CN1154375A - Polycarboxylates for automatic dishwashing detergents - Google Patents
Polycarboxylates for automatic dishwashing detergents Download PDFInfo
- Publication number
- CN1154375A CN1154375A CN 96122672 CN96122672A CN1154375A CN 1154375 A CN1154375 A CN 1154375A CN 96122672 CN96122672 CN 96122672 CN 96122672 A CN96122672 A CN 96122672A CN 1154375 A CN1154375 A CN 1154375A
- Authority
- CN
- China
- Prior art keywords
- weight
- mol
- multipolymer
- methyl
- polymerized unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Detergent Compositions (AREA)
Abstract
The invention provides a polycarboxylates additive for automatic dishwashing detergents, which is prepared by polymerizing following three or more monomers: single ethylene unsaturated C3-C6 mono carboxylic acid such as crylic acid, single ethylene unsaturated C4-C6 dicarboxylic acid such as maleic, single ethylene unsaturated crylic acid or methacrylic acid ester. The automatic dishwashing detergent prepared by these additives reduces film formation and smear on washing glassware.
Description
The present invention relates to be used for the polymeric additive of automatic dishwashing detergents (ADD) composition, more specifically, relate to the polycarboxylate polymer additive that is used for without phosphorus ADD composition.
At present, use phosphate builders and chlorine bleaching agent to prepare the ADD composition.Tripoly phosphate sodium STPP has been widely used as washing assistant, because it has multi-functional character: water sequestering action, dirt dissemination, soil release characteristics and buffering effect, chlorine bleaching agent can be removed multiple dirt, dirty and the tea stain as coffee, and can be dispersed into small molecules to protein(aceous)soil, prevent from tableware and glassware, to form stain, but many required component such as enzyme, washing assistant and tensio-active agent in chlorine bleaching agent and the without phosphorus ADD composition can not be compatible.At present the phosphatic concern in the detergent for washing clothes has been produced market to developing the demand of without phosphorus ADD composition, but such composition properties is relatively poor.Non-phosphorus builder, for example Citrate trianion, carbonate, supercarbonate and silicate-like builder are easy in conjunction with the calcium and the magnesium ion that make water generates hardness, and when drying, can on the surface of glassware, ceramic disc, flatware and machine intimate part, stay inorganic " incrustation scale ", for example lime carbonate or Magnesium Silicate q-agent.Show as white to bluish grey film or stain, make tableware and outward appearance defective.
Polymeric additive is required in the free phosphate detergent composition, because they have and phosphorus containg substances, i.e. and the different dirt dispersion force of phosphoric acid salt or phosphonate.Many polymeric additives are polycarboxylates: the monomeric multipolymer of monocarboxylic acid and di-carboxylic acid, for example at US4,559, in 159 by the disclosed multipolymer of people such as Denzinger, or the multipolymer of monocarboxylic acid and hydroxy alkyl ester, for example at US4, in 897,215 by the disclosed multipolymer of people such as Trieselt.These polycarboxylates of prior art are disclosed and are used for detergent for washing clothes, and do not mention all in two reference that they may have desired be suppressed at film forming and the effect that becomes stain on the glassware when being used for the ADD composition.Need a kind ofly to remove that film forming is used for the same effective without phosphorus ADD composition with phosphorous ADD composition with the polymeric additive that becomes stain on the glassware.
We have found a kind of component of polymer that is suitable as detergent additives, can give without phosphorus ADD composition improved prevention film-forming properties.Component of polymer of the present invention is a kind of multipolymer, contains the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, low alkyl group are unsubstituted and the weight-average molecular weight of multipolymer is 1000-30,000.
We further find a kind of component of polymer that is suitable as the detergent additives in the without phosphorus ADD composition, are a kind of multipolymer, and it contains the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, at least a low alkyl group is that replace and weight-average molecular weight multipolymer is 1000-30 with hydroxyl, 000, multipolymer PH be 2 or lower condition under carry out polymerization.
We also further find a kind of without phosphorus ADD composition with improved prevention film-forming properties, comprise the multipolymer of 1-20% weight in the composition, and the latter is contained the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, lower alkyl esters are unsubstituted and the weight-average molecular weight of multipolymer is 1000-30,000.
We also further find a kind of without phosphorus ADD composition with improved prevention film-forming properties, comprise the multipolymer of 1-20% weight in the composition, and the latter is contained the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, at least a low alkyl group is that replace and weight-average molecular weight multipolymer is 1000-30 with hydroxyl, 000, multipolymer PH be 2 or lower condition under carry out polymerization.
We further find a kind of film forming method on automatic dishwasher institute wash up that is used for reducing again, comprise that this multipolymer contains the unsaturated C of one or more single ethylene types of 40-85%mol with aqueous mixture wash dining set in automatic dishwasher of the without phosphorus ADD that contains a kind of multipolymer
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, low alkyl group are unsubstituted and the weight-average molecular weight of multipolymer is 1000-30,000.
We also further find a kind of film forming method on automatic dishwasher institute wash up that is used for reducing, comprise that this multipolymer contains the unsaturated C of one or more single ethylene types of 40-85%mol with aqueous mixture wash dining set in automatic dishwasher of the without phosphorus ADD that contains a kind of multipolymer
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, at least a low alkyl group is that replace and weight-average molecular weight multipolymer is 1000-30 with hydroxyl, 000, multipolymer PH be 2 or lower condition under carry out polymerization.
Term " multipolymer " refers to two or more polymer of monomers as used herein; Multipolymer of the present invention is three kinds or multiple polymer of monomers.Term " acid polymerized unit " refers to owing to making unsaturated monobasic of single ethylene type or di-carboxylic acid polymerization be present in unit in the polymer chain as used herein, yet, those skilled in the art can think that same unit can be owing to being present in the polymer chain corresponding acid anhydrides polymerization, so this term refers to and contains the unitary polymkeric substance that makes unsaturated monobasic of single ethylene type or di-carboxylic acid or corresponding acid anhydrides polymerization and generate.
Term " low alkyl group " refers to and contains C as used herein
1-C
8Line style or ramiform alkyl.Term " (methyl) acrylate " and " (methyl) vinylformic acid " be meant acrylate, methacrylic ester or acrylate and methacrylic ester the two; With vinylformic acid, methacrylic acid or vinylformic acid and methacrylic acid the two." the not replacing " meaning that is used for low alkyl group is that low alkyl group does not use the functional group such as hydroxyl to replace; Do not get rid of and have the hydrocarbon branch.
Polymeric additive composition of the present invention is the unsaturated C of one or more single ethylene types that contains 50-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The multipolymer of the polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, low alkyl group are unsubstituted and the weight-average molecular weight of multipolymer is 1000-30,000.As above indicated, the mixture of monobasic and di-carboxylic acid, corresponding acid anhydrides or respective acids and acid anhydrides is carried out copolymerization also can make the polymeric additive composition.
The unsaturated C of one or more single ethylene types
4-C
6The preferable range of the polymerized unit of di-carboxylic acid is 5-30%mol, more preferably 10-20%mol.The preferable range of the polymerized unit of one or more (methyl) lower alkyl acrylate is 10-30%mol, more preferably 15-25%mol.Di-carboxylic acid unit and the unitary mixing total amount of (methyl) alkyl acrylate mostly are the 60%mol of polymkeric substance most, because the unsaturated C of single ethylene type
3-C
6Monocarboxylic minimum be 40%mol.The weight-average molecular weight preferable range of multipolymer is 2000-15,000, and more preferably 3500-10,000.
Alkoxide component particular methanol, ethanol, propyl alcohol or the butanols of (methyl) lower alkyl acrylate can be line style or branched also, it further can be glycol, ethylene glycol, 1 for example, 2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol and 1, the 4-butyleneglycol, and be formed on the ester that alkoxide component partly replaces with single hydroxyl.Unsubstituted (methyl) lower alkyl acrylate is more preferably and is selected from the secondary propyl ester of methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, vinylformic acid, n-butyl acrylate, isobutyl acrylate, vinylformic acid 1-methyl propyl ester and vinylformic acid 2-methyl propyl ester and corresponding methacrylic ester and further preferably from methyl acrylate, methyl methacrylate, ethyl propenoate and Jia Jibingxisuanyizhi.The example that is used for (methyl) lower alkyl acrylate that replaces with hydroxyl of the present invention has vinylformic acid and hydroxyethyl methylacrylate, vinylformic acid and Rocryl 410 and vinylformic acid and methacrylic acid hydroxy butyl ester.
In these examples that low alkyl group replaces with hydroxyl, multipolymer be aggregated in PH be 2.0 or lower situation under carry out.Under the unsubstituted situation of low alkyl group also preferably PH be 2.0 or lower situation under carry out the polymerization of multipolymer.Therefore, because in can part when preparation contains the multipolymer of unsubstituted (methyl) lower alkyl acrylate and monobasic and di-carboxylic acid, preferably when preparation contains the multipolymer of methacrylic acid that low alkyl group part replaced by hydroxyl or lower alkyl acrylate, limit any acid and neutralize and be higher than 2.0 pH value to avoid producing.
Can water-soluble solution in the whole PH scope that polymeric additive preferably of the present invention runs at the preparation polymeric additive, when storing the ADD composition contain polymeric additive (no matter liquid or solid) and using polymeric additive in automatic dishwasher, promptly the PH scope is 5-12.The selectivity that this solubleness is brought has been determined the upper limit of the polymerized unit preferable range of vinylformic acid and methacrylic acid lower alkyl esters, depends on the solubleness of the polymkeric substance that contains these polymerized units.Like this, when the polymerized unit scope of (methyl) lower alkyl acrylate was 10-40%mol, the content of concrete ester preferably should not make polymeric additive soluble when preparing, storing or using in automatic dishwasher.Therefore, be higher than the polymerized unit that does not replace ester that alcoholic acid alcohol forms and be preferably limited to the 0-30%mol of total polymer, the more preferably scope of 0-15%mol and further preferred 0-10%mol.
A unexpected feature of polymeric additive of the present invention is that they are stable under the high PH level that runs into when being used for automatic dishwasher.Reasonably be that the polymerized unit that a those of ordinary skill of this area can be predicted ester issues unboiled water at the strong alkaline condition that is produced by the ADD composition component such as yellow soda ash and separates.Clearly, the ester units of polymeric additive is hydrolysis largely not, because the result will produce a kind of polymeric additive, its polymerized unit that contains is consistent with polymeric (methyl) polymerizing acrylic acid unit, and the performance test of polymeric additive of the present invention shows that they are better than for example toxilic acid and acrylic acid multipolymer.
The following examples are used to illustrate a kind of method of making component of polymer of the present invention; Open according to the present invention, those of ordinary skill in the art can obviously know other method of making this component of polymer.Component of polymer of the present invention can be made by polymerizable aqueous, solvent polymeric or mass polymerization.In addition, can adopt intermittently, co-fed (co-feed), tailing (heel), semicontinuous or continuous processing carry out polymerization.The co-fed technology polymerization of preferred employing.When method of the present invention adopted co-fed technology, initiator and monomer preferably joined in the reaction mixture with the materials flow and the constant speed of separating.If need, the adding mode of materials flow should be to add one or more this materials flows before other materials flow adds.If need, can before reinforced beginning, join a part of monomer or initiator in the reactor.Monomer can be done independent materials flow and join in the reaction mixture or be blended in one or more materials flows and add.
The weight-average molecular weight of polymeric additive composition is 1000-30,000.Molecular weight can change according to the relative quantity and the wetting ability that are incorporated into the monomer component in the multipolymer.If need, can when polymerization, use chain regulator or chain-transfer agent to help to control the molecular weight of resulting polymers.Can use any water-soluble chain regulator or chain-transfer agent commonly used.Suitable chain regulator includes but not limited to mercaptan for example 2 mercapto ethanol and 3-mercaprol, hypophosphite, saccharosonic acid, alcohols, aldehydes, hyposulfite and hydrosulphite.Preferably as chain regulator or chain-transfer agent be hydrosulphite, sodium metabisulfite for example.It is that 4500 polyacrylic acid standard is measured with respect to molecular weight that weight-average molecular weight herein and number-average molecular weight are used the hydrogel permeation chromatography.
The ADD composition that uses polymeric additive of the present invention can be powder type or liquid form; When according to the ADD composition when this uses, term " liquid " comprises gel and slurries.ADD composition of the present invention also contains ADD component well known by persons skilled in the art, for example washing auxiliary detergent, corrosion inhibitor, tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, detersive enzyme, dyestuff, perfume compound and inert diluent such as water and water-soluble inorganic an alkali metal salt.Polymeric additive consumption of the present invention accounts for the 1-20% weight of ADD composition gross weight, preferred 2-10% weight.
The washing auxiliary detergent that is used for ADD composition of the present invention has alkaline carbonate, borate, supercarbonate and oxyhydroxide, comprises the water-soluble organic washing-assisting detergent of poly carboxylic acid material such as nitrilotriacetic acid(NTA), Citrate trianion, tartrate and succinate, and zeolite.Can use with polymkeric substance detergent additives of the present invention although contain the washing assistant of phosphoric acid salt such as tripoly phosphate sodium STPP and trisodium phosphate, this is not preferred, and gained ADD composition contains phosphoric acid salt.The amount that washing assistant is present in the ADD composition is the 0-90% weight that accounts for ADD composition gross weight, preferred 20-90% weight.The amount of actual washing assistant depends on that washing composition is liquid or powder; The washing assistant that contains in the liquids in general composition is than lacking in the powder composition.
The corrosion inhibitor that is used for ADD composition of the present invention is an alkalimetal silicate, preferred SiO
2/ M
2The O ratio is 1: 1-3.5: 1 silicate (M wherein
2O represents the alkalimetal oxide part of silicate).The example of preferred alkalimetal silicate is a water glass.The amount that corrosion inhibitor is present in the ADD composition is the 0-50% weight that accounts for ADD composition gross weight, preferred 1-20% weight.
The tensio-active agent that is used for ADD composition of the present invention is low foam water soluble surfactants, for example negatively charged ion, nonionic, zwitter-ion and amphoteric tensio-active agent, and combination.The examples of anionic surfactants that is used for ADD composition of the present invention has C
9-C
20Vitriol, vitriol, hydroxyalkylated sulfonic acid salt, alkenyl and the alkyl-sulphate of ethoxylated alcohol and the sour condenses and the analogue of sulfonate, direactive glyceride vitriol, fat acyl chloride and hydroxyalkylated sulfonic acid salt of the salt of lipid acid, alkylbenzene sulfonate and especially linear alkyl benzene sulfonate salt (wherein alkyl has 10-16 carbon), alcohol.Because anion surfactant is easy to produce foam, therefore the content in the ADD composition should remain on minimum, and can require froth suppressor.
The example that is used for the nonionogenic tenside of ADD composition of the present invention has for example C of the segmented copolymer of alkylene oxide (as ethylene oxide) condenses, ammonium oxide, sugar derivatives such as sucrose palmitic acid ester, dialkyl sulphoxide, polyethylene oxygen and the polypropylene oxygen of list and polyhydroxy-alcohol, alkylphenol, fatty amide and aliphatic amide, hydrophobic modified polyethylene oxygen tensio-active agent, fatty amide
10-C
18The list of lipid acid or di-methylcarbinol acid amides, and analogue.
The example that is used for the zwitterionics of ADD composition of the present invention comprises the derivative of aliphatic quaternary ammonium compound, 3-(N for example, N-dimethyl-N-cetyltrimethyl ammonium) propane-1-sulfonate and 3-(N, N-dimethyl-N-cetyltrimethyl ammonium)-2-hydroxy propane-1-sulfonate.The example that is used for the amphoterics of ADD composition of the present invention comprises trimethyl-glycine, sultaine and fatty acid imidazoline carboxylate salt and sulfonate.
The total amount that tensio-active agent is present in the ADD composition of the present invention depends on selected tensio-active agent, and is preferably the 0.1-10% weight that accounts for ADD composition gross weight, more preferably 1-5% weight.The amount that anion surfactant (if use) exists is to account for below 5% weight of ADD composition gross weight, more preferably below 3% weight.
The SYNTHETIC OPTICAL WHITNER that is used for ADD composition of the present invention comprises halogen, superoxide and peracid SYNTHETIC OPTICAL WHITNER, for example Textone, clorox, dichloroisocyanuric acid sodium, Sodium peroxoborate and SPC-D and corresponding sylvite.The consumption of SYNTHETIC OPTICAL WHITNER accounts for the 0-20% weight of ADD composition gross weight, preferred 0.5-15% weight.Can comprise bleach-activating agent in the ADD composition of the present invention; Select such bleach-activating agent to make in cryogenic bleaching optimizing; this class bleach-activating agent comprises such as N; N, N ', N '-tetra acetyl ethylene diamine (TAED), nonyl oxygen benzene sulfonic acid sodium salt (SNOBS), glucose pentaacetate (GPA) and tetra-acetylated glycoluril (glycouril) are (TAGU).Those of ordinary skills can select to be suitable for the bleach-activating agent of selected SYNTHETIC OPTICAL WHITNER.
ADD composition of the present invention also can comprise the assistant agent commonly used up to 5% weight, for example perfume compound, dyestuff, froth suppressor, detersive enzyme such as proteolytic ferment and amylase, antiseptic-germicide and analogue.When washing composition is liquid form, can there be the stablizer or the viscosity modifier that account for ADD composition gross weight 0-5% weight, for example clay and polymer viscosifier.In addition, also can there be inert diluent, for example resembles the inorganic salt of sodium sulfate or potassium or sodium-chlor or potassium, and water.
The component that is selected to the ADD composition is preferably compatible mutually.For example dyestuff, perfume compound and enzyme are preferably all compatible with alkaline component with the bleaching component under storage and working conditions.Those skilled in the art can select the ADD composition component that can hold mutually.
ADD composition of the present invention can be used as the aqueous solution or dispersion is used for automatic dishwasher, and concentration is the 0.1-1.0% weight that accounts for liquid gross weight in the dishwasher, preferred 0.2-0.7% weight.Also available higher or lower concentration, but lower concentration can make the washing under the specific environment not enough, and greater concn improves wash result, but cost has increased.Preferred 35 ℃-70 ℃ of water temperature during washing, more preferably 40 ℃-60 ℃.
In the following example, all reagent all are high-quality commercially available (unless indicating in addition), and all percentage ratios and ratio are represented (unless indicating in addition) with weight.
Embodiment 1
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprises the polymerized unit of the ethyl propenoate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight in the additive.
In 2 liter of 4 neck round-bottomed flask of mechanical stirrer, reflux exchanger and thermopair is housed, add the metal promoted agent solution of ferrous sulfate in deionized water of 337.2g deionized water, 64.8g maleic anhydride, 1.6g sodium metabisulfite and 10.0g0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 242.5g glacial acrylic acid,
2) 81.7g ethyl propenoate,
3) the sodium metabisulfite material solution of 36.3g sodium metabisulfite in the 103.7g deionized water,
4) initiator solution of 12.97g Sodium Persulfate in the 105.3g deionized water.
Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, ethyl propenoate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of solution respectively, be made up of in 1.0g deionized water the 0.13g Sodium Persulfate a kind of the be made up of in the 1.0g deionized water with another kind of the 0.13g sodium metabisulfite, join in turn in the reaction mixture immediately following monomer, second batch of solution of following the monomer adding adds after 72 ℃ keep 15 minutes in reaction mixture.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 43 ℃.
When temperature reaches 43 ℃, add the superoxol of 5.0g 30%, further be cooled to 25 ℃, add the superoxol of 5.3g 30% again at this.
By slowly adding the aqueous sodium hydroxide solution of 345.5g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 41.5% weight solid solution.Weight-average molecular weight is 3890, and number-average molecular weight is 3080, and both ratio is 1.26.
Embodiment 2
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprise the polymerized unit of the ethyl propenoate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight in the additive, use the different step that causes different molecular weight during preparation.
In equipment as described in embodiment 1, add the metal promoted agent solution of ferrous sulfate in deionized water of 342.8g deionized water, 65.8g maleic anhydride, 0.8g sodium metabisulfite and 10.2g 0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 246.2g glacial acrylic acid,
2) 82.9g ethyl propenoate,
3) the sodium metabisulfite material solution of 19.7g sodium metabisulfite in the 105.3g deionized water,
4) initiator solution of 9.24g Sodium Persulfate in the 105.3g deionized water.
Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, ethyl propenoate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of solution respectively, be made up of in 2.6g deionized water the 0.5g Sodium Persulfate a kind of the be made up of in the 2.6g deionized water with another kind of the 0.5g sodium metabisulfite, and follow monomer and join in turn in the reaction mixture, after 72 ℃ keep 15 minutes, add the solution of following the monomer adding as mentioned above again.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 25 ℃.
By slowly adding the aqueous sodium hydroxide solution of 356.3g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 40.31% weight solid solution.Weight-average molecular weight is 6790, and number-average molecular weight is 4960, and both ratio is 1.37.
Embodiment 3
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprises the polymerized unit of the Hydroxyethyl acrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 19% weight of 50% weight and 31% weight in the additive.
In being equipped with, add the metal promoted agent solution of ferrous sulfate in deionized water of 110.80g deionized water, 26.91g maleic anhydride, 0.19g sodium metabisulfite and 3.69g 0.15% weight, form reaction mixture as 1 liter of 4 neck round-bottomed flask of device as described in the embodiment 1.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 71.76g glacial acrylic acid,
2) 44.85g Hydroxyethyl acrylate,
3) the sodium metabisulfite material solution of 7.23g sodium metabisulfite in the 56.51g deionized water,
4) initiator solution of 8.61g Sodium Persulfate in the 50.93g deionized water.
Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, Hydroxyethyl acrylate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of independent solution, each is made up of in 1.00g water the 0.05g Sodium Persulfate, follows monomer and joins in turn in the reaction mixture, and second batch of solution of following the monomer adding adds after 72 ℃ keep 15 minutes in reaction mixture.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 22 ℃.
By slowly adding the aqueous sodium hydroxide solution of 118.0g 50%, make reaction mixture neutralization, PH7.0 PH1.2 to 25 ℃ time the during from original 22 ℃, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 40.7% weight solid solution.Weight-average molecular weight is 4800, and number-average molecular weight is 3820, and both ratio is 1.25.
Embodiment 4
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprise the polymerized unit of the ethyl propenoate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight in the additive, use the different step that causes different molecular weight during preparation.
In being equipped with, add the metal promoted agent solution of ferrous sulfate in deionized water of 175.2g deionized water, 33.7g maleic anhydride, 0.2g sodium metabisulfite and 5.2g 0.15% weight, form reaction mixture as 1 liter of flask of device as described in the embodiment 1.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 126.0g glacial acrylic acid,
2) 42.5g ethyl propenoate,
3) the sodium metabisulfite material solution of 5.2g sodium metabisulfite in the 53.9g deionized water,
4) initiator solution of 1.86g Sodium Persulfate in the 53.9g deionized water.Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, ethyl propenoate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of independent solution, be made up of in 0.5g deionized water the 0.1g Sodium Persulfate a kind of the be made up of in the 0.5g deionized water with another kind of the 0.1g sodium metabisulfite, follow monomer and join in turn in the reaction mixture, after 72 ℃ keep 15 minutes, add again and follow the solution that monomer adds as mentioned above.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 25 ℃.
By slowly adding the aqueous sodium hydroxide solution of 169.7g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 40.0% weight solid solution.Weight-average molecular weight is 21300, and number-average molecular weight is 11400, and both ratio is 1.87.
Embodiment 5
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprise the polymerized unit of the ethyl propenoate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 10% weight of 70% weight and 20% weight in the additive, use the step that causes molecular weight similar to Example 1 during preparation.
In embodiment 1 described equipment, add the metal promoted agent solution of ferrous sulfate in deionized water of 336.5g deionized water, 33.8g maleic anhydride, 1.0g sodium metabisulfite and 10.1g 0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 280.2g glacial acrylic acid,
2) 80.1g ethyl propenoate,
3) the sodium metabisulfite material solution of 26.27g sodium metabisulfite in the 105.1g deionized water,
4) initiator solution of 10.5g Sodium Persulfate in the 105.1g deionized water.
Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, ethyl propenoate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of independent solution, be made up of in 2.6g deionized water the 0.5g Sodium Persulfate a kind of the be made up of in the 2.6g deionized water with another kind of the 0.5g sodium metabisulfite, and follow monomer and join in turn in the reaction mixture, after 72 ℃ keep 15 minutes, add the solution of following the monomer adding as mentioned above again.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 25 ℃.
By slowly adding the aqueous sodium hydroxide solution of 348.6g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 42.1% weight solid solution.Weight-average molecular weight is 4700, and number-average molecular weight is 3590, and both ratio is 1.31.
Embodiment 6
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprises the polymerized unit of the Hydroxyethyl acrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 19% weight of 70% weight and 11% weight in the additive.
In 1 liter of flask of device as described in embodiment 1, add the metal promoted agent solution of ferrous sulfate in deionized water of 110.80g deionized water, 26.91g maleic anhydride, 0.19g sodium metabisulfite and 3.69g 0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 100.46g glacial acrylic acid,
2) 16.15g Hydroxyethyl acrylate,
3) the sodium metabisulfite material solution of 7.23g sodium metabisulfite in the 56.51g deionized water,
4) initiator solution of 8.61g Sodium Persulfate in the 50.93g deionized water.
Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, Hydroxyethyl acrylate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of independent solution, each all is made up of in 1.00g water the 0.05g Sodium Persulfate, and follow monomer and join in turn in the reaction mixture, reaction mixture adds second batch of solution of following the monomer adding as mentioned above again after 72 ℃ keep 15 minutes.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 23 ℃.
By slowly adding the aqueous sodium hydroxide solution of 144.9g 50%, PH7.0 during H1.1 to 25 ℃ of initial p when making reaction mixture neutralize by 23 ℃, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 40.5% weight solid solution.Weight-average molecular weight is 4650, and number-average molecular weight is 3790, and both ratio is 1.22.
Embodiment 7
This embodiment is used to illustrate the preparation of ADD polymeric additive of the present invention, comprises the polymerized unit of the Propylene glycol monoacrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 30% weight of 50% weight and 20% weight in the additive.
In the 1/2 liter of 4 neck flask that is equipped with as device as described in the embodiment 1, add the FeSO of 75.00g deionized water, 6.00g 0.15% weight
47H
2The aqueous sodium hydroxide solution of the aqueous solution of O, 60.00g toxilic acid and 21.00g 50% weight forms reaction mixture.Stir down reaction mixture is heated to 72-73 ℃, begin to add the 4.00g Sodium Persulfate simultaneously in the 20.00g deionized water and the two kind independent materials of 40.00g Propylene glycol monoacrylate in the 100.00g glacial acrylic acid, begin to add a kind of independent material of 12.00g sodium metabisulfites in the 45.00g deionized water simultaneously through 100 minutes with preceding two kinds of materials through 120 minutes.Reinforced finishing measured the PH of reaction mixture, is PH1.8.At 72-73 ℃ reaction mixture was kept 10 minutes, add the solution of 0.20g Sodium Persulfate in the 3.00g deionized water.Stirred reaction mixture adds the another kind of solution that contains the 0.20g Sodium Persulfate in the 3.00g deionized water.Reaction mixture is cooled to 45 ℃; The aqueous sodium hydroxide solution that adds 20.80g50% weight, and with the superoxol treating mixture of 1.30g 30-33%.The aqueous sodium hydroxide solution that adds 131.10g 50% weight makes PH rise to 6.7 and add 30.00g deionized water diluted mixture thing.
The solid content of gained solution polymer is 46.7%, and weight-average molecular weight is 5340, and number-average molecular weight is 4000.The remaining vinylformic acid and the content of maleic acid monomer are respectively 194 and 2200ppm.
Embodiment 8
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprises the polymerized unit of the methyl acrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight in the additive.
In 1 liter of flask of device as described in embodiment 1, add the metal promoted agent solution of ferrous sulfate in deionized water of 130.0g deionized water, 25.0g maleic anhydride, 0.4g sodium metabisulfite and 3.9g 0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, afterwards, begins to add following four kinds of different materials simultaneously:
1) 93.5g glacial acrylic acid,
2) 31.5g methyl acrylate,
3) the sodium metabisulfite material of 10.0g sodium metabisulfite in the 40.0g deionized water is molten
4) initiator solution of 4.0g Sodium Persulfate in the 40.0g deionized water.
Whole sodium metabisulfite material solutions added through 75 minutes, and whole glacial acrylic acids, methyl acrylate and initiator solution added through 90 minutes.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare a kind of solution of in the 1.0g deionized water, forming by the 0.05g Sodium Persulfate, and follow monomer and join in the reaction mixture, after 72 ℃ keep 15 minutes, add the solution of following the monomer adding as mentioned above again.Reaction mixture was kept 15 minutes in 72 ℃ again, then be as cold as 25 ℃.
By slowly adding the aqueous sodium hydroxide solution of 130.9g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 41.7% weight solid solution.Weight-average molecular weight is 7220, and number-average molecular weight is 5080, and both ratio is 1.42.
Embodiment 9
This embodiment has illustrated the preparation of ADD polymeric additive of the present invention, comprises the polymerized unit of the Propylene glycol monoacrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 40% weight of 40% weight and 20% weight in the additive.
In the 1/2 liter of 4 neck flask that is equipped with as device as described in the embodiment 1, add the FeSO of 80.00g deionized water, 3.00g 0.15% weight
47H
2The aqueous sodium hydroxide solution of the aqueous solution of O, 80.00g toxilic acid and 82.75g 50% weight forms reaction mixture.Stir and down reaction mixture is heated to 92 ℃, and be incorporated in the 4.00g sodium hypophosphite in the 20.00g deionized water.Begin to add the 4.00g Sodium Persulfate simultaneously in the 20.00g deionized water and the two kind independent materials of 40.00g Propylene glycol monoacrylate in the 80.00g glacial acrylic acid, begin to add a kind of independent material of 4.00g sodium hypophosphites in the 20.00g deionized water simultaneously through 100 minutes with preceding two kinds of materials through 120 minutes.Reinforced finishing, reaction mixture kept 30 minutes in 92 ℃.With 47.00g deionized water diluted reaction mixture, be cooled to 45 ℃ of sodium hydroxide solutions that also add 92.70g 50% weight gradually and transfer PH to 6.8.
The solid content of gained solution polymer is 46.5%, and weight-average molecular weight is 3960, and number-average molecular weight is 3280.The remaining vinylformic acid and the content of maleic acid monomer are respectively 148 and 1200ppm.
Embodiment 10
With embodiment 1 described step, prepare ADD polymeric additive of the present invention, contain the polymerized unit of the methyl acrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight.The character and the performance of gained additive are shown in down Table II.
Embodiment 11
With embodiment 7 described steps, prepare ADD polymeric additive of the present invention, contain the polymerized unit of the vinylformic acid hydroxy butyl ester of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight.The character and the performance of gained additive are shown in down Table II.
Embodiment 12
With embodiment 1 described step, prepare ADD polymeric additive of the present invention, contain the polymerized unit of the Hydroxyethyl acrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight.The character and the performance of gained additive are shown in down Table II.
Embodiment 13
With embodiment 7 described steps, prepare ADD polymeric additive of the present invention, contain the polymerized unit of the butyl acrylate of the polymerized unit of Propylene glycol monoacrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 15% weight and 5% weight.The character and the performance of gained additive are shown in down Table II.
Embodiment 14
With embodiment 1 described step, prepare ADD polymeric additive of the present invention, contain the polymerized unit of the Propylene glycol monoacrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight.The character and the performance of gained additive are shown in down Table II.
Embodiment 15
With embodiment 7 described steps, prepare ADD polymeric additive of the present invention, contain the polymerized unit of the Propylene glycol monoacrylate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 10% weight of 70% weight and 20% weight.The character and the performance of gained additive are shown in down Table II.
In order to measure the validity of ADD polymeric additive in the foregoing description and the following Comparative Examples, during the typical ADD shown in the Table I fills a prescription down the adding of ADD additive, comprise component and the consumption indicated, stop performance thereby estimate its relative incrustation scale.
Table I
| Component formula I (% weight) Trisodium citrate dihydrate 10 yellow soda ash 30 |
| Britesil?H 2O 17 sodium perborate tetrahydrates, 7.5 TAED 22.5 proteolytic enzyme 31 amylase 4 1 Polytergent?SLF-18 53 sodium acid carbonates, 20 sodium sulphate, 2 water, 10 polymeric additives 6 |
1Britesil H
2O is SiO
2/ Na
2The O weight ratio is 2 hydration sodium polysilicate, by PQCorp., and Valley Forge, PA obtains,
2TAED is N, N, and N ', N '-tetra acetyl ethylene diamine,
3Used proteolytic enzyme is from NOVO Nordisk Bioindustrials, Danbury, and the Esperase 6.0T of CT,
4Used amylase is from NOVO Nordisk Bioindustrials, Danbury, and the Termamyl 60T of CT,
5Polytergent SLF-18 is the nonionic ethoxylated alcohol from Olin Corp..
The film forming that is used to measure above-mentioned ADD prescription is ASTM 3556-85 with becoming the stain performance promptly to stop the testing method of calcium type incrustation scale performance, it is glassware settling standard method of test during machinery washes the dishes, use the Libbey Collins glassware of four 250ml (10 ounces) to be improved with being set to the Kenmore automatic dishwasher (Kenmore is Sears, the trade mark of Roebuck and Co.) in standard wash cycle and heat drying cycle.Optionally put 14-18 service plate on the underframe of dishwasher and optionally putting several measuring cups and cup on the upper frame.Four LibbeyCollins glasswares optionally are placed on the upper frame as the tested glass thing.The water temperature of test usefulness is generally 48.5 ℃ and 51.5 ℃ (119 and 124) in normal period, and water has the hardness of 300ppm (with CaCO
3Meter), the Ca/Mg ratio is 3: 1.Do not use rinse aid or food dirt.Comprise washing for the first time, rinsing, main washing and twice post rinse normal period, the back is the heat drying cycle.When beginning to test, 25g washing composition sample is put into the washing composition jigger.When main washing begins, open machine and add 25g washing composition sample again.Glassware is washed 5 complete cycles, visual inspection period 3 and last cycle film forming and stain situation afterwards.
Should be noted that it is harsh especially carrying out the used condition of above-mentioned test, because 300ppmCaCO
3The firmness level be higher than most of in the world hardness of drinking water.Therefore, when using with stone water, the performance of polymeric additive of the present invention is especially good.
According to following numerical value, write down the results of property of above-mentioned test: film-forming properties numerical value does not have film 0 and almost cannot see 0.5 1 below average, 2 better-than-average 3 more 4 extremely many 4+ slightly
According to above-mentioned testing method, the polycarboxylate in the test embodiment of the invention 1 to 15 the results are shown in down Table II.In Table II and Table III, wardrobe are indicated the weight percentage of polymerized unit of every kind of polymeric components of perpendicular line display of vinylformic acid, toxilic acid and ester content.Mw and Mn represent weight-average molecular weight and number-average molecular weight respectively.
Table II embodiment vinylformic acid maleic acid ester content ester Mw Mn film
11 60 20 20 EA, 3,890 3080 0.7/0.8,2 60 20 20 EA, 6,790 4,960 0.55 3 50 19 31 HEA, 4,800 3,820 0.65 4 60 20 20 EA 21; 300 11,400 1.3 (c) 5 70 10 20 EA, 4,700 3590 0.65/0.70,6 70 19 11 HEA 4,650 3,790 1.1 (indigo plant), 7 50 30 20 HPA, 5,340 4,000 0.5 8 60 20 20 MMA, 7,220 5,060 0.5 9 40 40 20 HPA, 3,960 3,280 0.85 10 60 20 20 MA, 5,500 4,160 0.5 11 60 20 20 HBA 6,220 0.5
12 60 20 20 HEA 6910 4330 0.4
13 60 20 15/5 HPA/ 5550 0.6
BA
14 60 20 20 HPA 5860 3710 0.35
15 70 10 20 HPA 4030 0.5
1Measure the film forming degree during the 5th end cycle.
The ester symbol:
The BA=butyl acrylate
The EA=ethyl propenoate
HBA=vinylformic acid hydroxy butyl ester
The HEA=Hydroxyethyl acrylate
The HPA=Propylene glycol monoacrylate
The MA=methyl acrylate
The MMA=methyl methacrylate
Film: (C)=chilternu
With method known to those skilled in the art preparation contrast polycarboxylate material, estimate according to above-mentioned testing method equally.Contrast polycarboxylate embodiment labelled notation, evaluation result is listed in the table below among the III.
Table III Comparative Examples vinylformic acid maleic acid ester content ester Mw film
116 100 0 0-2000 1.8/2.0 (indigo plant) 17 100 0 0-4,500 1.1 18 100 0 0-10; 000 0.9 19 100 0 0-40,000 2.0 (chilternus) 20 90 10 0-3,200 1.5 21 80 20 0-4,300 1.8 22 50 50 0-3,500 1.5 23 30 70 0-4,200 2.52(chilternu) 24 80 0 20 HEA 3,930 3.5 (chilternu) 25 80 0 20 HPA 4,140 3.0
2(chilternu) 26 80 0 20 MMA 4,640 4 (chilternu) 27 80 0 20 MA 4,060 4 (chilternu) 28 80 0 20 HBA 5,180 2.5
2(chilternu) 29 80 0 15/5 HPA/BA 4,830 2.5 (chilternu) 30 80 0 20 EA 3,950 3.5 (chilternus) 32 70 30
30-3,500 1.9 33 70 30 0-30,000 1.2
1Except that mark, measure the film forming degree 5 all end of term.
2Because film forming is too strong, measure film-forming properties 3 all end of term.
3Not toxilic acid, but methacrylic acid.
Comparative Examples 31
As the another comparison of present composition performance, estimate commercially available prod, Cascade according to above-mentioned testing method to film-forming properties and stain
RThe performance of automatic dishwashing detergents.Based on US5,279,756 is open, thinks that Cascade is made up of following:
Table IV
Component Cascade prescription
Tripoly phosphate sodium STPP 33.0%
Yellow soda ash 21.0%
Nonionogenic tenside 2.0%
Water glass 22.7%
ACL-59 chlorizating agent 2.0%
Sodium sulfate 19.0%
Perfume compound 0.3%
During according to above-mentioned test evaluation, the Cascade automatic dishwashing detergents is 0.8 in the value of the film forming degree of 5 all after dates, and it is blue that film is.Like this, under this test condition, composition of the present invention is the same good with the commercially available ADD composition of common phosphorous hydrochlorate usually on the glassware film-forming properties that stops cleaning, and often is more better.
Phosphorous ADD prescription:
In order to illustrate that except that these prescriptions that do not conform to phosphorus, ADD polymeric additive of the present invention is also effective in phosphatic ADD prescription, preparation contains the ADD prescription of component and content shown in the Table V down.Formula I I represents to contain the phosphatic typical ADD of more amount (35% weight) and concentrates (so-called " excess ") prescription; Formula I II represents to contain a small amount of (20% weight) phosphatic typical ADD and concentrates prescription.Component as above Table I footmark is annotated described.
Table V
Formula I I formula I II
Component % weight g/ washes % weight g/ and washes
Tripoly phosphate sodium STPP 35 12.6 20 7.20 Trisodium citrate dihydrates----10 3.60
Yellow soda ash 22 7.92 30 10.8 Britesil H2O 12 4.32 12 4.32 sodium perborate tetrahydrates 7.5 2.7 7.5 2.7
TAED 2.5 0.90 2.5 0.90
Proteolytic enzyme 1.0 0.36 1.0 0.36
Amylase 0.5 0.18 0.5 0.18 Polytergent SLF-18 3.5 1.26 3.5 1.26
Sodium sulfate 14 5.04 9 3.24
Polymeric additive 2 0.72 4 1.44
The testing method that is used to measure prescription film-forming properties and stain is as described in the top embodiment 15.The performance numerical value of two kinds of phosphatic prescriptions of this test and shown in polymeric additive Table VI as follows.
Other polymer composition below the test in the phosphorous ADD composition in formula I I and III.
Embodiment 32 and 33
Embodiment 32 and 33 polymeric additive are the comparative polymer additives.The comparative additive of embodiment 32 contains the polymerized unit of the methacrylic acid of the polymerizing acrylic acid unit of 70% weight and 30% weight, and weight-average molecular weight is 3500.The comparative additive of embodiment 33 contains the polymerized unit of the toxilic acid of the polymerizing acrylic acid unit of 70% weight and 30% weight, and weight-average molecular weight is 30000.Test the performance of these polymeric additives in without phosphorus ADD composition, the results are shown in the Table III, and test their performances in phosphorous ADD composition, the results are shown in down in the Table VI.
Embodiment 34
This embodiment has illustrated the preparation of polymeric additive of the present invention, comprises the polymerized unit of the ethyl propenoate of the polymerized unit of toxilic acid of polymerizing acrylic acid unit, 20% weight of 60% weight and 20% weight in the additive.Polymeric additive is similar to the additive of embodiment 1 and 2, but molecular weight (Mw) is in the centre of these two embodiment additives.
In device as described in embodiment 1, add the accelerator solution of ferrous sulfate in deionized water of 342.8g deionized water, 65.8g maleic anhydride, 1.05g sodium metabisulfite and 10.2g 0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, keeps this temperature, and begins to add following four kinds of different materials simultaneously:
1) 246.2g glacial acrylic acid,
2) 82.9g ethyl propenoate,
3) the sodium metabisulfite material solution of 26.1g sodium metabisulfite in the 105.3g deionized water,
4) initiator solution of 9.24g Sodium Persulfate in the 105.3g deionized water.
The sodium metabisulfite material solution was added in the reaction mixture through 75 minutes, and vinylformic acid, ethyl propenoate and initiator solution are in 90 minutes adding reaction mixtures.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare two kinds of independent solution, be made up of in 2.6g deionized water the 0.5g Sodium Persulfate a kind of the be made up of in the 2.6g deionized water with another kind of the 0.5g sodium metabisulfite, and when maintenance phase of 15 minutes finishes, follow monomer and join in the reaction mixture, reaction mixture kept 15 minutes at 72 ℃ again, added afterwards again and followed the solution that monomer adds as mentioned above.Reaction mixture was kept again 15 minutes in 72 ℃, then be as cold as 25 ℃.
By slowly adding the aqueous sodium hydroxide solution of 358.8g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 40.55% weight solid solution.Weight-average molecular weight (Mw) is 5480, and number-average molecular weight (Mn) is 4270, and both ratio is 1.37.Test the performance of this polymerisate in phosphorous ADD prescription, the results are shown in down in the Table VI.
Embodiment 35
This embodiment has illustrated the preparation of comparative polymer additive, comprises the polymerized unit of ethyl propenoate of polymerizing acrylic acid unit, 20% weight of 80% weight in the additive.This polymeric additive is similar to the additive of embodiment 30, but the molecular weight of this embodiment additive is high slightly.
In 5 liter of 4 neck round-bottomed flask of mechanical stirrer, reflux exchanger and thermopair is housed, add the accelerator solution of ferrous sulfate in deionized water of 996.8g deionized water, 4.5g sodium metabisulfite and 27.2g 0.15% weight, form reaction mixture.Reaction mixture is heated to 72 ℃, keeps this temperature, and begins to add following four kinds of different materials simultaneously:
1) 1087.4g glacial acrylic acid,
2) 271.8g ethyl propenoate,
3) the sodium metabisulfite material solution of 77.0g sodium metabisulfite in the 317.1g deionized water,
4) initiator solution of 17.8g Sodium Persulfate in the 181.2g deionized water.
The sodium metabisulfite material solution was added in the reaction mixture through 75 minutes, and glacial acrylic acid, ethyl propenoate and initiator solution are in 90 minutes adding reaction mixtures.
Reinforced finishing keeps reaction mixture 15 minutes at 72 ℃.Prepare a kind of solution of in the 9.0g deionized water, forming by the 0.5g Sodium Persulfate, and when 15 minutes maintenance phases finished, follow monomer and join in the reaction mixture, reaction mixture kept 15 minutes at 72 ℃ again, added afterwards again and followed the solution that monomer adds as mentioned above.Reaction mixture was kept again 15 minutes in 72 ℃, then be as cold as 25 ℃.
By slowly adding the aqueous sodium hydroxide solution of 1117.0g 50%, make the reaction mixture PH7.0 that neutralizes, and keep temperature to be lower than 25 ℃.
The gained polymerisate is to contain 43.91% weight solid solution.Weight-average molecular weight (Mw) is 4330, and number-average molecular weight (Mn) is 3560, and both ratio is 1.22.Test the performance of this polymerisate solution in phosphorous ADD prescription, the results are shown in down in the Table VI.
Table VI embodiment vinylformic acid maleic acid ester content ester Mw film is the film result as a result
Formula I I formula I II 9 40 40 20 HPA 3,960 1.45 1.15 14 60 20 20 HPA 5,860 0.9 0.5 15 70 10 20 HPA 4,030 0.9 0.7 17 100 0 0-4,500 2 0.9 32 70 3030-3,500 1.0 1.1 33 70 30 0-30,000 1.8 0.7 34 60 20 20 EA, 5,480 0.6 0.3/0.5,35 80-20 EA 4,330 0.8 (mixing)
21.25 contrast
1-----3 2.5
1Contrast is the phosphorous prescription of no polymeric additive.
2Used term " mixes " the irregular film that is expressed as striped.
3Not toxilic acid but methacrylic acid.
Claims (40)
1. be adapted at being used to reduce film formed component of polymer in the without phosphorus automatic dishwashing detergents composition, contain the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, low alkyl group are unsubstituted and the weight-average molecular weight of multipolymer is 1000-30000.
2. the component of polymer of claim 1, the wherein unsaturated C of one or more single ethylene types
4-C
6Di-carboxylic acid exists with 5-30%mol.
3. the component of polymer of claim 1, the wherein unsaturated C of one or more single ethylene types
4-C
6Di-carboxylic acid exists with 10-20%mol.
4. the component of polymer of claim 1, wherein one or more (methyl) lower alkyl acrylate exist with 10-30%mol.
5. the component of polymer of claim 1, wherein one or more (methyl) lower alkyl acrylate exist with 15-25%mol.
6. the component of polymer of claim 1, wherein the weight-average molecular weight of multipolymer is 2000-15000.
7. the component of polymer of claim 1, wherein the weight-average molecular weight of multipolymer is 3500-10000.
8. the component of polymer of claim 1, wherein C
3-C
6Monocarboxylic acid is a vinylformic acid.
9. the component of polymer of claim 1, wherein C
4-C
6Di-carboxylic acid is a toxilic acid.
10. the component of polymer of claim 1, wherein (methyl) lower alkyl acrylate is selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate and (methyl) butyl acrylate.
11. be adapted at being used to reduce film formed component of polymer in the without phosphorus automatic dishwashing detergents, contain the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, at least a low alkyl group replaces with hydroxyl, and the weight-average molecular weight of this multipolymer is 1000-30000, PH be 2 or lower condition under polymerization.
12. the component of polymer of claim 11, wherein one or more unsaturated C
4-C
6Di-carboxylic acid exists with 5-30%mol.
13. the component of polymer of claim 11, wherein one or more unsaturated C
4-C
6Di-carboxylic acid 10-20%mol exists.
14. the component of polymer of claim 11, wherein one or more (methyl) lower alkyl acrylate 10-30%mol exists.
15. the component of polymer of claim 11, wherein one or more (methyl) lower alkyl acrylate 15-25%mol exists.
16. the component of polymer of claim 11, wherein the weight-average molecular weight of multipolymer is 2000-15000.
17. the component of polymer of claim 11, wherein the weight-average molecular weight of multipolymer is 3500-10000.
18. the component of polymer of claim 11, wherein C
3-C
6Monocarboxylic acid is a vinylformic acid.
19. the component of polymer of claim 11, wherein C
4-C
6Di-carboxylic acid is a toxilic acid.
20. the component of polymer of claim 11, wherein (methyl) lower alkyl acrylate is selected from (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate and (methyl) vinylformic acid hydroxy butyl ester.
21. a without phosphorus automatic dishwashing detergents composition comprises a kind of multipolymer of 1-20% weight, this multipolymer contains the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, low alkyl group is unsubstituted, and the weight-average molecular weight of this multipolymer is 1000-30000.
22. the without phosphorus automatic dishwashing detergents composition of claim 21, wherein multipolymer exists with the content of 2-10% weight.
23. the without phosphorus automatic dishwashing detergents composition of claim 21, wherein the content of washing assistant 20-90% weight exists.
24. the without phosphorus automatic dishwashing detergents composition of claim 21, wherein SiO
2/ M
2The O ratio is 1: 1-3.5: 1 alkalimetal silicate exists as the content of corrosion inhibitor with 1-20% weight.
25. the without phosphorus automatic dishwashing detergents composition of claim 21, wherein one or more low foam water soluble surfactants exist with the content of 0.1-10% weight.
26. the without phosphorus automatic dishwashing detergents composition of claim 25, wherein one or more tensio-active agents comprise nonionogenic tenside.
27. the without phosphorus automatic dishwashing detergents composition of claim 25, wherein one or more tensio-active agents comprise the anion surfactant that the content with 0.1-5% weight exists.
28. a without phosphorus automatic dishwashing detergents composition comprises a kind of multipolymer of 1-20% weight, this multipolymer contains the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, at least a low alkyl group replaces with hydroxyl, and the weight-average molecular weight of this multipolymer is 1000-30000, PH be 2 or lower condition under carry out polymerization.
29. the without phosphorus automatic dishwashing detergents composition of claim 28, wherein multipolymer exists with the content of 2-10% weight.
30. the without phosphorus automatic dishwashing detergents composition of claim 28, wherein washing assistant exists with the content of 20-90% weight.
31. the without phosphorus automatic dishwashing detergents composition of claim 28, wherein SiO
2/ M
2The O ratio is 1: 1-3.5: 1 alkalimetal silicate exists as the content of corrosion inhibitor with 1-20% weight.
32. the without phosphorus automatic dishwashing detergents composition of claim 28, wherein one or more low foam water soluble surfactants exist with the content of 0.1-10% weight.
33. the without phosphorus automatic dishwashing detergents composition of claim 32, wherein one or more tensio-active agents comprise nonionogenic tenside.
34. the without phosphorus automatic dishwashing detergents composition of claim 32, wherein one or more tensio-active agents comprise the anion surfactant that the content with 0.1-5% weight exists.
A 35. the minimizing film forming method of shape on institute's wash up in automatic dishwasher, be included in the aqueous mixture wash dining set of using the without phosphorus automatic dishwashing detergents that contains a kind of multipolymer in the automatic dishwasher, this multipolymer contains the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, low alkyl group is unsubstituted, and the weight-average molecular weight of this multipolymer is 1000-30000.
36. the method for claim 35, wherein automatic dishwashing detergents exists with the content of 0.1-1.0% weight, based on the gross weight of aqueous mixture.
37. the method for claim 35, wherein automatic dishwashing detergents exists with the content of 0.2-0.7% weight, based on the gross weight of aqueous mixture.
A 38. the minimizing film forming method of shape on institute's wash up in automatic dishwasher, be included in the aqueous mixture wash dining set of using the without phosphorus automatic dishwashing detergents that contains a kind of multipolymer in the automatic dishwasher, this multipolymer contains the unsaturated C of one or more single ethylene types of 40-85%mol
3-C
6The unsaturated C of the single ethylene type of one or more of monocarboxylic polymerized unit, 5-50%mol
4-C
6The polymerized unit of one or more of the polymerized unit of di-carboxylic acid and 10-40%mol (methyl) lower alkyl acrylate, at least a low alkyl group replaces with hydroxyl, and the weight-average molecular weight of this multipolymer is 1000-30000, PH be 2 or lower condition under carry out polymerization.
39. the method for claim 38, wherein automatic dishwashing detergents exists with the content of 0.1-1.0% weight, based on the aqueous mixture gross weight.
40. the method for claim 38, wherein automatic dishwashing detergents exists with the content of 0.2-0.7% weight, based on the aqueous mixture gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96122672 CN1154375A (en) | 1995-10-27 | 1996-10-25 | Polycarboxylates for automatic dishwashing detergents |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US008019 | 1995-10-27 | ||
| US729885 | 1996-10-11 | ||
| CN 96122672 CN1154375A (en) | 1995-10-27 | 1996-10-25 | Polycarboxylates for automatic dishwashing detergents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154375A true CN1154375A (en) | 1997-07-16 |
Family
ID=5127405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96122672 Pending CN1154375A (en) | 1995-10-27 | 1996-10-25 | Polycarboxylates for automatic dishwashing detergents |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154375A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490228B (en) * | 2006-07-24 | 2012-11-14 | 埃科莱布有限公司 | Warewashing composition for use in automatic dishwashing machines, and method for using |
| CN103314022A (en) * | 2010-10-29 | 2013-09-18 | 贝兰德科技股份有限公司 | Copolymer that can be dissolved or disintegrated in water |
| CN108138091A (en) * | 2015-10-09 | 2018-06-08 | 罗门哈斯公司 | For reducing the additive of the spot in automatic bowl system |
| CN112166177A (en) * | 2018-06-27 | 2021-01-01 | 罗门哈斯公司 | Method for cleaning plastics with dispersant copolymers |
| CN112166178A (en) * | 2018-06-27 | 2021-01-01 | 罗门哈斯公司 | Plastic cleaning process using dispersant copolymers |
-
1996
- 1996-10-25 CN CN 96122672 patent/CN1154375A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490228B (en) * | 2006-07-24 | 2012-11-14 | 埃科莱布有限公司 | Warewashing composition for use in automatic dishwashing machines, and method for using |
| CN103314022A (en) * | 2010-10-29 | 2013-09-18 | 贝兰德科技股份有限公司 | Copolymer that can be dissolved or disintegrated in water |
| US9399691B2 (en) | 2010-10-29 | 2016-07-26 | Bellandtechnology Ag | Water-soluble or water-disintegrable copolymer |
| CN103314022B (en) * | 2010-10-29 | 2016-11-09 | 贝兰德科技股份有限公司 | Water-soluble or disintegratable in water copolymer |
| EP2447292B1 (en) * | 2010-10-29 | 2017-03-29 | BellandTechnology AG | Water soluble copolymer which disintegrates in water |
| US9777090B2 (en) | 2010-10-29 | 2017-10-03 | Bellandtechnology Ag | Water-soluble or water-disintegrable copolymer |
| CN108138091A (en) * | 2015-10-09 | 2018-06-08 | 罗门哈斯公司 | For reducing the additive of the spot in automatic bowl system |
| CN112166177A (en) * | 2018-06-27 | 2021-01-01 | 罗门哈斯公司 | Method for cleaning plastics with dispersant copolymers |
| CN112166178A (en) * | 2018-06-27 | 2021-01-01 | 罗门哈斯公司 | Plastic cleaning process using dispersant copolymers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1193086C (en) | Water phase method for preparing low molecular polymer | |
| CN1222573C (en) | (Meth) acrylic acid (salt) polymer and manufacturing method thereof | |
| CN1246353C (en) | Polymer composition and method for removing dirt from fabric of said polymer | |
| CN1197947C (en) | Alkaline solid block composition | |
| CN1083492A (en) | The preparation of biodegradable multipolymer | |
| CN1196773C (en) | Detergent builder, production process therefor, and poly-(meth) acrylic acid (or salt) polymer and use thereof | |
| CN1008634B (en) | Contain the lotion-aid combination and the application thereof of ether carboxylate and polycarboxylate and/or ethoxylated amine | |
| CN1656204A (en) | Use of an amphoteric copolymer in a dish washing composition | |
| CN1531586A (en) | Low foaming/defoaming compositions containing alkoxylated quaternary ammonium compounds | |
| CN1154137A (en) | Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents | |
| CN1093560C (en) | Detergent builder, process for producing the same, and detergent composition containing said builder | |
| CN1059555A (en) | The improved scale remover that is used for granular laundry detergent | |
| CN1585786A (en) | Graft polymer with sidechains comprising nitrogen heterocycles | |
| CN1157424C (en) | Water-soluble polymer and use thereof | |
| US9347027B2 (en) | Automatic dishwashing detergent | |
| US9896647B2 (en) | Automatic dishwashing detergent with synergistic scale inhibition | |
| CN1298830C (en) | Antifouling detergent for hard surfaces | |
| CN1571830A (en) | Liquid detergent builder and liquid detergent containing the same | |
| CN1222606C (en) | Mild particulate laundry detergent compositions for washing textile fabrics by hand | |
| CN1154375A (en) | Polycarboxylates for automatic dishwashing detergents | |
| CN1166181A (en) | Washing method and detergent compsns. | |
| CN1950493A (en) | Copolymers comprising N-heterocyclic groups, and use thereof as an additive in detergents | |
| CN1207763A (en) | Detergent compositions contg. soil release polymers | |
| CN1284807C (en) | Water-soluble copolymer | |
| CN1738844A (en) | Partially esterified copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, vinylaromatic compounds and other monoethylenically unsaturated monomers containing heteroatoms |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |