DE2717809A1 - COMPOSITION SUITABLE FOR HIGH PERFORMANCE CLEANERS - Google Patents

Description

TD LT f * Patent attorneys:

IEDTKE - DÜHLING - RINNE · ■ UPUPE Dipl.-Ing Tiedtke

Dipl.-Chem. Bühling

2717809 Dipl.-Ing. Chins

Dipl.-Ing. Group

Bavariarlng 4, Postfach 20 24 8000 Munich 2

Tel .: (0 89) 53 96 53-56

Telex: 5 24 845 tipat

cable. Germaniapatent Munich

April 21, 1977

B 8121
ICI case H.28728 / 29038

IMPERIAL CHEMICAL INDUSTRIES LIMITED
London, UK

Composition suitable for high-performance cleaners

709844/0951

Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account 670-43-804

B 8121

The invention relates to compositions suitable for high performance cleaners, i.e. surface active ones Mixtures for "heavy-duty cleaning" such as tank cleaning, engine cleaning and metal degreasing are suitable.

In GB-PS 1 459 104 of the applicant are a Process for dispersing oil in water and compositions suitable therefor indicated. The procedure includes a contact of oil and water with an alkyd resin, which is the remainder of a water-soluble polyalkylene glycol as a resin component. In the GB-PS the cleaning of oil-contaminated storage containers or storage tanks given as an application example.

A particularly effective composition has now been developed for "heavy-duty cleaning", in particular for cleaning surfaces contaminated with oil or other organic hydrophobic materials e.g. using the method described in GB-PS 1,459,104.

The composition according to the invention suitable for high-performance cleaners is characterized by

a) an alkyd resin, in which a resin component by the A residue of a polyalkylene glycol is formed which is soluble in water,

b) an oxyethylene / oxypropylene copolymer, which is preferably 15 to 70 oxypropylene units and 12 to Contains 200 oxyethylene units and

c) a nonionic surface-active one different from the oxyethylene / oxypropylene copolymer according to (b) Middle.

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This composition contains the active ingredients for an effective high-performance cleaner, however it is highly viscous and difficult to handle. A solvent is therefore advantageously added. That Solvent can be a hydrocarbon solvent as described below, however the composition will preferably mixed with a solvent that is miscible with both oil and water is forming a concentrate that is relatively easy to move and convenient to pack and transport is. This concentrate can then be mixed with the same or a different solvent or diluent before use such as being diluted with water. A preferred oil and water miscible solvent is a glycol ether such as the methyl ether of a polypropylene glycol with 2 to 12 propylene oxide units.

The polyalkylene glycol component of the alkyd resin is soluble in water, the term "water-soluble" being understood is that the polyalkylene glycol at the temperature at which the composition is used as a cleaner, is below its cloud point.

Alkyd resins are generally the condensation products of a polybasic acid with a polyhydric alcohol and usually a monobasic acid. The alkyd resins useful in the invention include the water soluble! Polyalkylene glycol preferably as at least a portion of the polyhydric alcohol component. Additional polyhydric alcohols that can be employed include diols, suitably up to Contain 20 carbon atoms, such as mono-, di- and triethylene glycol, Mono-, di- and tripropylene glycol, mono-, di- and tributylene glycol and neopentyl glycol; water-insoluble Polyglycols such as polypropylene glycol and polybutylene glycol; Triols suitably containing up to 20 carbon atoms such as glycerin, trimethylolpropane

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and trimethylol ethane; Polyols also suitably containing up to 20 carbon atoms such as pentaerythritol, Dipentaerythritol and sorbitol; and ethoxylated amines, which also suitably have up to 20 carbon atoms contain, such as di- and triethanolamine.

The polybasic acid component of the alkyd resin can be saturated or - olefinically or aromatic - unsaturated be. Commonly used acids are aliphatic or aromatic dibasic acids with up to to 20 carbon atoms, preferably up to 10 carbon atoms such as ortho-, iso- or terephthalic acid, maleic acid, Fumaric acid, itaconic acid, mesaconic acid, citraconic acid, azelaic acid, succinic acid, adipic acid, glutaric acid or suberic acid. The polybasic acid can also be a tribasic, suitably aromatic acid with up to 20, preferably up to 10 carbon atoms such as trimellitic acid or tetrabasic such as e.g. Pyromellitic acid. "Dimer" acids, i.e. mixed dibasic acids and tribasic carboxylic acids obtained by the polymerization of unsaturated monobasic acids can also be used.

The optional monobasic acid component of the alkyd resin, which acts as a monofunctional chain end link acts, can come from a free acid or from an ester of the acid, in particular a glyceride. The acid can be an aromatic acid, especially an alkyl substituted benzoic acid, however is suitably an aliphatic saturated or ethylenically unsaturated acid of up to 30 carbon atoms and preferably having 6 to 22 carbon atoms. Mixtures of acids or their esters can also be used for the monobasic acid component can be provided, in particular naturally occurring mixtures such as tall oil acids or acids derived from linseed oil, soybean oil, whale oil,

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Dried castor oil, tung oil, fish oil, safflower oil, oiticica oil, cottonseed oil, or coconut oil. Individual acceptable acids include isooctanoic acid, 2-ethylhexanoic acid, isodecanoic acid, lauric acid, and pelargonic acid. Other monobasic acid chain end links known to the person skilled in the art can also be used, such as chain end links in general, for example monohydric alcohol chain end links, in particular C ₁ to CQ alkanols and monobasic amine end links, in particular primary C ₁ to CpQ

"Polyalkylene glycol" is the common name for Polymers of an alkylene glycol of the general formula,

H (O.C-C). where the structure .0.C-C.

II "Il

is derived from an olefin oxide and forms a polyoxyalkylene chain. For example, polyethylene glycol, H (OCH ₂ CH ₂ ) _n OH, is derived from ethylene oxide, CH ₉ CHp.

0

The water-soluble polyalkylene glycol is preferably polyethylene glycol, but low molecular weight can be used Polypropylene glycol or polyalkylene glycols with a major part of ethyleneoxy groups together with minor ones Proportions of randomly or blockwise distributed propyleneoxy and / or butyleneoxy groups are also used will. In addition to the water-soluble polyalkylene glycol residue, the alkyd resin can contain residues of one or more water-insoluble polyalkylene glycols such as those from higher molecular weight polypropylene or polybutylene glycols contain. Furthermore, the alkyd resin can contain residues of one or more polyalkylene glycols with water-soluble polyalkyleneoxy blocks together with water-insoluble polyalkylene

contain oxy blocks, such as polyethyleneoxy [water-soluble] / Polypropyleneoxy [water insoluble] block copolymers

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(Poly (ethylene / propylene) glycol. Alternatively, the blocks of propylene oxide and ethylene oxide units can be present in an alkoxylated amine such as a C to Cp _n diamine such as ethylene diamine

The alkyd resin contains at least 5 wt.% Of the resin of polyalkylene glycol and suitably at least 10%. The alkyd resin preferably contains 40 to 90%, in particular 50 to 80% by weight, of the polyalkylene glycol. Desirably, the alkyd resin has a viscosity of at least 1 poise (as a 95% (solids) solution in xylene).

The water-soluble polyalkylene glycol forming part of the alkyd resin suitably has a molecular weight in the range from 100 to 10,000, preferably 400 to 10,000 and especially 600 to 5,000 C ₁ - to Cg alcohol such as methanol or ethanol) or be esterified with a lower (C ^ - to Cr) alkanoic acid.

Although the polymeric nature of the alkyd and its carbon and hydrogen content help create a To impart an oleophilic character will reinforce the oleophilic character through a suitable selection of the components of the alkyd other than the water-soluble polyalkylene glycol are preferred. So be preferred Components selected that would be soluble in the oil under the cleaning conditions. "Oil-soluble" is understood here to mean that the component in question under the treatment conditions in the particular polluting oil is soluble and not self-associated. While the solubility properties of a given oil will vary, however, suitable components can easily be selected on the basis of simple experiments. An oil soluble Component of the alkyd resin can be among those mentioned above

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alkyd constituents described are selected. In particular, the oil-soluble component can be a long-chain one saturated or unsaturated aliphatic monobasic acid or a long-chain alkyl-substituted aromatic monobasic acid or a "dimer" acid. Similarly, the oil-soluble component can be a water-insoluble one Polyalkylene glycol such as polybutylene glycol or a polyalkylene glycol with a significant proportion be on blocks of butyleneoxy units.

Alkyd resins useful in the context of the invention can by reacting an alkyd resin containing carboxyl or ester groups with the polyalkylene glycol Hydroxyl ends by a standard esterification technique or Transesterification can be produced. Alternatively, the alkyd resin can be produced from the ingredients of which one or more of the polyalkylene glycol units. For example, a polyol, such as glycerin, with a Olefin oxide, such as ethylene oxide, are reacted in such a way that the OH groups of the glycerine with the formation of a glycerine / polyethylene glycol ether react. This product can then be mixed with the polybasic acid and, if necessary, with the monobasic acid Acid can be converted to alkyd under esterification conditions. In a similar way, a polybasic Acid with a Clefin oxide to the ester of the polyalkylene glycol be implemented and provided that it has been ensured that the polybasic acid one or more retains free COOH groups, it can be used for the alkyd formation reaction. With a third preparation method the alkyd resin can be prepared from its basic components, the polyalkylene glycol forms such a component.

The oxyethylene / oxypropylene copolymer preferably comprises a block of 20 to 40 propylene oxide units, especially about 30 units and an average of 20 to 30

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Ethylene oxide units per molecule, in particular about 26 ethylene oxide units per molecule.

The non-ionic surface-active agent preferably comprises one or more representatives from the group of ethoxylates from Cr to CpQ alcohol with 3 to 15 ethylene oxide units per molecule, ethoxylates of an alkylphenol and / or ethoxylates of a carboxylic acid.

The alcohol ethoxylate is suitably derived from an alcohol having 8 to 20, preferably 10 to 15, carbon atoms and is especially a primary alcohol with a minimum of branching in the carbon chain. Isodecanol or a mixture of primary C ₁ - and C 1-4 alcohols with 40 to 60 % straight chain and 60 to 40 % chains with a methyl branch in the 2-position is particularly suitable. The alcohol ethoxylate preferably comprises an average of 2 to 10, in particular 4 to 8, ethylene oxide units per molecule, and if the above-mentioned mixture of C.sub.1 and C.sub.14 alcohols is used, the average number of ethylene oxide units per molecule is advantageously 6 .

The alkyl phenol ethoxylate preferably includes a C1 to C6 alkyl group such as an octyl or nonyl group in para position to the ethoxylated phenolic hydroxyl group. The ethoxylate suitably includes 2 to 20 ethylene oxide units, preferably 3 to 10 ethylene oxide units.

The ethoxylate of the carboxylic acid is preferably derived from an aliphatic carboxylic acid having 8 to 20 carbon atoms in the molecule such as lauric acid, stearic acid or from a naturally occurring acid such as Coconut oil or tall oil acids. The ethoxylate contains

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preferably an average of 2 to 10 ethylene oxide units per acid molecule, in particular 3 to 7 ethylene oxide units.

The composition according to the invention can also be other known to contain ingredients used in detergents. So the composition can for example comprise an ingredient to reduce foaming of the composition in use. For this purpose are surface-active agents based on Fluorocarbon suitable such as those sold as MONFLOR ^ by Imperial Chemical Industries Limited Products that are only required in low concentrations of e.g. 1 to 100 ppm.

The diluent with which the composition or concentrate can be diluted is usually chosen so that it is a solvent for the hydrophobic material with the invention Composition of a surface such as the inside of a tank to be eliminated by cleaning. The compositions of the invention are on Most commonly used for cleaning surfaces with residues of crude oil or petroleum fractions are contaminated and it has been found that for this purpose a hydrocarbon diluent, preferably an aromatic hydrocarbon diluent most suitable, especially a diluent, is mixed aromatic hydrocarbons with 6 to 20 carbon atoms. Suitable diluents include kerosene, xylenes and turpentine substitute, although in many cases water itself can be used.

Compositions according to the invention preferably comprise

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1 to 20 parts by weight of alkyd resin, 0.1 to 10 parts by weight Oxyethylene / oxypropylene copolymer and 1 to 20 parts by weight non-ionic surfactant. Part of this composition can be used to form the concentrate be diluted with 5 to 100 parts by weight of solvent which is miscible with oil or with oil and water and for use as a cleaner, one part of concentrate can be mixed with another 5 to 10,000 parts of thinner be diluted.

The concentrate or the concentrate plus diluent according to the invention are suitably used in Water applied to the surface to be cleaned. You can use the concentrate or concentrate plus diluent expediently in a concentration in the range from 0.05 to 20% by weight of their total weight with the water are preferably used in a concentration of 0.1 to 10% by weight. The most effective method of application is in spraying the aqueous mixture onto the surface to be cleaned, the spray path being a part forms a circulation system through which the aqueous mixture is circulated in the circuit.

In addition to being effective in terms of removal, compositions according to the invention are hydrophobic Material from the surface to be cleaned has the additional advantage that it does not result in a stable one Emulsion lead so that the hydrophobic material that is washed off the surface can easily become one of the Water forms a separate phase and can thus be easily removed.

Possible uses of the compositions according to the invention include the following: tank cleaning, drum cleaning, Metal degreasing, engine cleaning, concrete degreasing (e.g. workshop and garage floors); as cleaning

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ger for surfaces with non-polymerized unsaturated Polyester resins, alkyd resins, natural fats and deposits of edible oils are contaminated and for general cleaning of ceramics, PVC, melamine / formaldehyde plastics etc.

The invention is explained below using an example in which the following test apparatus is used became:

The apparatus consisted of an h 1 beaker mounted on a hot plate with a thermometer to read the temperature of the solution during the test. However, a mild steel plate was clamped in the beaker above the liquid level and a glass tube extended to a nozzle was arranged at a distance of 5 cm from the plate. The glass tube was connected to a circulation pump via a rubber hose, the suction side of which was also connected to the solution in the beaker via a rubber hose. For the test, the plate was coated with a hydrophobic material (tank residues of heavy fuel oil) and the solution to be tested (500 ml) was placed in the beaker. The solution was then heated to 50 ⁰ C and taken Prmpr (with 100 1 / hr) into operation was promoted vobei the solution through the nozzle to the coated plate. The agitation was continued for 5 minutes and the cleaning of the plate was noted at regular intervals.

example

The composition according to the invention consisted of:

3.0 parts by weight of alkyd resin, the 1.75 mol of polyethylene glycol (MW 600) 0.6 mol pentaerythritol,

0.97 moles of trimellitic anhydride and 3.0

Moles of tall oil fatty acids includes; 7098U / 0951

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10.0 parts by weight of ethoxyxated isodecanol, the average Contains 6 ethylene oxide units per molecule;

5.0 parts by weight

ethoxylated tall oil, which has an average of 5 ethylene oxide units per molecule contains;

1.0 part by weight

a propylene glycol / propylene oxide reaction product having a molecular

weight from 1500 to 1800, that with ethylene oxide up to an ethylene oxide unit content of 10% by weight has been converted into the final molecule.

This composition was made by adding 10 parts by weight of the methyl ether of a polypropylene glycol converted into a concentrate with - on average - 3.7 propylene oxide units per molecule.

The concentrate was diluted with synthetic seawater (containing 3.5% by weight sodium chloride) to form a 0.1% by weight solution which was then used for the plate cleaning test described above. After the test time of 5 minutes, the plate was 90 % clean.

The concentrate was also diluted with kerosene (in the ratio of 5 parts kerosene per part concentrate) and the resulting mixture used as a metal cleaner. 50 liters of the mixture were placed in a vat and dipped a heavily soiled machine part into the mixture. The part was then lightly brushed and finally washed with water under a tap, when oil and grease from the shiny metal surface were removed.

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The concentrate was also used as a cleaner for the floor of a garage, some being concentrate with three parts of "CAROMAX" ® 20 (a mixture of methyl- and ethyl-substituted benzenes, naphthalenes, Aromatic hydrocarbons comprising indenes and methylindenes; with the resulting mixture a dirty and weathered garage floor was brushed. After a minute of contact, the Washed the soil with water, after which a substantial amount of the oil pollution was removed.

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Claims (12)

B 8121 Claims Composition suitable for high-performance cleaners, characterized by a) an alkyd resin in which a resin component is formed by the remainder of a polyalkylene glycol, which is soluble in water and preferably has a molecular weight in the range from 100 to 10,000 Has, b) an oxyethylene / oxypropylene copolymer and c) a nonionic surface-active one different from the oxyethylene / oxypropylene copolymer according to (b) Middle. 2. Composition according to claim 1, characterized indicates that the alkyd resin by the condensation product of a polybasic acid with a polybasic acid Alcohol and a monobasic acid or a monohydric alcohol or a monobasic amine is, wherein the polyalkylene glycol makes up at least a portion of the polyhydric alcohol. 3. Composition according to claim 2, characterized in that the polyhydric alcohol also contains a diol up to 20 carbon atoms such as mono-, di- or triethylene glycol, mono-, di- or tripropylene glycol, Mono-, di- or tributylene glycol, neopentyl glycol, polypropylene glycol or polybutylene glycol, a triol with up to 20 carbon atoms such as glycerine, trimethylolpropane or trimethylolethane, a polyol with up to 20 carbon atoms such as pentaerythritol, dipentaerythritol or sorbitol or an ethoxylated amine with 7098U / 09S1 ORIGINAL INSPECTED B 8121 up to ku carbon atoms such as diethanolamine or triethanolamine includes. 4. Composition according to claim 2 or 3, characterized in that that the polybasic acid is an aliphatic or aromatic dibasic or polybasic Acid with up to 20 carbon atoms such as ortho, iso or terephthalic acid, maleic acid, fumaric acid, Itaconic acid, mesaconic acid, citraconic acid, succinic acid, adipic acid, trimellitic acid, pyromellitic acid or "Dimer" acids. 5. Composition according to one of Claims 2 to 4, characterized in that the monobasic acid is replaced by an aliphatic saturated or unsaturated acid with up to 30 carbon atoms, preferably 6 to 22 Carbon atoms such as tall oil acids, isooctanoic acid 2-ethylhexanoic acid, isodecanoic acid, lauric acid, pelargonic acid or from linseed oil, soy oil, whale oil, dried Acids derived from castor oil, tung oil, fish oil, safflower oil, oiticica oil, cottonseed oil or coconut oil are formed will. 6. Composition according to one of the preceding claims, characterized in that the water-soluble polyalkylene glycol by polyethylene glycol, a low molecular weight Polypropylene glycol or a polyalkylene glycol with a major proportion of ethyleneoxy groups with a smaller proportion of randomly or blockwise distributed propyleneoxy or butyleneoxy groups is formed. 7. Composition according to any one of the preceding claims, characterized in that the water-soluble Polyalkylene glycol in an amount of at least 5% by weight 7098U / 0951 B 8121 -x- and preferably 40 to 90% by weight. 8. Composition according to one of the preceding claims, characterized in that the oxyethylene / 5 oxypropylene copolymers 15 to 70 and preferably one Block of 20 to 40 propylene oxide units and 12 to 200, preferably 20 to 30 ethylene oxide units per Contains molecule. 9. Composition according to one of the preceding claims, characterized in that the nonionic surface-active agent different from oxyethylene / oxypropylene copolymers by an ethoxylate of a Cg to C ₂₀ , preferably Cq to C ₂₀ alcohol such as isodecanol or a mixture of primary C ₁ , - and C ₁ (- alcohols with 40 to 60 % straight-chain components and 60 to 40 % chains with a methyl branch in the 2-position, the alcohol 3 to ^ 5, preferably 4 Contains to 8 ethylene oxide units per molecule or that the nonionic surface-active agent is formed by an ethoxylate of an alkylphenol, preferably a C ^ - to C ₁ g-para-alkylphenol such as para-octyl- or para-nonylphenol, which is preferably 2 to 20 ethylene oxide units or that the nonionic surface-active agent by an ethoxylate of a carboxylic acid, preferably a Cg to CpQ carboxylic acid such as lauric acid, stearic acid, coconut oil acids o the tall oil acids is formed, which preferably has 2 to 10 ethylene oxide units per molecule. 10. Composition according to one of the preceding claims, characterized by a content of one preferably a solvent formed by hydrocarbons or a solvent miscible with oil and water 709844/0951 B 8121 agents such as a glycol ether such as polypropylene glycol methyl ether with 2 to 12 propylene oxide units. 11. Composition according to one of the preceding claims, characterized by 1 to 20 parts by weight of alkyd resin, 0.1 to 10 parts by weight of oxyethylene / oxypropylene copolymer, 1 to 20 parts by weight non-ionic surfactant Medium and optionally 5 to 100 parts by weight of solvent. 12. Use of a composition according to one of the preceding claims, in particular for cleaning purposes, characterized in that the composition is first treated with a diluent, preferably a hydrocarbon or oil- and water-miscible solvents such as water, kerosene, xylenes, turpentine oil substitute, mixed, aromatic. Hydrocarbons with 6 to 20 Carbon atoms or a glycol ether is diluted, the diluent preferably 5 to 10,000 Parts by weight. 7098U / 09S1