example 1 h, only a corresponding amount of HBVE was used in place of VME.

Comparative Example 1l

(62) Preparation of HBVE-135 EO

(63) The procedure was as in Example 1i, only a corresponding amount of HBVE was used in place of VME.

Example 2

Preparation of Polymers, Method (A)

(64) In method (A), the VME or HBVE alkoxylates are initially charged for the polymerization

Example 2a

(65) Copolymer of 89% by weight VME-23EO and 11% by weight acrylic acid

(66) Polymerization at pH 2-3 (azo starter)

(67) 35.6 g of VME ethoxylate (23EO) according to Example 1 b were dissolved in 63.5 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.1 g) of a solution A (4.4 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.1 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(68) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Example 2b

(69) The procedure was as in Example 2a, only the amount of initiator was reduced from 1.6 g to 1.2 g. Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Example 2c

(70) The procedure was as in Example 2a, only the amount of initiator was reduced from 1.6 g to 0.8 g. Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2a

(71) Copolymer of 89% by weight HBVE-24EO and 11% by weight acrylic acid

(72) 35.6 g of HBVE-24EO according to comparative example 1i were dissolved in 63.5 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.1 g) of a solution A (4.4 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.1 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(73) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2b

(74) The procedure was as in Example 2, only the amount of initiator was reduced from 1.6 g to 1.2 g. Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2c

(75) The procedure was as in Example 2, only the amount of initiator was reduced from 1.6 g to 0.8 g. Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

(76) A GPC measurement of the reaction products from example 2a and comparative example 2a showed an additional strongly pronounced low molecular weight peak in the case of HBVE-24EO (comparative example 2a). In the case of the HBVE ethoxylates, a large proportion of the monomers was hydrolyzed during the polymerization.

(77) Furthermore, in 1H-NMR measurements of comparative examples 2a, 2b and 2c, vinyl compound was no longer observed.

Example 2d

(78) Copolymer of 85% by weight VME-23EO and 15% by weight Na acrylate

(79) Polymerization at pH 7-8 (azo starter)

(80) 34.0 g of VME ethoxylate-23EO according to Example 1b were dissolved in 63.5 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.2 g) of a solution A (6.0 g of acrylic acid Na salt dissolved in 18.4 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.1 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture is then stirred at 70 C. for 2 h.

(81) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2d

(82) Copolymer of 85% by weight HBVE-24EO and 15% by weight Na acrylate

(83) Polymerization at pH 7-8 (azo starter)

(84) 34.0 g of HBVE-24EO according to example 1i were dissolved in 63.5 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.2 g) of a solution A (6.0 g of acrylic acid sodium salt dissolved in 18.4 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.1 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(85) No hydrolysis of HBVE ethoxylate was observed at neutral pH. .sup.1H-NMR measurement of the polymer revealed that ca. 8% of the HBVE ethoxylate used had not been polymerized. The molar mass of the HBVE ethoxylate/acrylic acid copolymer was distinctly lower than that of the VME ethoxylate-acrylic acid copolymer.

(86) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Example 2e

(87) Copolymer of 89% by weight VME-23EO and 11% by weight acrylic acid

(88) Polymerization at pH 1.9 (peroxide starter)

(89) 42.7 g of VME ethoxylate-24EO according to example Id were dissolved in 38.8 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The solution was heated under nitrogen to 95 C. and addition of solutions A (5.3 g of acrylic acid dissolved in 41.4 g of water) and B (1.9 g of sodium peroxodisulfate dissolved in 31.4 g of water) initiated, wherein solution A was added over 4 hours and solution B over 5 hours. The reaction mixture was then stirred at 95 C. for 2 h.

(90) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2e

(91) Copolymer of 89% by weight HBVE-24EO and 11% by weight acrylic acid

(92) Polymerization at pH 1.9

(93) 42.7 g of HBVE-24EO according to comparative example 1j were dissolved in 38.8 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The solution was heated under nitrogen to 95 C. and addition of solutions A (5.3 g of acrylic acid dissolved in 41.4 g of water) and B (1.9 g of sodium peroxodisulfate dissolved in 31.4 g of water) initiated, wherein solution A was added over 4 hours and solution B over 5 hours. The reaction mixture was then stirred at 95 C. for 2 h.

(94) An intense hydrolysis of HBVE ethoxylate was observed. A large peak at low molar masses was observed in the GPC.

(95) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Example 2f

Polymerization in Bulk

(96) Copolymer of 89% by weight VME-24EO and 11% by weight acrylic acid

(97) 71.2 g of VME-24EO according to example 1 d and 2.4 g of 2-mercaptoethanol were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The mixture was heated under nitrogen to 85 C. and addition of 8.7 g of acrylic acid and 3.2 g of tert-butyl peroctoate initiated, wherein the acrylic acid was added over 3 hours and initiator over 4 hours. The reaction mixture was then stirred at 85 C. for 4 h.

(98) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2f

(99) Copolymer of 89% by weight HBVE-24EO and 11% by weight acrylic acid

(100) 71.2 g of HBVE-24EO according to comparative example 1j and 2.4 g of 2-mercaptoethanol were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The mixture was heated under nitrogen to 85 C. and addition of 8.7 g of acrylic acid and 3.2 g of tert-butyl peroctoate initiated, wherein the acrylic acid was added over 3 hours and initiator over 4 hours. The reaction mixture was then stirred at 85 C. for 4 h.

(101) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

(102) Polymers according to the invention can also be prepared in bulk (without solvent). For polymerization in bulk, the monomers are treated with an azo starter. For example, the copolymerization of VME ethoxylate and acrylic acid in bulk is also possible using peroctoate as initiator at 85 C. Regulators can also be used in the polymerization in bulk, for example, mercaptoethanol or mercaptopropionic acid.

Example 2g

Polymerization of Long-chain VME Ethoxylates

(103) Copolymer of 81% by weight VME-67EO and 19% by weight acrylic acid

(104) Polymerization at pH 2-3 (azo starter)

(105) 32.6 g of VME ethoxylate (67EO) according to Example 1 h were dissolved in 63.5 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.3 g) of a solution A (7.6 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.1 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(106) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2g

(107) Copolymer of 81% by weight HBVE-67EO and 19% by weight acrylic acid

(108) Polymerization at pH 2-3 (azo starter)

(109) 32.4 g of HBVE ethoxylate (67EO) according to comparative example 1 k were dissolved in 57.6 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.6 g) of a solution A (7.6 g of acrylic acid dissolved in 24.0 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.4 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(110) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

(111) A GPC measurement of the reaction products from example 2g and comparative example 2g showed an additional strongly pronounced low molecular weight peak in the case of HBVE-24EO (comparative example 2g). In the case of the HBVE ethoxylates, a large proportion of the monomers was hydrolyzed during the polymerization. Furthermore, in 1H-NMR measurements of comparative examples 2g, vinyl compound was again observed.

Example 2h

(112) Copolymer of 81% by weight VME-135EO and 19% by weight acrylic acid

(113) Polymerization at pH 2-3 (azo starter)

(114) 32.3 g of VME ethoxylate (135EO) were dissolved in 63.5 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.3 g) of a solution A (7.7 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.2 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(115) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

Comparative Example 2h

(116) Copolymer of 81% by weight HBVE-135EO and 19% by weight acrylic acid

(117) Polymerization at pH 2-3 (azo starter)

(118) 32.3 g of HBVE ethoxylate (135EO) according to comparative example 11 were dissolved in 57.6 g of water in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. A portion (1.6 g) of a solution A (7.7 g of acrylic acid dissolved in 24.0 g of water) and a portion (2 g) of a solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) dissolved in 38.4 g of water) were added. The polymerization was started by heating the solution under nitrogen to 70 C. and the remaining amounts of solutions A and B were then added, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(119) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 1.

(120) TABLE-US-00001 TABLE 1 Results of the polymer syntheses (*amount of residual monomer by NMR, AA = acrylic acid, amounts in % by weight) Amount of residual Initiator pH during M.sub.n M.sub.w monomer Experiment Monomers Type Amount Polymerization [g/mol] (g/mol) M.sub.w/M.sub.n [mol %] Example 2a 89% VME-23EO, 11% AA Azo 1.6 g 2.4 6348 34566 5.44 Example 2b 89% VME-23EO, 11% AA Azo 1.2 g 2.3 6137 41648 6.78 Example 2c 89% VME-23EO, 11% AA Azo 0.8 g 2.4 6591 42874 6.50 Comparative 89% HBVE-24EO, 11% AA Azo 1.6 g 2.4 1267 12459 9.83 example 2a Comparative 89% HBVE-24EO, 11% AA Azo 1.2 g 2.4 1141 4366 3.82 example 2b Comparative 89% HBVE-24EO, 11% AA Azo 0.8 g 2.5 1478 17994 12.20 example 2c Example 2d 85% VME-23EO, 11% AA Azo 1.6 g 8.1 4974 20834 4.18 0.0 Comparative 85% HBVE-24EO, 11% AA Azo 1.6 g 7.8 1928 9555 4.95 8.2 example 2d Example 2e 89% VME-24EO, 11% AA Peroxide 1.9 g 1.9 2629 7008 2.66 Comparative 89% HBVE-24 EO, 11% AA Peroxide 1.9 g 1.9 864 2701 3.12 example 2e Example 2f 89% VME-24EO, 11% AA Peroxide 3.2 g 14637 139210 9.51 n.d. Comparative 89% HBVE-24EO, 11% AA Peroxide 3.2 g 7727 13592 1.75 n.d. example 2f Example 2g 81% VME-67EO, 19% AA Azo 1.6 g 2.5 28707 140920 4.90 Comparative 81% HBVE-67 EO, 19% AA Azo 1.6 g 2.4 8605 37977 4.41 example 2g Example 2h 81% VME-135EO, 19% AA Azo 1.6 g 2.5 23495 159210 6.78 Comparative 81% HBVE-135 EO, 19% AA Azo 1.6 g 2.4 14976 56306 3.76 example 2h

Example 3

Preparation of Polymers, Method (B)

(121) In method (B), the VME or HBVE alkoxylates are not initially charged for the polymerization but added gradually during the polymerization.

Example 3a

(122) Copolymer of 89% by weight VME-23EO and 11% by weight acrylic acid (molar ratio 1:2)

(123) Polymerization at pH 2.8 (peroxide starter)

(124) 66 g of water, a portion (2.9 g) of solution A (35.6 g of VME-23EO according to Example 1b and 4.4 g of acrylic acid dissolved in 18 g of water) and a portion (1.9 g) of solution B (0.8 g (75% solution) of tert-butyl perpivalate and 36 g of isopropanol) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the polymerization started with addition of the remaining amounts of solutions A and B, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. Isopropanol was distilled off.

(125) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

Example 3b

(126) Copolymer of 89% by weight VME-23EO and 11% by weight acrylic acid

(127) Polymerization at pH 2.6 (azo starter)

(128) 66 g of water, a portion (2.9 g) of solution A (35.6 g of VME-23EO according to Example Ib, 4.4 g of acrylic acid dissolved in 18 g of water) and a portion (1.9 g) of solution B (1.6 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 168 g of water) and 36 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(129) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

Comparative Example 3a

(130) Copolymer of 86% by weight HBVE-24EO and 14% by weight Na acrylate

(131) Polymerization at pH 8.5 (peroxide starter)

(132) 288.7 g of water, a portion (14 g) of solution A (150.8 g of HBVE-24EO according to comparative example 1i, 80.6 g of 30% acrylic acid Na salt solution and 48.5 g of water) and a portion (6.7 g) of solution B (3.5 g (75% solution) of tert-butyl perpivalate and 131.2 g of isopropanol dissolved) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. The reaction mixture was maintained constantly at pH 7.5-8.0. Isopropanol was then distilled off.

(133) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

Comparative Example 3b

(134) Copolymer of 86% by weight HBVE-24EO and 14% by weight Na acrylate

(135) Polymerization at pH 2-3 (azo starter)

(136) 252 g of water, a portion (14 g) of solution A (150.8 g of HBVE-24EO according to Example 1i, 80.6 g of 30% acrylic acid Na salt solution and 48.5 g of water) and a portion (8.6 g) of solution B (3.5 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 168 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h. The reaction mixture was maintained constantly at pH 7.5-8.0.

(137) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

Example 3c

(138) Copolymer of 97% by weight VME-135EO and 3% by weight Na acrylate

(139) Polymerization at pH 9.4 (peroxide starter)

(140) 39.4 g of water, a portion (4.4 g) of solution A (36.4 g of VME-135EO according to Example 1 h, 3.7 g of 30% acrylic acid Na salt solution and 48 g of water) and a portion (1.16 g) of solution B (0.75 g (75% solution) of tert-butyl perpivalate and 22 g of isopropanol dissolved) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. Isopropanol was distilled off.

(141) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

Example 3d

(142) Copolymer of 97% by weight VME-135EO and 3% by weight Na acrylate

(143) Polymerization at pH 8.6 (azo starter)

(144) 45 g of water, a portion (4.4 g) of solution A (36.7 g of VME-135EO according to Example 1 h, 3.7 g of 30% acrylic acid Na salt solution and 48 g of water) and a portion (0.88 g) of solution B (0.75 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 17 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(145) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

Comparative Example 3c

(146) Copolymer of 94% by weight HBVE-135EO and 6% by weight Na acrylate

(147) Polymerization at pH 7.7 (peroxide starter)

(148) 238.7 g of water, a portion (14.0 g) of solution A (164.9 g of HBVE-135EO according to comparative example 1j, 33.7 g of 30% acrylic acid Na salt solution and 131.4 g of water) and a portion (6.7 g) of solution B (3.5 g (75% solution) of tert-butyl perpivalate and 131.2 g of isopropanol dissolved) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. The reaction mixture was maintained constantly at pH 7.5-8.0. Isopropanol was then distilled off.

(149) Data relating to the synthesis and also M.sub.n, M.sub.w and PDI of the resulting polymer are summarized in Table 2.

(150) TABLE-US-00002 TABLE 2 Results of the polymer syntheses (*amount of residual monomer by NMR, AA = acrylic acid or Na acrylate, amounts in % by weight) Unreacted Initiator pH during M.sub.n M.sub.w ethoxylate Experiment Monomers Type Amount Polymerization [g/mol (g/mol) M.sub.w/M.sub.n monomer [%]* Example 3a 89% VME-23EO, 11% AA Peroxide 1.9 g 2.8 27709 42697 1.54 0.0 Comparative 86% HBVE-24EO, 14% AA Peroxide 3.5 g 8.7 12238 15404 1.26 17 example 3a Example 3b 89% VME-23EO, 11% AA Azo 1.9 g 2.6 23197 37150 1.6 0.0 Comparative 86% HBVE-24EO, 14% AA Azo 8.6 g 8.5 18028 25349 1.41 50 example 3b Example 3c 97% VME-135EO, 3% AA Peroxide 0.75 g 9.4 15682 20930 1.33 0.0 Comparative 94% HBVE-135EO, 6% AA Peroxide 3.5 g 7.7 36819 39428 1.07 37 example 3c Example 3d 97% VME-135EO, 3% AA Azo 0.75 g 8.6 18776 29705 1.58 0

Example 4

Polymerization of VME Ethoxylates with Methacrylic Acid

(151) ##STR00020##

Example 4a

(152) Copolymer of 87% by weight VME-24EO and 13% by weight Na methacrylate

(153) Polymerization at pH 7.5-8.0 (azo starter), method (A)

(154) 57 g of water, 34.8 g of VME-24EO, a portion (1.4 g) of solution A (17.2 g of 30% methacrylic acid Na salt solution and 12 g of water) and a portion (2.0 g) of solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 38.4 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(155) The results are summarized in table 3.

Example 4b

(156) Copolymer of 82% by weight VME-23EO and 18% by weight Na methacrylate

(157) Polymerization at pH 7.5-8.0 (peroxide starter), method (A)

(158) 70 g of water, 33 g of VME-23EO, a portion (2.1 g) of solution A (24 g of 30% methacrylic acid Na salt solution and 20 g of water) and a portion (0.8 g) of solution B (1.6 g (75% solution) of tert-butyl perpivalate and 14.4 g of isopropanol) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. Isopropanol was distilled off.

(159) The results are summarized in table 3.

Example 4c

(160) Copolymer of 87% by weight VME-23EO and 13% by weight Na methacrylate

(161) Polymerization at pH 2.5-3.0 (peroxide starter), method (A)

(162) 70 g of water, 35 g of VME-23EO, a portion (2.0 g) of solution A (5.2 g of methacrylic acid dissolved in 36 g of water) and a portion (0.8 g) of solution B (1.6 g (75% solution) of tert-butyl perpivalate and 14.4 g of isopropanol) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. Isopropanol was distilled off.

(163) The results are summarized in table 3.

Example 4d

(164) Copolymer of 89% by weight VME-23EO and 11% by weight Na methacrylate

(165) Polymerization at pH 7.5-8.0 (azo starter), method (B)

(166) 66 g of water, a portion (2.9 g) of solution A (35.6 g of VME-23EO, 4.4 g of methacrylic acid dissolved in 18 g of water) and a portion (1.9 g) of solution B (1.6 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 36 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(167) The results are summarized in table 3.

Example 4e

(168) Copolymer of 89% by weight VME-23EO and 11% by weight Na methacrylate

(169) Polymerization at pH 7.5-8.0 (peroxide starter), method (B)

(170) 66 g of water, a portion (2.9 g) of solution A (35.6 g of VME-23EO, 4.4 g of methacrylic acid dissolved in 18 g of water) and a portion (1.9 g) of solution B (0.8 g (75% solution) of tert-butyl perpivalate and 36 g of isopropanol) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. Isopropanol was distilled off.

(171) The results are summarized in table 3.

Comparative Example 4f

(172) Copolymer of 87% by weight HBVE-23EO and 13% by weight Na methacrylate

(173) Polymerization at pH 7.5-8.0 (azo starter), method (A)

(174) ##STR00021##

(175) 57.6 g of water, 35 g of HBVE-24EO, a portion (1.5 g) of solution A (17 g of 30% methacrylic acid Na salt solution and 12 g of water) and a portion (2.0 g) of solution B (1.6 g of 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 38.4 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(176) The results are summarized in table 3.

Comparative Example 4g

(177) Copolymer of 87% by weight HBVE-23EO and 13% by weight Na methacrylate

(178) Polymerization at pH 7.5-8.0 (azo starter), method (B)

(179) 66 g of water, a portion (2.9 g) of solution A (35.6 g of VME-23EO, 4.4 g of methacrylic acid dissolved in 18 g of water) and a portion (1.9 g) of solution B (1.6 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (Wako VA-44) and 36 g of water) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 70 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 70 C. for 2 h.

(180) The results are summarized in table 3.

Example 4h

(181) Copolymer of 87% by weight VME-24EO and 13% by weight Na methacrylate

(182) Polymerization at pH 7.5-8.0 (peroxide starter)

(183) 66 g of water, a portion (2.9 g) of solution A (35.6 g of VME-23EO, 4.4 g of acrylic acid dissolved in 18 g of water) and a portion (1.9 g) of solution B (0.8 g (75% solution) of tert-butyl perpivalate and 36 g of isopropanol) were initially charged in a glass reactor equipped with stirrer, reflux condenser, thermometer, nitrogen line and addition lines. The initial charge was heated under nitrogen to 75 C. and the addition of the remaining amounts of solutions A and B was started, wherein solution A was added over 3 hours and solution B over 4 hours. The reaction mixture was then stirred at 75 C. for 2 h. Isopropanol was distilled off.

(184) The results are summarized in table 3.

(185) TABLE-US-00003 TABLE 3 Results of examples 4a-4h Temp. M.sub.n M.sub.w Unreacted No. Macromonomer Process Initiator [ C.] pH [g/mol) [g/mol) M.sub.w/M.sub.n macromonomer [%]* Example 4a VME-24EO (A) 4% W-VA44 70 8.3 24789 33344 1.34 Example 4b VME-24EO (A) 4% perpivalate 75 7.9 17980 41600 2.31 Example 4c VME-24EO (A) 4% perpivalate 75 2.4 43381 68891 1.59 Comparative HBVE-24EO (A) 4% W-VA44 70 7.8 18408 24217 1.32 example 4d Comparative HBVE-24EO (B) 4% perpivalate 75 8.8 17271 23080 1.34 ~75 example 4e Example 4f VME-24EO (B) 4% perpivalate 75 8.5 9054 20575 2.75 ~48 Comparative HBVE-24EO (B) 4% W-VA44 70 8.4 16875 24364 1.44 ~20 example 4g Example 4h VME-24EO (B) 4% W-VA44 70 8.6 7968 14725 1.85 ~6

Example 5

Copolymerization of VME Alkoxylates with HEMA and HPMA Phosphate Compared to HBVE Alkoxylates

Example 5a

Copolymer of 80% by Weight VME-67EO and 20% by Weight Hydroxyethyl Methacrylate Phosphate

(186) The experimental apparatus consists of 1000 ml jacketed reactor, thermostat, stirring motor with propeller stirrer, temperature sensor, pH probe and N.sub.2 inlet. 172.80 g of water and 103.38 g of VME-67 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated.

(187) At ca. 60 C., 25.94 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 137.12 g of water is added. A pH of ca. 1.0-1.5 is reached. Subsequently, 9.02 g of 50% NaOH are added thereto in order to establish a pH of ca. 3. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 1.32 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 13.2 g of water are then added. After a reaction time of 3 h, the reactor content is cooled to 25 C.

(188) The resulting yellowish slightly cloudy product has a pH of ca. 2.5 and a solids content of 30%. The mean molar mass of the polymer (Mw) is 29 000 g/mol. The polydispersity is 1.25. The conversion is ca. 75% of polymer (determination by GPC).

(189) The results are summarized in table 4.

Example 5b

Copolymer of 84% by Weight VME-135EO and 16% by Weight Hydroxyethyl Methacrylate Phosphate

(190) The same apparatus was used as for example 5a.

(191) 172.80 g of water and 106.38 g of VME-135 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 19.79 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 104.6 g of water is added. A pH of ca. 1.0-1.5 is reached. Subsequently, 7.05 g of 50% NaOH are added thereto in order to establish a pH of ca. 3. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 1.26 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 11.3 g of water are then added. After a reaction time of 3 h, the reactor content is cooled to 25 C.

(192) The results are summarized in table 4.

Beispiel 5c

Copolymer of 89% by Weight VME-135EO and 11% by Weight Hydroxyethyl Methacrylate Phosphate

(193) The same apparatus was used as for example 5a.

(194) 328.3 g of water and 202.12 g of VME-135 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 25.06 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 132.5 g of water are added. A pH of ca. 1.0-1.5 is reached. Subsequently, 8.90 g of 50% NaOH are added thereto in order to establish a pH of ca. 3. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 2.27 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 21.6 g of water are then added. After a reaction time of 3 h, the reactor content is cooled to 25 C.

(195) The results are summarized in table 4.

Example 5d

Copolymer of 92% by Weight VME-135EO and 8% by Weight Hydroxyethyl Methacrylate Phosphate

(196) The same apparatus was used as for example 5a.

(197) 328.3 g of water and 202.12 g of VME-135 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 16.71 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 88.31 g of water are added. A pH of ca. 1.0-1.5 is reached. Subsequently, 5.78 g of 50% NaOH are added thereto in order to establish a pH of ca. 3. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 2.19 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 21.6 g of water are then added.

(198) After a reaction time of 3 h, the reactor content is cooled to 25 C.

(199) The results are summarized in table 4.

Example 5e

Copolymer of 84% by Weight VME-10PO-125EO and 16% by Weight Hydroxyethyl Methacrylate Phosphate

(200) The same apparatus was used as for example 5a.

(201) 328.3 g of water and 202.12 g of VME-10PO-125 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 37.59 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 198.7 g of water are added. A pH of ca. 1.0-1.5 is reached. Subsequently, 13.45 g of 50% NaOH are added thereto in order to establish a pH of ca. 3. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 2.4 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 21.6 g of water are then added.

(202) After a reaction time of 3 h, the reactor content is cooled to 25 C.

(203) The results are summarized in table 4.

Example 5f

Copolymer of 84% by Weight VME-135EO and 16% by Weight Hydroxypropyl Methacrylate Phosphate

(204) The same apparatus was used as for example 5a.

(205) 328.3 g of water and 202.12 g of VME-135 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 38.81 g of hydroxypropyl methacrylate phosphate (HPMA-P) in 198.7 g of water are added. A pH of ca. 1.0-1.5 is reached.

(206) Subsequently, 11.5 g of 50% NaOH are added thereto in order to establish a pH of ca. 3. On addition of the HPMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 2.4 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 21.6 g of water are then added.

(207) After a reaction time of 3 h, the reactor content is cooled to 25 C.

(208) The results are summarized in table 4.

Example 5g

Copolymer of 98% by Weight VME-135EO and 2% by Weight Maleic Anhydride

(209) The same apparatus was used as for example 5a.

(210) 218.88 g of water and 134.75 g of VME-135 EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 2.67 g of maleic anhydride (MA) in 7.9 g of water are added. Subsequently, 2.68 g of 40% KOH are added thereto in order to establish a pH of ca. 3. On addition of the MA solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 1.37 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 12.37 g of water are then added.

(211) After a reaction time of 3 h, the reactor content is cooled to 25 C.

(212) The results are summarized in table 4.

Comparative Example 5a

Copolymer of 84% by Weight HBVE-135EO and 16% by Weight Hydroxyethyl Methacrylate Phosphate

(213) The same apparatus was used as for example 5a.

(214) 217.15 g of water and 133.68 g of HBVE-135EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 25.72 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 135.95 g of water are added. Subsequently, 9.13 g of 50% NaOH are added thereto in order to establish a pH of ca. 6.5. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 1.59 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 11.34 g of water are then added.

(215) After a reaction time of 3 h, the reactor content is cooled to 25 C.

(216) The results are summarized in table 4.

Comparative Example 5b

Copolymer of 89% by Weight HBVE-135EO and 11% by Weight Hydroxyethyl Methacrylate Phosphate

(217) The same apparatus was used as for example 5a.

(218) 217.15 g of water and 133.68 g of HBVE-135EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 17.15 g of hydroxyethyl methacrylate

(219) phosphate (HEMA-P) in 90.64 g of water are added. Subsequently, 9.5 g of 50% NaOH are added thereto in order to establish a pH of ca. 6.5. On addition of the HEMA-P solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 1.51 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 11.34 g of water are then added. After a reaction time of 3 h, the reactor content is cooled to 25 C.

(220) The results are summarized in table 4.

Comparative Example 5c

Copolymer of 98% by Weight HBVE-135EO and 2% by Weight Maleic Anhydride

(221) The same apparatus was used as for example 5a.

(222) 434.3 g of water and 267.37 g of HBVE-135EO are added to the reactor. N.sub.2 is then introduced and the oxygen displaced. The thermostat is set at T=75 C. and the reactor content is heated. At ca. 60 C., 5.48 g of maleic anhydride (MA) in 28.62 g of water are added. Subsequently, 5.3 g of 40% KOH are added thereto in order to establish a pH of ca. 6.5. On addition of the MA solution, the temperature falls down to 50 C. The reactor content is subsequently heated to 60 C. 2.73 g of Wako VA-044 (2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride) in 24.55 g of water are then added. After a reaction time of 3 h, the reactor content is cooled to 25 C.

(223) The results are summarized in table 4.

(224) TABLE-US-00004 TABLE 4 Results of examples 5a to 5g and comparative examples 5a to 5c (*conversion determined by GPC) Weight ratio macromonomer/ M.sub.n M.sub.w Solids content Conversion* Example Macromonomer comonomer [g/mol] [g/mol] PD [% by wt.] [%] Example 5a VME-67EO 80/20 (HEMA-P) 22100 27400 1.24 30 93 Example 5b VME-135EO 84/16 (HEMA-P) 19000 25600 1.35 33 78 Example 5c VME 135EO 89/11 (HEMA-P) 19900 27600 1.39 32 82 Example 5d VME-135EO 92/8 (HEMA-P) 50593 91007 1.79 33 70 Example 5e VME-10PO-125EO 84/16 (HEMA-P) 55000 80300 1.46 31 81 Example 5f VME-135EO 84/16 (HEMA-P) 17100 21900 1.28 31 74 Example 5g VME-135EO 98/2 (MSA) 19700 25400 1.29 37 62 Comparative HBVE-135EO 84/16 (HEMA-P) 32200 84600 2.63 31 6 example 5 a Comparative HBVE-135EO 89/11 (HEMA-P) 23900 34500 1.44 33 5 example 5 b Comparative HBVE-135EO 98/2 (MA) 37 0 example 5 c
Application Tests
Test Methods:

(225) Spread test using polycarboxylate ether plasticizer based on VME ethoxylate compared to HBVE ethoxylate.

(226) A mortar composed of 450 g of Heidelberg cement CEM I, 42.5 R, 1350 g of standard sand and 225 g of water (less the water to be added with the plasticizer) was prepared according to DIN EN 196-1. The plasticizer (between 0.1 and 0.3% by weight based on the cement) was added after 90 seconds during the mortar preparation, together with the antifoaming agent triisobutyl phosphate (7% by weight based on the dry weight of the plasticizer). After the addition, mixing was continued for 60 s. The mortar was then loaded into a conical metallic mold which was placed centrally on a jolting table at the origin of a rectangular coordinate system with two axes (units cm). Excess mortar was wiped off the upper edge and the mold lifted off such that a conical mortar cake remained on the spread table. After 15 strokes (upward strokes) by means of the jolting table, the diameter of the cake was determined along the axes. The greater the diameter of the mortar cake, the better the flow properties of the mortar. The measurement was repeated with the same mortar sample after 30, 60 and 90 minutes. The temperature was 23+/1 C.

(227) The polymers used in each case, amount thereof and test results are summarized in Table 5.

(228) TABLE-US-00005 TABLE 5 Results of the performance tests Amount of Polymer Diameter after x min. relative [cm] Polymer pH during M.sub.n M.sub.w to cement 1 30 60 90 No. Process No. Type of polymer polymerization [g/mol] [g/mol] M.sub.w/M.sub.n [% by wt.] min. min. min. min. V1 (A) Blank sample without polymer 17.65 15.7 14.95 13.35 V2 (A) V2a 89% HBVE-24EO, 11% AA 2-3 1267 12459 9.83 0.12 19.55 17.2 15.4 15.4 V3 (A) V2b 89% HBVE-24EO, 11% AA 2-3 1141 4366 3.82 0.12 19.3 17.5 16.8 14.85 V4 (A) V2c 89% HBVE-24EO, 11% AA 2-3 1478 17994 12.2 0.12 19.55 17.6 16.75 15.7 1 (A) 2a 89% VME-23EO, 11% AA 2-3 6348 34566 5.44 0.12 20.7 18.55 16.75 15.9 2 (A) 2b 89% VME-23EO, 11% AA 2-3 6137 41648 6.78 0.12 21.15 18.25 17.2 16.45 3 (A) 2c 89% VME-23EO, 11% AA 2-3 6591 42874 6.5 0.12 21.05 18.35 16.85 16.25 V5 (A) V2c 89% HBVE-24EO, 11% AA 2-3 1478 17994 12.2 0.24 21.1 19.45 18.4 16.3 4 (A) 2b 89% VME-23EO, 11% AA 2-3 6137 41648 6.78 0.24 26 22.2 19.6 18.35 5 (A) 2d 85% VME-23EO, 11% AA 2-3 4974 20834 4.18 0.115 20.55 18.35 17.55 16.65 6 (A) 2d 85% VME-23EO, 11% AA 7-8 4974 20834 4.18 0.23 23.15 19.45 18.4 17.5 7 (B) 3a 89% VME-23EO, 11% AA 2-3 27709 42697 2.7 0.1 29.3 24.9 22.25 21.3 8 (B) V3a 86% HBVE-24EO, 14% AA 8-9 12238 15404 1.26 0.12 21.1 18.7 17.5 16.25 V6 (B) V3b 86% HBVE-24EO, 14% AA 7-9 18028 25349 1.41 0.12 22.5 19.1 17.3 16.6 9 (B) 3b 89% VME-23EO, 11% AA 2-3 23197 37150 2.7 0.1 28.05 23.15 22.25 19.55 10 (B) 3c 97% VME-135EO, 3% AA 8-10 15682 20930 1.33 0.11 19.2 16.8 15.65 15.15 11 (B) V3c 94% HBVE-135EO, 6% AA 7-9 36819 39428 1.07 0.11 19.3 16.9 16 15 12 (B) 3d 97% VME-135EO, 3% AA 8-10 18776 29705 1.58 0.11 19 16.95 15.95 15.1 13 (A) 4a VME-24EO, MAS 8-9 24789 33344 1.34 0.11 21.7 18.45 17.95 17.65 14 (A) 4b VME-24EO, MAS 8-9 17980 41600 2.31 0.11 27.3 21.85 18.60 16.45 15 (A) 4c VME-24EO, MAS 2-3 43381 68891 1.59 0.11 21.35 18.35 17.55 16.25 V7 (A) V4d HBVE-24EO, MAS 7.8 18408 24217 1.32 0.11 19.7 18 17 16.25 V8 (B) HBVE-24EO, MAS 8-9 14585 19709 1.35 0.11 19.5 17.2 16.65 16.35 16 (B) VME-24EO, MAS 8-9 27877 40371 1.45 0.11 21.85 18.75 17.6 16.85 V9 (B) V4e HBVE-24EO, MAS 8-9 17271 23080 1.34 0.11 20.35 17.8 16.55 15.45 16 (B) 4f VME-24EO, MAS 8-9 9054 20575 2.75 0.11 20.95 17.70 16.75 15.80 V10 (B) V4g HBVE-24EO, MAS 8-9 16875 24364 1.44 0.11 20.45 17.60 16.70 16.00 17 (B) 4h VME-24EO, MAS 8-9 7968 14725 1.85 0.11 20.15 17.50 16.30 15.85
Comments on the Performance Experiments

(229) The examples in the table show that the experiments using the VME ethoxylates have a better effect with respect to the mortar plastification than the HBVE-based experiments.

(230) In the blank experiment, the diameter of the mortar cake after 1 min was 17.65 cm. The addition of 0.12% of an HBVE-based plasticizer (comparative example V2) leads after 1 min to a mortar cake diameter of 19.55 cm. With the corresponding VME-based product (example 2), 21.15 cm are reached. The VME-based product is also better on doubling the concentration; 26 cm (experiment 4) are achieved with the VME-based product and only 21.1 cm with the HBVE-based product.

(231) The experiments also show that better performance results are achieved with polymers prepared according to method (B) than with polymers prepared according to method (A): At an amount of 0.12% by weight, the best experiment with a VME-based product prepared according to method (A) gave 21.15 cm. In experiments 7 and 9, ca. 28 to 29 cm were achieved with a VME-based product prepared according to method (B) even though the amount of polymer, at 0.1% by weight, was lower than in experiment 2 (0.12% by weight).

(232) Although we do not wish to be committed to a theory, it seems that the effect is due to the fact that the compounds (I) relatively easily self-polymerize due to their relatively high reactivity. Since the compounds (I) are initially charged in method (A) and the comonomers are added gradually, the formation of block structures is favored. Method (B), in which both monomers are added gradually, seems to lead to a more uniform incorporation of the VME monomers into the copolymer. A significantly better effect as concrete plasticizer can evidently thereby be achieved.