DETERGENT POLYMER AND COMPOSITION
20220010239 · 2022-01-13
Inventors
- Frédéric BRUYNEEL (Monza MB, IT)
- Fabio COSTINITI (Vigodarzere PD, IT)
- Diego BOSCARDIN (Barlassina MB, IT)
- Eric KOAY (Gerenzano VA, IT)
- Ruggero SALA (Parabiago MI, IT)
Cpc classification
C08G73/0605
CHEMISTRY; METALLURGY
International classification
C08G73/10
CHEMISTRY; METALLURGY
Abstract
The present invention refers to a novel polymer that possesses metal ion removal properties, compositions comprising it, its use in cleaning application and the process for its manufacture. The present invention also relates to an improved the process for the manufacturing of known polymer as well, and the use of these known polymers in cleaning applications.
Claims
1. An aspartic acid/N-hydroxyaspartamide/succinimide polymer and/or its salts, wherein said polymer comprises non-hydrolyzed succinimide units.
2. The polymer according to claim 1, wherein said succinimide units are comprised in the range of 10% to 90% with respect to the total number of repeat units in the polymer.
3. The polymer according to claim 1 of any of Formula I ##STR00002## wherein repeat units are randomly bonded in said polymer.
4. The polymer according to claim 1, wherein its molecular weight is comprised in the range of 400 to 5000 Da
5. A detergent composition characterized in that it comprises the polymer according to claim 1 and suitable excipients.
6. The detergent composition according to claim 5, characterized in that it comprises said polymer in an amount comprised in the range from 0.1% to 3% weight/weight (w/w) with respect to the total weight of the composition
7. Method of domestic or industrial cleaning with the polymer according to claim 1, said method comprising removing stains or spots in domestic or industrial laundry and dishwashing cleaning with said polymer, wherein said polymer chelates ions from transitional metals.
8. A process for the synthesis of the polymer according to claim 1 comprising the following steps: a) providing a solution of a salt of hydroxylamine; b) adding poly-succinimide to said solution of step a), whereby allowing the reaction of said poly-succinimmide with said salt of hydroxylamine; and c) adding basic reagents, in sub-stoichiometric amount with respect to the initial amount of succinimide units found in the poly-succinimide, in one step or in more than one step after addition of said poly-succinimide in step b) is over; wherein said process is carried out by controlling the ring opening of said poly-succinimide so that said polymer resulting from step c) comprises non-hydrolyzed succinimide units.
9. The process according to claim 8, wherein said addition of basic reagent of step c) is carried out a temperature comprised in the range of 20° C. to 80° C. for a time comprised in the range of 0.5 to 3 hours.
10. The process according to claim 8, wherein after said addition of basic reagent, the reaction mixture is further kept at a temperature comprised in the range of 20° C. to 80° C. for a time comprised in the range of 0.5 to 3 hours.
11. The process according to claim 8, wherein the molecular weight of said poly-succinimide added in step b) is comprised in the range of 1 to 50 KDa
12. The process according to claim 8, having a molar ratio of hydroxylamine/succinimide repeat units of the starting poly-succinimide of 0.2/1
13. A process for the preparation of an aspartic acid/N-hydroxyaspartamide/succinimide derived polymer and/or its salts, comprising the following steps: a′) providing a solution of a salt of hydroxylamine; b′) adding poly-succinimide to said solution of step a′), whereby allowing the reaction of said poly-succinimmide with said salt of hydroxylamine; and c′) adding basic reagents in one step or in more than one step after addition of said poly-succinimide in step b′) is over; wherein said process is carried out by controlling the ring opening of said poly-succinimide so that said polymer resulting from step c′) does not comprise non-hydrolyzed succinimide units.
14. The process according to claim 13, wherein basic reagents of step c′) are added in at least three steps and/or are added in a stoichiometric amount or more than stoichiometric amount with respect to the initial amount of succinimide units found in the poly-succinimide.
15. A polymer obtainable according to claim 14.
16. Method of domestic or industrial cleaning with the polymer according to claim 15, said method comprising removing stains or spots in domestic or industrial laundry and dishwashing cleaning with said polymer, wherein said polymer chelates ions from transitional metals.
Description
DESCRIPTION OF THE FIGURES
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EXPERIMENTAL SECTION
[0081] Unless otherwise specified, the molecular weight of the present invention are determined by gel permeation chromatography (GPC) using calibration made with standard samples of poly-acrylates sodium salts (PaaNa) of known molecular weight (1 KDa to 30 KDa). GPC was carried out with Agilent Infinity II 1260 using 2 columns (in series) PL aquagel-OH 20 8 μm 7.5×300 mm, using a mobile phase made of Buffer phosphate at pH 7.2 and a flow set at 1 mL/min, and a refractive index (RI) detector. All sample were first diluted to 0.5 wt % and filtered on 0.2 μm. The molecular weight of starting material poly-succinimide was determined by carrying out a GPC analysis slurrying 1.0 g samples of the product with 1.0 g of water and dissolved in 0.9 g 40% aqueous NaOH to give clear light tan solutions of sodium poly-aspartate.
Example 1
[0082] Synthesis of the Polymer of the Invention
Example 1.1
[0083] Synthesis of the Polymer of the Invention in Solid Form
[0084] 1.8 Kg of water are introduced into a stirred vessel with a capacity of 5 L and heated to 40° C. 0.24 Kg of solid hydroxylammonium sulfate salts (purity >95%) are added in one portion and the mixture is stirred for 15 min until a homogeneous solution is formed. 1.5 Kg of commercial poly-succinimide having a determined MW of 6.1 KDa is added portion wise to the stirred vessel to produce a steerable suspension. 0.358 Kg of 47% strength aqueous potassium hydroxide solution are metered into this suspension at a temperature not exceeding 45° C. during 2 hours. The mixture is then stirred at 40° C. for 1 hour. Then 0.36 Kg of 47% strength aqueous sodium hydroxide solution are metered into this suspension at a temperature not exceeding 40° C. during 2 hours. Then, after 1 additional hour, 0.001 Kg of 30% strength aqueous hydrogen peroxide solution is added as final bleaching step for 1 hours. The temperature is then decreased to 30° C. The amount of sodium hydroxide solution added is 40 mole % with respect to the initial amount of succinimide units found in the poly-succinimide. The suspension is then filtered using a lab scale centrifuge (Rousselet Robatel, type RA 20VxR, serial nbr 25102), running at 200 rpm and equipped with polypropylene filter basket of 120 mm mesh. The solid recovered is further air dried, providing 1.1 Kg of a light orange powder corresponding to more than 70% recovery yield. Molecular weight of the final polymer in around 2.5 KDa.
Example 1.2
[0085] Synthesis of the Polymer of the Invention in Liquid Form 0.79 Kg of water are introduced into a stirred vessel with a capacity of 2 L and heated to 40° C. 0.08 Kg of solid hydroxylammonium sulfate salts (purity >95%) are added in one portion and the mixture is stirred for 15 min until a homogeneous solution is formed. 0.48 Kg of commercial poly-succinimide having a determined MW of 5.3 KDa was added portion wise to the stirred vessel to produce a steerable suspension. 0.079 Kg of 49% strength aqueous sodium hydroxide solution are metered into this suspension at a temperature not exceeding 60° C. during 30 min. The mixture is then stirred at 60° C. for 3 hours. Then 0.4 Kg of 49% strength aqueous sodium hydroxide solution are metered into the suspension at a temperature not exceeding 70° C. during 1 hour. Then, after 1 hour, 0.2 Kg of 49% strength aqueous sodium hydroxide solution are added over the course of 1 hour, and the reaction mixture is stirred at 60° C. for 1 hour. The temperature is then decreased to 30° C. and 0.003 Kg of a 30% strength aqueous hydrogen peroxide solution is added as final bleaching step. The amount of sodium hydroxide solution added is 180 mole % with respect to the initial amount of succinimide units found in the poly-succinimide. The solution has a pH of 10 and a solid content of 42% by weight (determined by drying at 125° C. using thermobalance). The polymer has a MW of 2.2 KDa.
Example 1.3
[0086] Synthesis of the Polymer of the Invention in Liquid Form
[0087] The liquid product of Example 1.2 is introduced into a stirred vessel with a capacity of 2 L and heated to 70° C. 0.2 kg of 49% strength aqueous sodium hydroxide solution are added over the course of 1 hour, and the reaction mixture is stirred at 60° C. before being cooled down again to 30° C. The solution has a pH of 11 and a solid content of 38% by weight (determined by drying at 125° C. using thermobalance). The polymer has a MW of 1.1 KDa. The polymer product of the present example has been found having improved biodegradability properties.
Example 1.4
[0088] Synthesis of the Polymer Invention in Liquid Form—Industrial Pilot Scale
[0089] 350 Kg of water are introduced into a stirred vessel with a capacity of 1000 L and heated to 40° C. 41 kg of solid hydroxylammonium sulfate salts (purity >95%) are added in 2 portions and the mixture is stirred for 15 min until a homogeneous solution is formed. 238 Kg of commercial poly-succinimide having a determined MW of 5.3 KDa is added portion wise to the stirred vessel to produce a steerable suspension. 40 Kg of 49% strength aqueous sodium hydroxide solution are metered into this suspension at a temperature not exceeding 60° C. over 30 min. The mixture is then stirred at 60° C. for 2 hours. Then 198 Kg of 49% strength aqueous sodium hydroxide solution are metered into the suspension at a temperature not exceeding 65° C. over 1 hour. Then, after 1 hour, 125 kg of 49% strength aqueous sodium hydroxide solution are added over the course of 1 hour, and the reaction mixture is stirred at 60° C. for 1 hour. Then and 2 Kg of a 30% strength aqueous hydrogen peroxide solution are added as final bleaching step before letting the product cool down to 30° C. The amount of sodium hydroxide solution added is 182 mole % with respect to the initial amount of succinimide units found in the poly-succinimide. The solution has a pH of 12, a solid content of 43% by weight, and a density of 1.3 g/mL. The polymer has a MW of 1.16 KDa. The pH was further adjusted to 10 by diluting with 54 Kg of a 50% strength aqueous sulfuric acid. The solid content was increased to 46 wt % (determined by drying at 125° C. using thermobalance).
Example 1.5
[0090] Synthesis of the Polymer of the Invention in Liquid Form
[0091] 0.3 Kg of water are introduced into a stirred vessel with a capacity of 1 L and heated to 40° C. 0.25 Kg of commercial poly-succinimide having a determined MW of 6.1 KDa is added portion wise to the stirred vessel to produce a steerable suspension. 0.035 Kg of solid hydroxylammonium chloride (purity >95%) are dissolved into 0.15 Kg of water, neutralised by addition of 0.05 Kg of a 50% strength aqueous sodium hydroxide solution, and are metered in the mixture. The mixture is stirred at 40° C. for 3 hours. 0.16 Kg of 50% strength aqueous sodium hydroxide solution are metered into this suspension again at a temperature not exceeding 45° C. over 30 min. The mixture is then stirred at 45° C. for 2 hours. The temperature is then decreased to 30° C. and 0.0165 Kg of a 30% strength aqueous hydrogen peroxide solution is added as final bleaching step. The amount of sodium hydroxide solution added is 99 mole % with respect to the initial amount of succinimide units found in the poly-succinimide. The Solution has a pH of 8 and a solid content of about 40% by weight (determined by drying at 125° C. using thermobalance). The polymer has a MW of 2.3 KDa.
Example 1.6
[0092] Synthesis of the Polymer Invention in Liquid Form—No Bleaching Step
[0093] The same reaction as for Example 1.5 is conducted without the final bleaching step. The solution has a pH of 8.8 and a solid content of about 40% by weight; determined by drying at 125° C. using thermobalance). The polymer Has a MW of 2.35 KDa.
Example 2
[0094] .sup.13C-NMR Spectroscopic Analysis
[0095] An analysis carried out to the polymer obtained in Example 1.5 above provided the following results
[0096]
[0097] .sup.13C-NMR (H2O/D2O):181 to 177 ppm (C═O β-peptide) and (C═O α-peptide), 176 to 172 ppm (CONH β-peptide) and (CONH α-peptide), 165 and 164 ppm (hydroxamate β-peptide) and (hydroxamate α-peptide) 51.38 ppm (C(α).β.-peptide), 39 ppm (C(β),α-peptide), 37.69 (C(β), β-peptide).
[0098] The assignment of the relevant signals was carried out in accordance with Makromol. Chem. 194, 1095 (1993).
Example 3
Application Examples
Example 3.1
[0099] Removal of Fe.sup.3+ (Modified Hampshire Test)
[0100] The principle of the modified Hampshire test is as follows: it is a titration analysis where the complexing agent (e.g. the polymer of the invention or comparative builders) is added to water at pH 10-11, and then a solution of FeCl.sub.3 is added to the same water. When the complexing capacity of the complexing agent is exhausted, a brown precipitation of Fe(OH).sub.3 can be observed. The test runs at room temperature. Test procedure (at room temperature) is as follows: dilute 0.80 g (±0.01 g) of complexing agent (the ones cited on Table 1) in 750 ml of distilled water in a beaker. Adjust pH between 10 and 11 by adding NaOH or HCl as required. Add stepwise a 0.25 M solution of FeCl.sub.3 until the beaker content becomes turbid (i.e. until Fe(OH).sub.3 precipitates) and record the volume of FeCl.sub.3 solution used (titration volume). During FeCl.sub.3 addition, keep pH between 10 and 11 by adding stepwise a solution of NaOH. After the precipitation, control pH and fill up with distilled water to 800 ml. To determine the exact titration volume, make additional tests, in different beakers, repeating the steps above but adding smaller amounts of the solution of FeCl.sub.3 starting from the titration volume previously determined (approximately: first titration volume minus 2 ml, 4 ml, 6 ml, etc.). After 3 hours, observe the beaker content. Record the titration volume of the beaker in which the first traces of brown precipitation can be observed: these ml minus 2 ml is the titration volume.
[0101] Calculation of Fe(III) chelation is done as follows:
TABLE-US-00001 TABLE 1 Complexing Agent Fe.sup.3+ chelation (mg/g) Sodium polyaspartate (P-free 200 (comparative)) HEDP (containing 1250 phosphorous (comparative)) Polymer of the invention 950
[0102] The polymer of the invention used for the present example is the one prepared according to Example 1.1 above
[0103] HEDP (etidronic acid) is a known phosphorus based additive in cleaning. Sodium polyaspartate (PASP) is a known P-free and biodegradable builder and co-builder.
[0104] Results of the present example show that the polymer of the invention is able to chelate an amount of Fe.sup.3+ almost 10 times higher compared to sodium polyaspartate, a known and widely used P-free builder. Moreover, the polymer of the invention provides comparable chelating properties with respect to HEPD, which is a known phosphorous-based chelating agents, i.e. the most effective chelating agents known in cleaning applications, yet not biodegradable. Therefore, the polymer of the invention possesses surprising chelating properties, comparable to those of phosphorous-based chelating agents according to the prior art, and, contrary to the latter, are also biodegradable and thus environmentally friendly.
[0105] Stain Removal Tests (Examples 3.2 and 3.3)
[0106] As the following examples will show, the polymer of the invention is versatile across several cleaning applications, especially in every domestic and industrial cleaning applications (i.e. laundry and dishwashing), and with several types of stains and spots.
[0107] Indeed, the polymer of the invention, when included in detergent compositions, provides effective stain removal in laundry applications in several types of stains (as it can be seen on Example 3.2) and effective spot and film prevention in dishwashing applications (as it can be seen on Example 3.3). Such effective stain removal and spot and film prevention is comparable, or often improved, with respect to known P-free builders and phosphorous-based builders, as it can be seen from Examples 3.2 and 3.3.
Example 3.2
[0108] Laundry Washing Tests
[0109] The laundry application test of the present example compares the laundry washing properties of four detergent compositions having the same base (shown on Table 2) and different co-builders in the same amounts (shown on Table 3).
TABLE-US-00002 TABLE 2 Chemical name, trade name Function % (w/w) LAS (Linear Sodium Alkyl Anionic Surfactant 8.8 Benezene Sulfonate) Ethoxylated Fatty Alcohol Non ionic surfactant 4.7 C12-18 (7EO) Sodium soap Anionic Surfactant 3.2 Sodium aluminium silicate Builder 28.3 zeolite 4A Sodium carbonate Builder/Alkali 11.6 Na Percarbonate Bleach 15.0 TAED Bleach Activator 1.5 (tetraacetylethylenediamine) Sodium salt of a co-polymer of Co-builder 3.0 acrylic and maleic acid Protease Enzyme (Protease) 0.4 Sodium silicate Builder 3.0 Carboxymethylcellulose Anti-redeposition 1.2 Sulphate Filler q.s. / Total 99.4
TABLE-US-00003 TABLE 3 % as active in Name detergent composition EDTMPA Na.sup.+ salt + HEDP 0.5 + 0.1 Na.sup.+ salt (comparative) DTMPA Na.sup.+ salt + HEDP Na.sup.+ 0.5 + 0.1 salt (comparative) EDDS (comparative) 0.6 Polymer of the invention 0.6
[0110] The polymer of the invention used for the present example is the one prepared in Example 1.1 above.
[0111] EDTMPA (ethylenediamine tetra (methylene phosphonic acid)) Na.sup.+ salt+HEDP (1-hydorxyethylidene (1,1-diphosphonic acid)) Na.sup.+ salt (comparative) and DTMPA (diethylenetriamine penta (methylene Phosphonic acid) Na.sup.+ salt+HEDP Na.sup.+ salt (comparative) contain phosphate and are standard and known phosphonate mixtures comprised in European powder detergent compositions. EDDS (ethylenediaminedisuccinic acid) (comparative) is a P-free chelating agent, biodegradable but expensive, can also be comprised in European powder detergent compositions.
[0112] Each detergent composition (containing the different co-builders of Table 3) is tested as follows: [0113] water hardness=25° fH (Ca:Mg—2:1); [0114] temperature=40° C.; [0115] Miele washing machines (cotton program); [0116] 4 cycles washes (external replication); [0117] stains: selection of 9 stains from the minimum AISE (International Association for Soaps, Detergents and Maintenance Products) protocol: blueberry, grass, red wine, espresso coffee, chocolate drink, cooked beef, sheep blood, fluid make up and squeezy mustard; [0118] detergent composition dosage: 65 g; [0119] performance check by stain removal.
[0120] Results of the present example are shown in the graphics on
[0121] For the determination of the Y-axis values (i.e. the SRI-values) of the graphics of
[0122] Results of the present example show improved performances between detergent compositions comprising the polymer of the invention and detergent compositions comprising co-builder benchmarks on bleachable stains (i.e. blueberry, grass, red wine, espresso coffee, squeezy mustard), and comparable performances on every other tested stain. This proves the versatility of the polymer of the invention, as it can effectively remove several types of stains in laundry applications, and it can effectively prevent several types of spots and films in dishwashing applications too (as it will be shown in the following example).
Example 3.3
[0123] Dishwashing Tests
[0124] The dishwashing test of the present example compares the spotting and filming prevention of two detergent compositions. Such two detergent compositions consist of the same base (“Base A”) and different co-builders. “Base A” of the tested detergent compositions is represented on Table 4.
TABLE-US-00004 TABLE 4 Chemical name, trade name Function % (w/w) Na Citrate Builder/Chelant 15.0 MGDA (methylglycindiacetic Builder/Chelant 15.0 acid) Na Carbonate Builder/Alkali 20.0 Na Bicarbonate Builder/Alkali 25.0 Silicate SKS ®-6 Corrosion inhibitor 3.0 Na Percarbonate Bleach 12.0 TAED Bleach Activator 2.0 (tetraacetylethylenediamine) Non ionic low foaming Non ionic surfactant 3.0 surfactant Protease Enzyme (Protease) 0.5 Amylase Enzyme (Amylase) 0.5 Sulphonated co-Polymer Co-builder 3.0 Sulphate Filler q.s. / Total 99.4
[0125] Last 0:6% of the two detergent compositions comprising “Base A” is a co-builder, in particular is either HEDP Na.sup.+ (comparative) or the polymer of the invention, as shown on Table 5.
TABLE-US-00005 TABLE 5 Chemical name, trade name Function Base A % HEDP Na.sup.+ (comparative) Co-builder 0.6 or Polymer of the invention
[0126] The polymer of the invention used for the present example is the one prepared in Example 1.1 above.
[0127] HEDP is a known phosphorus based additive in cleaning and is present in several conventional detergent composition, according to the prior art.
[0128] The two detergent compositions comprising “Base A” are tested as follows: [0129] water hardness=25° fH (Ca:Mg—2:1); [0130] Miele dishwashing machines (daily wash program); [0131] number of washes: 5 cumulative; [0132] number of glasses: 3; [0133] detergent composition dosage: 18 g; [0134] dirt: 20 g.
[0135] The dirt is prepared by mixing all the ingredients of Table 6 with a food processor.
TABLE-US-00006 TABLE 6 Component Quantity Ketchup 25 g Mustard 25 g Gravy 25 g Potato starch 5 g Egg yolk 3 g Margarine 100 g Milk 50 ml Water 700 ml
[0136] The performance checked on the present example is the spotting and filming prevention of the detergent compositions.
[0137] Results are evaluated with a panel test on glasses, and the ranking is from 1 (poor) to 10 (excellent).
[0138] Results of the present test for the detergent compositions comprising “Base A” are reported in
[0139] Another dishwashing test is carried out on other two detergent compositions. Such two other detergent compositions consist of the same base (“Base B”) and different co-builders. “Base B” of the detergent compositions is represented on Table 7.
TABLE-US-00007 TABLE 7 Chemical name, trade name Function % (w/w) Na Citrate Builder/Chelant 30.0 Na Carbonate Builder/Alkali 20.0 Na Bicarbonate Builder/Alkali 25.0 Silicate SKS-6 Corrosion inhibitor 3.0 Na Percarbonate Bleach 12.0 TAED Bleach Activator 2.0 (tetraacetylethylenediamine) Non ionic low foaming Non ionic surfactant 3.0 surfactant Protease Enzyme (Protease) 0.5 Amylase Enzyme (Amylase) 0.5 Sulphonated co-Polymer Co-builder 3.0 Sulphate Filler q.s. / Total 99.4
[0140] Last 0.6% of detergent compositions comprising “Base B” is a co-builder, in particular is either HEDP Na.sup.+ (comparative) or the polymer of the invention, as represented on Table 4 above.
[0141] Testing conditions, dirt composition, performance check and evaluating methods of the dishwashing test on the two detergent compositions comprising “Base B” are the same as the ones of the dishwashing test carried out with the detergent compositions comprising “Base A”.
[0142] Results of the test for the detergent compositions comprising “Base B” are reported in
[0143] From the results of these dishwashing tests represented from
[0144] These results also confirm the versatility of the polymer of the invention: indeed, the polymer of the invention grants suitable dishwashing properties when comprised in different detergent compositions having different bases.
Example 4
[0145] Biodegradation Tests
[0146] Biodegradation tests are performed using the standard “closed bottle” methods in accordance with OECD Guidelines 301 B, 301 F and 301 D (Ready Biodegradability), as well as OECD Guidelines 306 (Biodegradability in Seawater—Closed Bottle Method).
[0147] Full details of procedures and methods of calculation are publicly available in OECD Guideline for Testing of Chemicals 301 B, 301 F, 301 D and 306.
[0148] Study report LC-0053 and LC-0051 for OECD 306, study report LC-0050 and LC-0052 for OECD 301D all available.
[0149] Tests result are provided in Table 8 as percentage of biodegradation.
TABLE-US-00008 TABLE 8 OECD OECD OECD OECD / 301B 301F 301D 306 Polymer of the invention (Ex 1.5) 25 32 Polymer of the invention (Ex 1.6) 22 24 Polymer of the invention (Ex 1.3) 79.48% 62.82% lot 18E122 Polymer of the invention (Ex 1.3) 87.55% 82.85% lot 18G088 Pasp (1) (comparative) 54 50 Pasp (2) (comparative) 80.71% Baypure ® DS100/40% 67.92% (comparative) Carboxyline ® CMI .sup. >20% (comparative)
[0150] Baypure® DS100/40% is polyaspartate available from Lanxess, DE and Carboxyline® CMI is carboxymethylinulin from Cosun, NE. Pasp (1) and (2) were obtained directly from hydrolysis of the polysuccinimide used as raw material to produce SPE1504.