Polymers containing S-vinylthio alkanols

Abstract

Process for preparing polymers comprising S-vinylthioalkanol as monomer by radical polymerization, the polymerization being carried out in aqueous solution, with the proviso that no N-vinylpyrrolidone as monomer is used for preparing the polymers, and also polymers prepared by such processes. Copolymer consisting of S-vinyl-2-thioethan-1-ol and one or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid, itaconic acid, maleic acid, maleic anhydride, and vinylphosphonic acid. Mixtures, preferably aqueous compositions, comprising polymers or copolymers. Use of polymers, copolymers, or aqueous compositions as concrete plasticizers, wetting agents, in cosmetics, as adhesive constituent, in emulsion polymerization, for metal surface treatment, in coatings applications, in paints, in laundry detergents, in washing detergents, as encapsulating material or as enveloping material.

Claims

1. A polymer containing S-vinyl-2-thioethan-1-ol and acrylic acid wherein no further monomers are used.

2. The polymer according to claim 1, wherein from 1 to 99 mol % of S-vinyl-2-thioethan-1-ol and from 99 to 1 mol % of acrylic acid is used, based on the total amount of monomers.

Description

EXAMPLES

(1) Measurement Methods:

(2) K Values:

(3) The K values were measured in accordance with H. Fikentscher, Cellulose-Chemie, vol. 13, pages 58 to 64 and 71 to 74 (1932) in 1 weight % strength aqueous or methanolic solution at 25 C.

(4) GPC Measurement:

(5) The GPC measurements were conducted in N,N-dimethylacetamide (DMAC) with polymethyl methacrylate (PMMA) (molecular weight distribution of from M=800 to M=1 820 000) as standard. Columns used:

(6) TABLE-US-00001 Columns Diameter Length Separation Cutoff point mm cm material g/mol Designation 8 5 Polyester GRAM preliminary copolymer column 8 30 Polyester 100-10 000 GRAM 30 A copolymer 8 30 Polyester 1000-1 000 000 GRAM 1000 A copolymer 8 30 Polyester 1000-1 000 000 GRAM 1000 A copolymer

Example 1: Preparation of S-vinyl-2-thioethan-1-ol/acrylic acid copolymer (ratio 50 mol/50 mol)

(7) A reactor vessel provided with stirrer, temperature monitoring, nitrogen inlet, and a number of feed ports was charged with 58.0 g of deionized water, 1.3 g of feed 1, 1.2 g of feed 2, and 1.1 g of feed 3.

(8) Feed 1: 26 g of S-vinyl-2-thioethan-1-ol.

(9) Feed 2: 18 g of acrylic acid and 6 g of deionized water.

(10) Feed 3: 1.32 g of azo initiator (2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, Wako VA-044) and 20 g of deionized water.

(11) The initial charge was gassed with nitrogen for 15 minutes and heated to 70 C. under a nitrogen atmosphere. Then the remainder of feed 1 and of feed 2 was added dropwise over the course of 3 hours, and the remainder of feed 3 over the course of 4 hours.

(12) This was followed by stirring at 70 C. for 2 hours. The result was a pale yellow, clear polymer solution having a solids content of 29.8% and a K value of 23.2 (1% in methanol).

(13) GPC gave an Mn of 3348 g/mol, an Mw of 6026 g/mol, and PDI (Mw/Mn) of 1.8 (calibration plot for PMMA).

(14) Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol were detectable by .sup.1H NMR spectroscopy. In order to detect potential hydrolysis products, .sup.1H NMR standard-addition tests were additionally conducted with 2-thioethan-1-ol and also with ethylene glycol.

(15) The upper critical solution temperature (UCST) of the copolymer in water was about 50 C.

Example 2: Preparation of S-vinyl-2-thioethan-1-ol/acrylic acid copolymer (ratio 40 mol/60 mol)

(16) A reactor vessel provided with stirrer, temperature monitoring, nitrogen inlet, and a number of feed ports was charged with 63.8 g of deionized water, 1.5 g of feed 1, 2.5 g of feed 2, and 1.6 g of feed 3.

(17) Feed 1: 29.2 g of S-vinyl-2-thioethan-1-ol.

(18) Feed 2: 30.3 g of acrylic acid and 20.0 g of deionized water.

(19) Feed 3: 1.8 g of Wako VA-044 and 30 g of deionized water.

(20) The initial charge was gassed with nitrogen for 15 minutes and heated to 70 C. under a nitrogen atmosphere. Than the remainder of feed 1 and of feed 2 was added dropwise over the course of 3 hours, and the remainder of feed 3 over the course of 4 hours.

(21) This was followed by stirring at 70 C. for 2 hours. The result was a pale yellow, clear polymer solution having a solids content of 27.6% and a K value of 24.7 (1% in methanol).

(22) Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol were detectable by .sup.1H NMR spectroscopy. In order to detect potential hydrolysis products, .sup.1H NMR standard-addition tests were additionally conducted with 2-thioethan-1-ol and also with ethylene glycol.

(23) The upper critical solution temperature (UCST) of the copolymer in water was about 37 C.

Example 3: Preparation of S-vinyl-2-thioethan-1-ol Homopolymer

(24) A reactor vessel provided with stirrer, temperature monitoring, nitrogen inlet, and a number of feed ports was charged with 29.8 g of deionized water, 30.0 g of ethanol, 2.0 g of feed 1 and 1.1 g of feed 2.

(25) Feed 1: 41.7 g of S-vinyl-2-thioethan-1-ol.

(26) Feed 2: 1.25 g of Wako VA-044 and 20 g of deionized water.

(27) Feed 3: 0.83 g of Wako VA-044 and 13.33 g of water.

(28) The initial charge was gassed with nitrogen for 15 minutes and heated to 70 C. under a nitrogen atmosphere. Then the remainder of feed 1 was added dropwise over the course of 3 hours, and the remainder of feed 2 over the course of 4 hours. This was followed by stirring at 70 C. for 2 hours. Subsequently feed 3 was added dropwise over the course of 45 minutes and stirring took place at 70 C. for 2 hours.

(29) The result was a pale yellow, clear polymer solution having a solids content of 28.3% and a K value of 23.3 (1% in methanol).

(30) The residual monomer content was about 2 mol %, based on the total amount of monomer employed. GPC gave an Mn of 6718 g/mol, an Mw of 16 680 g/mol, and PDI 2.5 (calibration plot for PMMA).

Example 4: Preparation of S-vinyl-2-thioethan-1-ol/acrylic acid copolymer (ratio 10 mol/90 mol)

(31) A reactor vessel provided with stirrer, temperature monitoring, nitrogen inlet, and a number of feed ports was charged with 73.6 g of deionized water, 6.0 g of feed 1 and 2.25 g of feed 2.

(32) Feed 1: 77.82 g of acrylic acid, 12.50 g of S-vinyl-2-thioethan-1-ol, and 30.0 g of deionized water.

(33) Feed 2: 5.42 g of azo initiator (2,2-azobis(2-methylpropionamidine) dihydrochloride, Wako V-50) and 40.0 g of deionized water.

(34) The initial charge was gassed with nitrogen for 15 minutes and heated to 88 C. under a nitrogen atmosphere. Then the remainder of feed 1 was added dropwise over the course of 3 hours, and the remainder of feed 2 over the course of 4 hours. This was followed by stirring at 88 C. for 2 hours.

(35) The result was a pale yellow, clear polymer solution having a solids content of 40.6% and a K value of 12.7 (1% in water).

(36) Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol were detectable by .sup.1H NMR spectroscopy. In order to detect potential hydrolysis products, .sup.1H NMR standard-addition tests were additionally conducted with 2-thioethan-1-ol and also with ethylene glycol.

Example 5: Preparation of S-vinyl-2-thioethan-1-ol/acrylic acid copolymer (ratio 20 mol/80 mol)

(37) A reactor vessel provided with stirrer, temperature monitoring, nitrogen inlet, and a number of feed ports was charged with 79.75 g of deionized water, 6.2 g of feed 1 and 2.3 g of feed 2.

(38) Feed 1: 69.18 g of acrylic acid, 25.0 g of S-vinyl-2-thioethan-1-ol, and 30.0 g of deionized water.

(39) Feed 2: 5.65 g of Wako V-50 and 40.0 g of deionized water.

(40) The initial charge was gassed with nitrogen for 15 minutes and heated to 88 C. under a nitrogen atmosphere. Then the remainder of feed 1 was added dropwise over the course of 3 hours, and the remainder of feed 2 over the course of 4 hours. This was followed by stirring at 88 C. for 2 hours.

(41) The result was a pale yellow, clear polymer solution having a solids content of 39.2% and a K value of 10.5 (1% in water).

(42) Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol were detectable by .sup.1H NMR spectroscopy. In order to detect potential hydrolysis products, .sup.1H NMR standard-addition tests were additionally conducted with 2-thioethan-1-ol and also with ethylene glycol.

Example 6: Preparation of S-vinyl-2-thioethan-1-ol/acrylic acid/itaconic acid/vinylphosphonic acid copolymer (ratio 5 mol/55 mol/30 mol/10 mol)

(43) A reactor vessel provided with stirrer, temperature monitoring, nitrogen inlet, and a number of feed ports was charged with 42.67 g of deionized water, 9.32 g of vinylphosphonic acid (95% strength), and 32.0 g of itaconic acid. The initial charge was gassed with nitrogen for 15 minutes and heated to 98 C. under a nitrogen atmosphere. Then 32.5 g of acrylic acid, 4.3 g of S-vinyl-2-thioethan-1-ol, and 30.0 g of deionized water were added dropwise over the course of 5 hours, and 3.1 g of Wako V-50 and 48.0 g of deionized water over the course of 6 hours. This was followed by stirring at 98 C. for 2 hours.

(44) This gave a clear yellow polymer solution having a solids content of 39.9% and a K value of 13.0 (1% in water). 2.9 mol % of vinylphosphonic acid, based on the total amount of vinylphosphonic acid employed, was detectable in the .sup.1H and .sup.31P NMR spectrum.

Example 7: Application Examples

(45) The copolymers from examples 4 and 5 were used for coating test panels of hot-dip-galvanized steel (Gardobond OE HDG 3; 105190 m).

(46) As a pretreatment, the test panels were immersed for 30 seconds in a mildly alkaline cleaning agent solution (Surtech 133 from Surtech) and then rinsed off immediately with fully demineralized water and subsequently dried using nitrogen. The clean panels were immersed for 1 second in a 25 weight % strength aqueous solution of the copolymer, squeezed off with a system of rollers, and dried in a forced-air drying cabinet at 160 C. for 12 seconds. In the course of this operation, the peak metal temperature (PMT) did not exceed 50 C.

(47) The resulting test panels were investigated for their corrosion resistance in a DIN EN ISO 9227 salt spray test.

(48) TABLE-US-00002 Polymer corroded area after salt spray test: No coating 100% (fully corroded) AA/S-Vinyl-2-thioethan-1-ol 90/10 about 30% AA/S-Vinyl-2-thioethan-1-ol 80/20 about 10%

(49) The data demonstrate the passivating effect through the copolymers of the invention.