Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/04—Anhydrides, e.g. cyclic anhydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F244/00—Coumarone-indene copolymers

Definitions

• This invention relates to synthetic detergent compositions. More particularly, it relates to the use of the watersoluble organic polymer salts of copolymers of 3a,4,5,6, 7,7a-hexahydro-4,7-methanoindene and maleic anhydride as the builders for synthetic anionic, nonionic and/or amphoteric surface active compounds which are suitable as detergents in aqueous solutions.
• the term builder signifies a substance used with or in a detergent to aid in cleansing.
• detergents contain a surface active material, a builder for promoting the functions of said surface active material, and small quantities of substances which protect against recontamination, a bleaching agent, a fluorescent dyestuff, a sizing agent, etc.
• inorganic builders such as alkali metal carbonates, bicarbonates, phosphates, polyphosphates, borates and silicates, as well as organic builders such as sodium salts of EDTA (ethylenediaminetetraacetic acid) and NTA (nitrilotriacetic acid), among which the most popular is sodium tri-polyphosphate (hereinafter referred to as STP), which is one of the condensation polyphosphates.
• EDTA ethylenediaminetetraacetic acid
• NTA nitrilotriacetic acid
• Condensation polyphosphates such as sodium tripolyphosphate possess an excellent activity as a detergent builder, but, on the other hand, when condensation polyphosphates are mixed with a detergent, they are hydrolyzed under the usual aqueous solution conditions, thus converting them to lower condensation compounds. Hence, they lose their activity as a builder and, thus, deteriorate the detergency efiiciency of the detergent agents. Moreover, when the Waste liquor containing these substances flows into rivers and into sewage water, a great many duckweeds grow to ruin the environmental beauty. In addition, the eifluence of such agents into public waters causes many hazards which have been recently greatly documented. These problems are not solved when utilizing other inorganic and organic builders, because of the disadvantages that these materials have an inferior detergent effect and are not able to produce a detergent composition having excellent detergency efficiency.
• One of the objects of the present invention is to provide a novel synthetic detergent composition having an excellent detergent efiiciency and which can be readily disposed without significant environmental or ecological problems,
• Another object of the invention is to provide a method for the preparation of the described detergent compositions which may be carried out effectively and advantageously as desired.
• Formula III denotes the copolymerized CM-resin.
• the process for preparing such a CM- resin is as follows.
• the 3a,4,5,6,7,7a-hexahydro4,7-methanoindene and maleic anhydride reactants are subjected to radical copolymerization in a molar ratio of 2:8 to 8:2 in the presence or absence of a solvent at a reaction temperature of 50 to 200 C. under a pressure of 1 to 20 kg./cm. or under a reduced pressure.
• a mixture of these monomers as the starting material for a CM-resin undergoes a radical copolymerization relatively easily.
• the polymerization is eifected on the basis of the reaction of the double bonds of the monomers.
• the radical initiator employed as the catalyst is added in an amount of from 0.01% to 10% by weight, based on the weight of the monomers.
• the radical initiator to be employed include, for example, azo-bisisobutyronitrile, benzoyl peroxide, di-tertiary-butyl peroxide, hydrogen peroxide, lauryl peroxide, dipropionyl peroxide, acetyl peroxide, peracetic acid, perbenzoic acid, tertiary-butyl hydroperoxide, acetylbenzoyl peroxide, diethyl peroxide, urea peroxide, tetraphosphorus peroxide, alkali metal persulfates, alkali metal perborates, alkali metal percarbonates, ammonium persulfate, ammonium perborate, ammonium percarbonate, etc.
• An autoclave is employed in the case of the high temperature reaction in a solvent of a lower boiling point.
• a specific example of preparing a CM-resin to be cmployed in connection with the present invention can be illustrated as follows. 134 parts of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and 98 parts of maleic anhydride are dissolved in 232 parts of acetone and mixed with 2 parts of benzoyl peroxide as a polymerization initiator and the mixture is agitated at 65 C. for 20 hours. After a sufiicient development of the reaction, the reaction mixture is poured in a sufficient quantity of methanol to precipitate the produced copolymer. The recovered copolymer of CM-resin has a molecular weight of 400600 and a saponification value of 350. The yield is 155 parts by weight.
• the CM-resin obtained in this manner is a polybasic acid, it easily forms water-soluble alkali metal salts when dissolved in an aqueous alkaline solution, such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution or an aqueous ammonium hydroxide solution. Accordingly, the sodium salt of the CM-resin is easily prepared in a known manner, for example, such as the reaction of a CM-resin with an aqueous sodium hydroxide solution.
• an example for the preparation of the sodium salt of a CM-resin can be carried out in the following specific manner.
• a certain volume of 510% sodium hydroxide solution containing 2 moles of NaOH is gradually mixed with 1 mole of the CM-resin with agitation.
• the resulting mixture is dried by any suitable method, such as by means of vacuum drying, freezedrying, spray-drying, or the like, in order to obtain the sodium salt of the CM-resin.
• CM-resins of the invention are available at less expense in accordance with the development of the petrochemical industry.
• CM-resin utilizable in accordance with this invention are water-soluble CM-resins as discussed above, but in practice the alkali metal salts and/or the ammonium salts of CM-resins are most conveniently and advantageously utilized.
• the technique of the present invention is characterized by utilizing as the builder a watersoluble CM-resin and, therefore, the detergency set forth in the following examples is at least superior to the detergency efficiency of the conventionally employed STP. Furthermore, since the builder of the present invention does not contain phosphorus, solutions containing this builder may be discharged into sewage water without the fear of the growth of duckweeds thus radically eliminating public hazards and other environmental problems.
• the sodium salt of the CM-resin obtained in accordance with the present invention possesses a considerable detergency efiiciency by itself and, furthermore, that a detergent composition containing the same with the builder of the surface active material LAS has a very excellent detergency efiiciency.
• Example 2 Employed in the present example are the additive compounds ofpolyoxyethylene nonyl phenyl ether (hereinafter referred to as POENE) with 8 moles and 20 moles of ethylene oxide, respectively (hereinafter referred to as POENE-8 and POENE-20, respectively), as examples of nonionic surface active materials.
• POENE-8 and POENE-20 The following detergent solutions are prepared:
• CM-resin (4) An aqueous solution of 0.04% POENE-ZO and 0.05
• CM-resin Washing is conducted in the same manner and under the same conditions as described in Example 1. The results are shown in Table 2.
• CM-resin builders of the present invention show excellent effects not only with LAS and POENE, specifically exemplified above, but also with any conventional surface active material.
• the water-soluble salts of CM-resins are effective in connection with detergency efficiency as builders in detergent compositions regardless of the particular type of surface active material employed. Therefore, the present invention offers great technical advantages of obtaining detergents suitable for fully automated washing machines.
• a detergent composition consisting essentially of a surface active agent selected from the group consisting of anionic and nonionic surface active agents, and in an amount effective as a builder, a water-soluble salt of a copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and maleic anhydride.
• a detergent composition consisting essentially of a surface active agent selected from the group consisting of anionic and nonionic surface active agents as a detergent and an effective amount of a builder to aid the efficiency of the detergent, the improvement which comprises a water-soluble salt of a copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and maleic anhydride as a builder, said methanoindene and maliec anhydride being in a molar ratio of about 2:8 to 8:2 respectively.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Detergent Compositions (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=11693728

Family Applications (1)

Country Status (3)

Cited By (2)

• 1970
  • 1970-02-02 JP JP45008460A patent/JPS4832403B1/ja active Pending
• 1971
  • 1971-02-02 US US00112060A patent/US3730913A/en not_active Expired - Lifetime
  • 1971-02-02 DE DE2104854A patent/DE2104854C3/de not_active Expired

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