IE48107B1

IE48107B1 - Novel betaine derivatives

Info

Publication number: IE48107B1
Application number: IE881/79A
Authority: IE
Original assignee: Johnson & Johnson; Mona Industries Inc
Priority date: 1978-05-05
Filing date: 1979-08-08
Publication date: 1984-10-03
Also published as: GB2020289B; NL193247C; ATA335679A; IE790881L; ES480266A1; PT69574A; MX150948A; GR64909B; AT376685B; AU4693379A; NZ190363A; PH16742A; AR228016A1; FR2424925A1; NL193247B; NL7903526A; CH650001A5; BE876055A; FR2424925B1; AU528547B2

Abstract

The compounds have the formula:- or in which A is O<(-)>, OM, or -O-Y-R<(+)>; B is O<-> or OM'; X<(-)> is an anion; z is 0-2 and only one of A and B is O<(-)>; R is a group of formula [R'CON(R<2>)-(CH2)n-N(R<3>)(R<4>)-]<(+)>- or in which R<1> is C5-22 alkyl, alkenyl, alkoxy or hydroxyalkyl or up to C20 aryl or aralkyl; R<2> is H, alkyl, hydroxyalkyl, alkenyl, cycloalkyl or polyoxyalkylene; R<3> and R<4> are alkyl, hydroxyalkyl, carboxyalkyl, polyoxylalkylene or R<3> and R<4> form a heterocycle with the N atom; n is 2-12; Z is N, S or O; o is 0-3; p is 1-3 and o + p is 3-4; R<6> is C2-6 alkyl or hydroxyalkyl; Y is alkylene optionally substituted by alkoxy, or hydroxy or interrupted by up to 3 O atoms; M and M' are H, alkyl, hydroxyalkyl, cycloalkyl, aralkyl, aryl or a salt radical provided when either is an organic radical the other is H or a salt radical. The compounds are used as surfactants.

Description

The present invention relates to novel compositions of matter consisting of specific betaine derivatives referred to hereinafter as phosphobetaines and phosphitaines. More particularly, this invention relates to novel amphoteric and zwitterionic betaine surfactants having at least one phosphorous-containing anion in the molecule.

Betaines and certain substituted betaines are known in the art but prior to the present invention the novel phosphobetaines of this invention had not been disclosed or suggested. The phosphobetaines of the present invention exhibit outstanding foaming, viscositybuilding, wetting, cleansing, detergency, anti-static and emulsifying properties and are therefore useful in industrial applications calling for high performance surface active agents. The compounds are also highly stable species and are extremely well tolerated by human tissue, i/e., they exhibit exceptionally low ocular irritation and oral toxicity, and are therefore eminently suited and useful as surface active agents in personal care compositions.

The novel phosphobetaine compounds of the invention may be represented by the following general formula: (ί) ο wherein A is selected from Οθ, OM and -O-Y-R® θ B is selected from 0 and OM' $ is an anion z is Ο, 1 or 2 with the proviso that only one of A and B can be O and z is of a value necessary for charge balance (i.e., when A and B are Cr and OM'., or OM and 0®, respectively, z is 0; when A and B are 0M and OM*, or -O-Y-Rr and 0 , respectively, z is 1; when A is -0-Y-I^ and B is OM', z is 2), R is an amidoamine moiety of the formula -1 Φ - C - N - (CH2)n wherein R^ is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms, R is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cyeloalkyl of up to 6 carbon atoms, preferably of from 2 to carbon atoms, or polyoxyalkalene of up to carbon atoms, 4 R and R , which nay be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms; n is an integer from 2 to 12.

The term polyoxyalkylene radical as used above 2 3 4 in the definition of R , R and R embraces radicals of the ' 55' formula (R - 0 - R ) , wherein R and R are alkyl of from 1 to 4 carbon atoms and m is an integer from about 2 to 10.

The following further definitions apply to formula (I): Y is hydroxy, alkoxy or hydroxyalkyl substituted alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms, which alkylene chain may optionally be substituted with loweralkyl; the alkoxy, hydroxy or hydroxyalkyl substituent being, e.g., of not more than 10 carbon atoms in each case.

M and M', which may be the same or different, are (a) hydrogen, (b) an organic radical selected from alkyl or hydroxyalkyl of up to 6 carbon atoms, polyhydroxyalkyl of up to 10 carbon atoms, glyceryl, cycloalkyl of up to 6 carbon atoms, aryl or arylalkyl of up to 10 carbon atoms, or (c) a salt radical selected from alkali metals (e.g., sodium or potassium), alkaline earth metals (e.g., magnesium or calcium), and mono-, di-, or tri-ethanolamine. With reference to formula (III) below, wherein both M and M' are contained, there is the proviso that when either M or M' is an organic radical (b), the other of M and M' must be hydrogen or a salt radical (c).

The novel phosphitaine compounds of the invention may be represented by the following general formula: (la) R 0® wherein R and Y are as defined above.

Particularly preferred sub-groups of the compounds of formula (I) can be represented as follows: ® ll R - Y - 0 - P - OM (XI) (III) ο * ll iF-y-o-p-om I _ OM' _ 3^ (IV) " i^-y-o-p-o-y-r® l_ — The confounds of general formula (IV) are bisphosphobetaines containing two amine moieties.

Compounds (III) and (IV) require the presence of an anion (X®) for charge balance. Said 3Ϊ® radical can be an anion such as hydroxy or a halide, sulfate, phosphate, or a negatively charged (anion) radical supplied by a solvent or a reactant used in the synthesis of compounds of formulas (III) and (IV). For instance, if® may be the halide moiety (Hal) released in the reactions below.

The phosphobetaine compounds (I) of the invention can be prepared from the corresponding phosphate esters and amine reactants, as follows: II 1) R + Hal-Y-O-P-B -Hal X® ffl 11 R^-Y-O-P-B 3f® wherein R is an amine reactant of the formula N - (CH2)_n in which the radicals are defined as above.

More specifically, the respective groups of phosphobetaine compounds of the invention as set forth above under formulas (II), (III) and (IV) can be synthesized by a number of processes which are set forth schematically below: Process A (Amine + Phosphate Ester Halide) 2) Y - 0 - P - OM (II) -Hal R + Hal - Y - 0 - $ - OM (Ila) I OH wherein Hal = halogen and the other radicals are defined as above 3) II y - ο - ρ - OM I OM' - Hal II R + Hal -Y-O-P-OM I OM' wherein the radicals are defined as above; 4) φ m R-Y-O-P-O-Y-R Hal ©X 2R + Hal - Y - 0 (HI) (Ilia) ,® (IV) u - P - 0 - Y Hal (IVa) I OM wherein the radicals are defined as above.

An alternate process for making certain of the inventive phosphobetaine compounds utilizes a novel reaction between the amine reactant (R) and a cyclic hydroxypropylenecontaining phosphate ester reactant, as shown schematically below: Process B (Amine + Cyclic Phosphate Ester) ) II R® - (CoH_0H) - 0 - P - OM oe (II') 6) R + HO(C,H,-) - 0 - P , J o , OM (lib) R - (C3H5OH) - 0 - P - 0 - (CgHgOH) - R i® X -Hal (IV) 2R + H0(C3H5) -O-P-O-Y- Hal (IVb) wherein the reactants are defined as before, it being θ understood that the anion X can be supplied by the halide (Hal) group which is split from reactant Illb θ (in which case X = Hal) or from another source, as explained above. The designations HO(C3H3) or (C^Hj-OH) herein refer to a hydroxypropylene function in which the cyclic oxa- moiety is linked to any one of the three carbons and the cyclic oxa- moiety is linked to one of the three carbons, preferably at the 3- or 2-position of the propyl group.

The phosphitaine compounds of the invention can be prepared from the corresponding phosphite esters and amine reactants, as follows: (6a) R + Hal - Y oH o OG> wherein R is an amine reactant of the formula R " 1 R1 - C - N R in which the radicals are defined as above. 4810^ The reactants required in the process can be prepared as follows: Preparation of Intermediate R Reactants The amine reactant R applicable to all of 5 the syntheses is, in general, prepared by reacting an acid with an aminoalkyl-substituted tertiary amine to result in the amidoamine function. Alternatively, an acid can be reacted with an aminoalkyl-substituted secondary amine, followed by further treatment of the reaction product with alkylene oxide.

Reaction (7) below yields the non-cyclic reactants R: 7) Rx - C - OH + HN(CH-) N 2 n R -C-N(CH2)n-N + H2O wherein R is defined as above.

X -4-8107 Preparation of Phosphate Ester Intermediate Reactants The preparation of the phosphate ester intermediate reactants as set forth in reaction sequences 1, 2 and 3 above are also prepared by reactions which are illustrated as follows: 9) CH2-CH>CH2-Hal+ HO-l’-OH OM 0 / \ II · ) CH..-CH-CH2-Hal+ MOP-OM' L . I Oil Hal-Y-O-P-OM (Ila) I OH Hal-l-O-l’-OM (ilia) I OM' ID 2 /\ Hal-Y^-P-O-Y-Hal (IVa) CH,-CH-Ob-Hal + HOP-OH 2 I ι OM OM For certain reactants Ila. viz., those wherein M is hydrogen or an alkali or alkaline earth metal cation, the following intermediate synthesis can lobe used: 0 il il 12) Ι’,Ο. + Hal-Y-OH -? Hal-Y-O-P-OH + (Hal-Y-0),-P-Oli I OH MOH s' x^HoO M’Oll h2o.

II Hal).Y-O-P-Oll I OM (Hal-Ϊ-Ο), -P i I OM'1 ο ο II ι ο ο « ' Β 1' 13) H0-&-O-P-CH + Hal-Y-CK-»Hal-Y-O-P-CH + (Hal-Y-O) ,-1 II I 2 CH CH CH MCH Β B -·> Hal-Y-O-P-CH AND (Hal-Y-0) ,-F-OM Η,Ο | 2Z CM wherein M is an alkali or alkaline earth metal salt cation (e.g., sodium, potassium, magnesium or calcium).

Reactions 12 and 13 are carried out in two steps. The first is conducted under anhydrous conditions to generate a chlorophosphate. Subsequently, this material is diluted to 40% with water and one mole equivalent of M0H, e.g., sodium hydroxide. io The phosphate ester intermediate reactants required for synthesis route (B) supra, can be prepared as follows: 14) 0 / \ CH2-CH-(CH2’Hal) (I M - 0 - ? - OH I OH pH 10-10.5 v 0 HO(C3H5) - 0 - P - 0M (lib) ) Λ CH2-CH- CH2-Hal 4-8107 I OH S Ϊ H0-( C3II5) -o-p-och2c’hcii2 -Hal (IVb) (Ixlb) It will be noted that Reactions 14 and 15 utilize reactants similar to the reactants needed in Reactants 10 and 11 supra (although with the more limited hydroxypropyl definition), but that different, cyclic products are obtained. The different products are the result of a different pH adjustment; thus, while reaction 10 is carried out at a pH of about 4-5, reaction 11 is carried out at a pH of 9.5 to 10.5, resulting in a cyclic product. This cyclic product may contain also some vicinal epoxy material so that the formula s HO(C3Hg) - 0 - P - OM I-0 (lib) should be understood as including not only one or more of the isomers resulting from linkage of the oxa-oxygen to any one of the hydroxy-propylene carbons (to make a 5-, or 6-membered ring, but also the following structure; Cff, - CH - CH, - 0 - P - OM 2 j OH Operation at a higher pH, e.g., 10.5 or higher, would favor formation of the vicinal epoxy-containing material.

Preparation of Phosphite Ester Intermediate Reactant The preparation of the phosphite ester intermediate reactant is conducted as illustrated below: 16) CH2-CHCH2-Hal + HO-|-H OH -Hal-Y-0- '-CH In carrying out the reactions 1 to 4 as set forth above leading to the ultimate phosphobetaine compound of the invention and reaction 16 as set forth above leading to the ultimate phosphitaine compound of the invention, the amine intermediate reactant (R is reacted with the appropriate phosphate ester intermediate reactant or phosphite ester intermediate reactant and these reactions are generally carried out in an agueous system at 80-100°c. The phosphobetaine or phosphitaine product will have a final pH at 10% of 6-8, depending on the specific nature of the product, i.e., the nature of the amine reactant employed.

These novel phosphobetaine and phosphitaines are good surfactants and quite unexpectedly exhibit good foam volume and superior foam stability in comparison to commercially available amphoteric and zwitterionie surfactants.

One method of exhibiting these properties is by an adaptation of the well-known Ross-Miles foam test principle (Oil and Soap 18, 99-102 (1941) in the following manner.

Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion of 2.5 grams lanolin and 100 grains of dioxane. The lanolin is first mixed with 25 cc. of dioxane. This mixture is heated over a steam bath to 45°C. in order to dissolve the lanolin in the dioxane. The remainder of the 5 dioxane is then added and mixed. This lanolin-dioxane solution, which is stored in an amber bottle, should be prepared fresh on the day that the tests are run.

The composition to be tested is diluted by adding 376 cc. of distilled water to 4 grams of the composition and then by adding 20 cc. of the lanolindioxane solution described above while mixing. Heat is produced when the lanolin-dioxane solution is added to the solution of the composition in water and care must be taken in adjusting the temperature of this solution to 24-25°C. Both of these intermediate solutions should therefore be adjusted to 23°C. before mixing.

The cooling of the lanolin-dioxane solution should be gradual in order to avoid precipitation of the lanolin. This will produce a final solution with a temperature of 24-25°C.

The final solution of the composition to be tested, water, dioxane and lanolin described above, is then run in a modified Boss-Miles foam column in the usual way. All tests are conducted in duplicate, and the average of the two results is taken. Foam stability is determined by measuring the decay in foam height after two minutes, expressed as a percentage of the original height.

Typical foam values obtained utilizing the above procedure for a group of ccttpounds which included an alkylamidophosphobetalne, an alkylamido betaine and an alkylamido sultaine are listed below: Ebam % Decay \folune After (ml) 2 min. 250 4.0 240 10 210 19 225 31.0 200 60.0 above results. the Sample ' Nattier Lauric Myriscic Amido 5 3-Hydroxypropyl Phosphobecaine . 7 Cocamido Disodium 3-Hydroxypropyl Phosphobetaine θ Cocamido Disodium Ethyl Phosphobetaine 25 Cocamido Propylbetaine Cocamido Propylsultaine As can be seen from the phosphobetaines of the present invention exhibit excellent foam volume and stability whereas the stability of the betaines and sultaines is significantly less.

In another series of tests., a group of compounds which 2o included additional species of the phosphobetaine and phosphitaine compounds of the invention were tested by a cylinder shake test for the evaluation of foaming characteristics.

In this test, test solutions containing 0.1% by weight of the candidate surfactant in water of 100 ppm hardness (calcium to magnesium ratio 3:2) were used and placed in 100 ml stoppered cylinders which had been cleaned so that water drains down its walls in an unbroken film. Each cylinder filled with test solution was shaken 20 times in a standard manner and net foams 3Q in ml is noted one minute and again five minutes after shaking. The tests were run in three replicates. The results were as follows: - 48107 Example 1 5 Lauric/Myristic Type Hunter Minute Minutes Lauric/Myristic Amido Betaine — 67 60 Sodium Lauryl Sulfate — 85 74 Lauric/Myristic Amido 3 Hydroxy Propyl Monosodium Phosphobetaine 2 88 78 Lauric/Myristic Amido 3 Hydroxy Propyl Disodium Phosphobetaine 7 85 78 Lauric/Myristic Amido 3 Hydroxy Propyl Glyoeryl Phosphobetaine 2 86 78 Lauric/Myristic Amido Carboxy Disodium Phosphobetaine 33 87 73 N-cocamidoethyl-N-hydroxyethyl Glycine -- 76 67 Lauric/Myristic Amido Propyl Monosodium Phosphitaine 43 88 76 Coco Type Exanple Nunber 1 Minute 5 Minutei Cocobetaine — 65 56 Cocamidobetaine __ 70 63 Cocamido Monosodium Phosphobetaine I 79 74 Cocamido Glyceryl 3 Hydroxy Propyl Phosphobetaine 11 71 74 Coco Imidazoyl Monosodium Phosphobetaine 19 83 78 Coco Imida2oyl Disodium Phosphobetaine 50 80 75 Bis (Coco Imidazoyl) Phosphobetaine 34 75 69 Cocamido Propyl Monosodium Phosphitaine 44 79 70 In addition, the compounds of the present invention possess a surprisingly low ocular irritation potential when compared to commercially available amphoteric and zwitterionie surfactants. The test employed is the modified Draize Test (J.H. Draize et al., Toilet Goods Assn. No. 17, May, 1952, No. 1 Proc. Sci.

Sect.).

In this method, an 0.1 ml sample of a neutral solution of the conpound under investigation is dropped into one eye of an albino rabbit, the other eye serving as a control. Six rabbits are employed for each compound.

Observations are made after 1, 24, 48, 72 and 96 hours and 7 days after initial instillation; second and third instillations are made after the 24 and 48 hour readings. Results may vary from substantially no change or only a slight irritation in the appearance of the rabbit's eye after 7 days to severe irritation and/or complete corneal opacity. Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number indicating greater ocular irritation and the scores are added to give a total numerical value for each reading for 6 rabbits and average. The averaged score is an indication of the irritation potential of the composition under test. Based on the averaged score, descriptive irritation evaluation may be given, e.g., none, slight, moderate, severe, etc.

Typical results for a group of ccnpounds vfcich included a betaine, sultaine and a phosphobetaine in accordance with the present invention vten subjected to the above test procedure are as follows: Eye Irritation Potential 1 24 48 72 96 Irritant Compound hr. hr. hr. hr. hr. 9SL7 Rating Iauric/Myristic Amido 3-hydroxy propyl ptospbobetaine 7.7 0.3 1.3 1.0 0.0 0.0 slight Cocamido propylbetaine 11.7 4.2 9.3 13.2 11.2 5.8 severe Cocamido propylsultaine 15.0 8.5 15.6 25.0 _ w- severe Bis Coco Imidazoline phosphobetaine 10.5 4.7 5.0 3.3 3.7 0.7 slight Cocanddo Glyceryl phosphobetaine 9.2 5.0 4.3 9.0 5.7 0.7 slight All tests were conducted at a concentration of 3% wt./wt.

Supportive of above test data, further series of tests were carried out as above but using only one test rabbit per compound, obtained: the following results were Example Nunfcer 1 2 Day 3 4 7 Irritant Rating Iauric/Myristic Qisodinn Amido Phosphobetaine 7 7 0 1 1 0 very slight Glyceryl CA-35 15 4 0 0 0 0 very slight Iauric/Myristic Carboxy Disodium Phosphobetaine 33 2 2 0 0 0 very slight Comparison Anphoteric 20* — 21 15 7 5 0 moderate Qocdbetaine — 23 26 19 17 25 severe Cocamidobetaine — 21 19 14 9 6 severe Sodium Lauryl sulfate — 18 16 16 16 10 severe CA-35** — 26 21 21 16 0 severe *N-cocamidoethyl-^hy3roxyethyl glycine **2-undecyl-l-hydroxyethyl propicnic acid imidazoline.

As can be .readily Been, the phosphobetaines in accordance with the present invention exhibit only slight ocular irritation whereas the betaines and sultaines are severe irritants.

The preparation of specific compounds of the invention is illustrated by the following specific examples. For simplicity, there are first set forth the specific phosphate ester intermediate reactants (prepared according to reaction sequences 9-15 supra) 1° and the specific phosphate ester intermediate reactant (prepared according to reaction sequence 16 supra) which were used in the examples, in conjunction with certain tertiary amine reactants which are specifically set forth in each example.

Phosphate Ester Intermediate Reactants Reactant A - Prepared According to Reaction Sequence 9 OH 0 I H .

C1CH2 - CH - CH20 - P - ONa OH Reactant B- Prepared According to Reaction Sequence 10 OH o OH OH I II II C1CH2 - CH - CH20 - P - OCH2 - CH - CH2 OH Reactant C - Prepared According to Reaction Sequence 11 OH 0 0· II I / \ li NaO-P-OCIL-CH-CH, and/or C1L-CH-CH-0-P-0M I I 2 2 ι 0- 0Ka Reactant D - Prepared According to Reaction Sequence 12 OH 0 OH II C1CH2-CH-CH2O-P-OCH2-CH-CH2C1 ONa Reactant H OH C1CH2 - CH - CH2O - P - OH and ClCH2-C-O-P-QNa ONa ch2 OH and OH 0 0 ι κ 1 (ClCH2-CH-CH20)2-P and (C1CH2-CH"O)2-P- ONa ONa CH, OH Phosphite Ester Intermediate Reactant Reactant J OH 0 C1CH2 - CH - CH20 - P - OH H Example 1 .5 parts of Reactant A and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to 50°C. 19.5 parts of molten 3-cocoamidopropyl dimethylamine are slowly charged under good agitation. Heating is continued to 90-95°C and held at this temperature for 3 to 4 hours.

Reaction reaches 97% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structures [J f"3 0H f R1 - c - H - 2), - £&] - CH2 - CH - CH,0 - P - 0© 15 I I 2 I 11 ch3 OH R1 = C? to C17 alkyl Example 2 .8 parts of Reactant A and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 19.2 parts of a 70/30 blend of lauramidopropyl dimethylamine and myristamidopropyl dimethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C and held at this temperature for 3 to 4 hours. Reaction reaches 97% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: 11 R - C - N - (CH,), | t» J R1 - 70% alkyl 30% C13 alkyl CH>? ®N - CH2 CH OH I CH CH, A I! P - OH Example 3 23,9 parts of Reactant A and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 16.1 parts of caprylamidopropyl dimethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C and held at this temperature for 3 to 4 hours. Reaction reaches 97% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: Clh Oil · 0 J ' 11 R1 - C - N - (Cll2)3 - - CH2 - CH - CHjO - P - 0° H Clt3 R1 = C? alkyl Oil Example 4 18.5 parts of Reactant A and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 21.5 parts of 3-oleamidopropyl dimethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C. and held at this temperature for 3 to 4 hours. Reaction reaches 97% during this time via inorganic chloride and tertiary amine analysis.

The product is an agueous solution of a novel product having the following structure: CH, OH 1 - C - N - (CH2)3 - - CH, - CH - CH,0 - P - I H alkyl CH, OH Example 5 23.6 parts of Reactant A" and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 16.4 parts of a blend of 70/30 3-lauramidopropyl diethylamine and 3-myristamidopropyl diethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C and held at this temperature for 3 to 4 hours. Reaction reaches 97% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: I R - C - N - (CH2)3 H .

R1 = 70% CX1 alkyl 30% C33 alkyl ch2ch3 OH J I H e - w - ch2 - ch - ch2o - p - o© ch2ch3 OH EXAMPLE 6 26.8 parts of Reactant B and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 13.2 parts of 3-caproamidopropyl dimethylamine are slowly charged to the above solution using good agitation. Heating is continued to 9O-95°C. and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: R - C - N 1 H R = C5 alkyl Γ3 (C!I2) 3 I CH.

CHOH - CH CH,0 - P - 00 I 0CH„CH-CH, 2, , 2 OH OH Example 7 26.2 parts of Reactant °B and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 13.8 parts of a 70/30 blend of 3-lauramidopropyl diethylamine and 3-myristamidopropyl diethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: 0 II CH.CH, 1 OH | 0 It r< - c - fi |(ch2)3 - ®N - CH, I Z - CH - CHjO · - P 1 1 H 1 CH2CH3 0® R = 70SC11 alkyl 30% *13 alkyl Example 8 .4 parts of Reactant D and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to 50°C. 19.6 parts of molten 3-cocamidopropyl dimethylamine are slowly 2—via-v-ιιλ I I 2 OH OH charged under good agitation. Heating is continued to 90-95°C and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: CH. oh II I I R - C - N-(CH2)3 - 5¾ - CH2-CH-CH,0 H CH3 R » C7 - C17 alkyl P · i© OH OH I I OCH2-CH-CH2 Example 9 Iq 26.4 parts of Reactant D and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 13.6 parts of a 70/30 blend of 3-lauramidopropyl diethylamine and 3-myristamidopropyl diethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: fl ?H2CH3 ?H 2 ?H R-C-N-(CH-),-*N - CH,-CH-CH,0-P-OCH,-CH-CH, I 2 3 I 2 2 ] . 2 2 H CH2CH3 0 R = 70% c^ alkyl 30% C13 alkyl 46107 Example 10 14.4 parts of Reactant "C and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to 50°C. 25.6 parts of molten 3-cocamidopropyl dimethylamine are slowly charged under good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: CH3 OH 0 OH CH3 0 R-C-N-(CH,),-^-CH,-(!:H-CH,O-$-OCH,-CH-CH,-®N-(CH,),-N~C-R CH, 2 ^3 1 R = Cy - C1? alkyl Example ll 15 15.3 parts of Reactant C and 60.0 parts of water are charged in a reacting vessel under good agitation. Heat is applied to approximately 50°C. 24.7 parts of 70/30 blend of 3-lauramidopropyl dimethylamine and 3-myristamidopropyl dimethylamine are slowly charged to the above solution using good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: ? I °H J*3 £ R-C-N- (CH2) 3-'tN-CH2-CH-CH2O-P-OCH2-CH-CH2- N- (CH^-^-C-EL H CH3 0® CH3 H R = 70% C^ alkyl 30% C13 alkyl Example 12 27.9 parts of Reactant C and 60.0 parts of water are charged In a reacting vessel under good agitation. Heat is applied to approximately 50°C. 12.1 parts of 3-caproamidopropyl diethylamine are slowly charged to the above solution using good agitation. Heating is continued to 9O-95°C. and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: R = C? alkyl Example 13 26.7 parts of Reactant C and 60.0 parts of water are charged into a reacting vessel under good agitation. Heat is applied to approximately 50°C. 13.3 parts of 3-benzamido propyl dimethylamine are slowly charged to the above solution using good agitation.

Heating is continued to 9O-95°C. and the heated mixture held at this temperature for 3 to 4 hours. Reaction reaches 98% during this time via inorganic chloride and tertiary amine analysis.

The product is an aqueous solution of a novel product having the following structure: R - C - N - (CHn)i 4 J OH II ONa R1 = phenyl I! A CH2 - CH20 - P - 0 '3 Example 14 .30 parts of Reactant B and 60.0 parts of water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50°C. 19.70 parts of 3-cocamidopropyl dimethylamine are charged under good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°N is vanishingly small.

The product is an aqueous solution of a novel product having the following structure: ϊ Τ'3 ?H 0 R - C - N(CH2)3 - - CH2 - CHCH2 - 0 - P - (P H CH, ONa and CH, OH (R - C - n(ch2)3 - % - ch2chch2o)2 - P - cP ch3 and CH, II ¢,1 - c - k(ch2) - ns - ch2 - c - o - p - (P CH, ch2 ONa and Cl© CH, (R - C - N(CH2)3 R = C? to C^7 alkyl N - CH2 - C - O)2 - P - 0 CH, CHOH Cl Example 15 18.04 parts of Reactant C and 60.0 parts of water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50°C. 21.96 parts of N-amidoethyl-N-hydroxyethyl-glyclne (alkyl being 70% C^| and 30% C^3) are charged under good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°N is vanishingly small.

The product is an aqueous solution of a novel product having the following structure: /^2 II C - ONa N - CH,CH, - N - CH,CH,OH | 2 2 \ 2 2 H CH2 - CH OH CH-0 - P - 0 2 I ONa R = 70/30 Lauric/Myristic Example 16 18.29 parts of Reactant C and 60.0 parts water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50°C. 21.71 parts of N-alkylethyl-N-hydroxyethyl-glycine (alkyl being lauric) are charged under good agitation. Heating is continued to 90-95°C’. and the heated mixture held at this temperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°n is vanishingly small.

The product is an aqueous solution of a novel product having the following structure: II J /cn2-c -ONa R - C - N - CH-CH, - - CH,CH,OH 0 1 \ II β H CH, - CH - CH,0 - P - 0® I I OH ·ONa R = Cl;L alkyl Example 17 17.48 parts of Reactant C" and 60.0 parts water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50°C. 22.52 parts of N-alkylethyl-N-hydroxyethyl-glycine (alkyl being 20 Cy to C1?) are charged under good agitation. Heating . 48107 is continued to 90-95°C. and the heated mixture held at this tenperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°N is vanishingly small.

The product is an aqueous solution of a novel product having the following structure: II . CH, - C - ONfc 11 ffi / R - C - N - CH,CH2 -N - CH-CH-OH 0 1 \ ϋ ~ H ' CH, - CH - CH,0 - P - 0° , 2 , CH ONa R » C? to C1? Example 18 18.73 parts of Reactant B and 60.0 parts water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50°C. 21.27 parts of N-alkylethyl-N-hydroxyethyl-glycine (alkyl being lauric) are charged under good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°N is vanishingly small.

The product is an aqueous solution of a novel product having the following structure: II R - C - N I H ch2ch2 cn2 - C - ONa H - CH2CH2OH \ OH 'CH , CH - CH,0 - P - OCH,CHCH, 2 I 2 L I CH OS OH R = C^^ alkyl 48ΐθ7 Example 19 12.60 parts of Reactant D and 60.0 parts of water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50eC. 27.31 parts of N-alkylethyl-N-hydroxy-ethyl-glycine (alkyl being lauric) are charged under good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°N is vanishingly small. io The product is an aqueous solution of a novel product having the following structure: Example 20 .73 parts of Reactant A and 60.0 parts of water are charged into a suitable reaction vessel under good agitation. Heat is applied to 50°C. 24.27 parts of N-alkylethyl-N-hydroxy-ethyl-glycine (alkyl being myristic) are charged under good agitation. Heating is continued to 90-95°C. and the heated mixture held at this temperature for 4 hours. Reaction is complete when inorganic chloride reaches theoretical and residual 3°N is vanishingly small.

The product is an aqueous solution of novel product having the following structure: ο II R - C Ν - CK2CK2 " Η >/ CH2 - C · CH2CH2OH CH, - CH . I ONa CH ch2o R = CL1 alkyl Example 21 ?H3 r - C - N - (CH2)3 H N - CH2 - CH ch3 oh ch2° H To 60.00 parts of soft water In a suitable reactor, charge 20.06 parts of Reactant "J trader good agitation. Heat to 40-45’C. and charge 19.94 parts of a 70/30 blend of 3-lauramido-propyl-dimethyl— amine + 3myristamido-propyl-dimethyl-amine under good agitation. Heat to 90-95’C. and hold 4-5 hours. Reaction is complete when theoretical inorganic chloride is generated and when residual tertiary nitrogen levels become vanishingly small.

The product is an aqueous solution of the above material.

R + 7O7.-Ci;l/3O%-C13 alkyl Example CH, R - C - N - (CH2)3 - N - CH2 - CH - CH2O - P - O' CHOH <3 4810T To 60.00 parts of soft water in a suitable reactor, charge 20.82 parts of Reactant J under good agitation. Heat to 45-50°C. and charge 19.18 parts of 3-lauramido-propyl-dimethyl-amine under good agitation. Heat to 90-95°C. and hold 4-5 hours. Reaction is complete when theoretical inorganic chloride is generated and when residual tertiary nitrogen levels become vanishingly small.

The product is material. R = Cjj alkyl an aqueous solution of the Example 23 0 H < CH, sl 0 II R - C - N - (CHj,3 - N - CH, 1 z CH - CH,0 I p I 1 H 1 CH, 1 OK 1 H To 60.00 parts of soft water in a suitable 15 reactor, charge 24.45 parts of Reactant J under good agitation. Heat to 45-50°C. and charge 15.55 parts of 3-capramido-propyl-dimethyl-amine under good agitation. Heat to 90-95°C. and hold 4-5 hours. Reaction is complete when theoretical inorganic chloride is generated and when 2o residual tertiary nitrogen levels become vanishingly small The product is an aqueous solution of the above material.

R = C5 alkyl Example 24 CH, 0 11 ®l H , R - C - N - (CH,), - - CH, - CH - CH,0 - P - I 2 | I 1 H CH3 OH To 60.00 parts of soft water in a suitable reactor, charge 18.13 parts of Reactant J under good agitation. Heat to 45-5O°C. and charge 21.87 parts of 3-oleamido-propyl-dimethyl-amine under good agitation.

Heat to 9O-95°C. and hold 4-5 hours. Reaction is complete when theoretical inorganic chloride is generated and when residual tertiary nitrogen levels become vanishingly small.

The product is an aqueous solution of the above material.

R = C17 alkyl (j Example 25 CH, 0 II ©ι II e R - C - N - (CH,)CH, - CH - CH20 - P - CT I 2 3 I 2 I I H CH3 OH H To 60.00 parts of soft water in a suitable reactor, charge 19.68 parts of Reactant J under good agitation. Heat to 40-50°C. and charge 20.32 parts of 3-cocoamido-propyl-dimethyl·-amine. Under good agitation heat to 90-95°C. and hold 4-5 hours. Reaction is complete when theoretical inorganic chloride is generated and when residual tertiary nitrogen levels become vanishingly small.

The product is an aqueous solution of the above material.

R = C-j to PREPARATION OF REACTANT SPECIES Example 26 REACTANT A 60.00 parts of deionized water are charged into a suitable reactor to which 22.58 parts of Na^PO^ and 0.70 parts of NaOH are charged under good agitation. Mix well until a solution is obtained. 17.42 parts of 20 Epichlorohydrin is charged under good agitation. The reactor is sealed and 5 PSIG (Q. 35 kg/crr? gauge) Nj is applied. Heat to 8085°C. holding the heated mixture at this temperature for 2 hours after the batch clears (approximately 3 hours total). Reaction is complete when theoretical reduction in acid value is obtained. Inorganic chloride will be less than 0.50%. 4810? The produce Is an aqueous solution of a novel product having the following structure: OH 0 I 11 CICH, - CH - CH,0 - p - OH - I ONa Example 27 REACTANT B 60.00 parts of deionized water are charged into a suitable reactor to which 17.37 parts of Ν32ΗΡ0^ are charged. Mix well until a solution is obtained. 22.63 parts of Epichlorohydrin are charged under good agitation. lhe reactor is sealed and 5 PSIG (0.35 kg/cm. gauge)N2 is applied. Heat tc 80-85°C. holding the heated mixture at this temperature for approximately 2 hours after the batch clears (approximately 3 hours total). Reaction is complete when theoretical chloride is obtained and theoretical reduction in acid value is realized.

The product is an aqueous solution of a novel product having the following structure: OH 0 OH I II I CICH, - CH - CH-0 - p - OCH - CH - CH2 I 2 I2 ONa oh Example 28 REACTANT C 60.00 parts of deionized water are charged into a suitable reactor to which 17.37 parts of are charged. Mix well until a solution is obtained. 22.63 parts of Epichlorohydrin are charged under good agitation.

The reactor is sealed and 5 PSIG (0.35 kg/cm . gauge)is applied. Heat to 5 80-85°C. holding the heated mixture at this temperature for 2 hours after the batch clears (approximately 3 hours total). Reaction is complete when theoretical reduction in acid value and theoretical inorganic chloride values are obtained. io The product is an aqueous solution of a novel product having the following structure: 0. o z°\ HO - P - CCH2 - CH - CH2 La and HO(C3 ς)0 - ? ONa Example 29 REACTANT D 60.00 parts of deionized water are charged into a suitable reactor to which 17.09 parts of NaHjPO^ and 0.70 parts of NaOH are charged. Mix well until a solution is achieved. 22.91 parts of Epichlorohydrin is charged under good agitation. Reactor is sealed and 5 PSIG (0.35 kg/cm gauge) Nj is applied. Heat is applied to approximately 80-85eC. and the heated mixture held at this temperature for approximately 3 hours after the batch clears (approximately 5 hours total). Reaction is complete when acid value is reduced by the theoretical amount. Inorganic chloride will be less than 0.5%.

The product is an aqueous solution of a novel product having the following structure: OH 0 OH I Ϊ I C1CH2 - CH - CH2O - I - OCH2 - CH - CH2C1 OH Example 30 REACTANT H 68.09 parts of 3-chloro-l,2-propanediol are slowly charged to 31.91 parts of polyphosphoric acid under good agitation. Heat slowly to 9O-95°C. holding the heated mixture at this temperature for approximately 2 hours. Reaction is complete when theoretical reduction in acid value is obtained. 35.17 parts of the above are mixed with 60.00 parts soft water. 4.83 parts NaOH are slowly added. Reaction is complete when theoretical reduction in acid value is achieved.

The product is an aqueous solution of a novel product having the following structure: OH 0 HO I 1 I I Cl-CH,CHCH,0 - P - OH and C1-CH,C - 0 - P - ONa 2 ι 21 ι ONa CH, OH OH (C1-CH,CHCH,O). - P and (Cl-CH-CHO), - P - ONa 2 2 2 \ 2 ONa CH, I 2 OH Example 31 REACTANT J To 60.00 parts of soft water in a suitable reactor, slowly charge 21.17 parts of NaH^PO^ under good agitation. Heat to 40-50°C. Slowly charge 18.83 parts epichlorohydrin under good agitation. Seal reactor and apply 5 PSIG (0.35 kg/cm gauge) nitrogen. Heat to 90-95°C. and hold 3-4 hours. Reaction is complete when theoretical reduction in acid value has occurred. The product is an aqueous solution of a novel reactant having the following structure: OH 0 I II C1CH, - CH - CH,0 - P - OH

Claims

Claims:

1. A compound of the formula: or I 0-P C0 wherein Λ Φ A is selected from 0 , OM, and -O-Y-R B is selected from 0® and OM' is an anion z is 0, 1 or 2 with the proviso that only one of A and B can be 0® and z is of a value necessary for charge balance; R is an amidoamine moiety of the formula: E 1 Ϊ f C - N - (CH,) i n © wherein R 1 is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms, R is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5 carbon atoms, or polyoxyalkalene of up to 10 carbon atoms, and R^, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms; 5 n is an integer from 2 to 12; Y is hydroxy, alkoxy or hydroxyalkyl substituted alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms, which alkylene chain may optionally be substituted with lower alkyl; M and Μ', which may be the same or different, are (a) hydrogen, (b) an organic radical selected from alkyl or hydroxyalkyl of up to 6 carbon atoms, polyhydroxyalkyl of up to 10 carbon atoms, glyceryl, 5 cyeloalkyl of up to 6 carbon atoms, aryl or arylalkyl of up to 10 carbon atoms, or (c) a salt radical selected from alkali metals, alkaline earth metals, and mono-, di-, or tri-ethanolamine, provided that when either M or M' is an organic radical (b), the 10 other cf M and M* must be hydrogen or a salt radical (c).

2. A compound as claimed in claim 1 of the formula: wherein the R, Y and M radicals are defined as before.

3. A compound as claimed in claim 1 of the formula: ϊΡ-Υ-0-P-H i® wherein the R and Y radical* are defined as before.

4. A compound as claimed in claim 1 of the formula: - Y - 0 - P - OM l I OM wherein the R, Y and M and X radicals are defined as before.

5. A compound as claimed in claim 1 of the formula: Λ If R -Y-O-P-O-Y-R X' le wherein the R, Y and X radicals are defined as before

6. A compound as claimed in claim 1 wherein R is an amidoamine moiety of the formula: R - C - N - (CH„) ζ n R 4 J wherein R·*· is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms, R is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5 carbon atoms, or polyoxyalkalene of up to 10 carbon atoms, 3 4 R and R , which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms; n is an integer from 2 to 12. 48ίογ

7. A compound as claimed in any of claims 1 to 6, wherein the Y radical has a hydroxy, alkoxy or hydroxyalkyl substituent of not more than 10 carbon atoms.

8. A compound as claimed in claim 1, wherein said 5 compound is a lauric/myristic amido 3-hydroxypropyl phosphobetaine .

9. A compound as claimed in claim 1, wherein said compound is cocamido disodium 3-hydroxypropyl phosphobetaine.

10. A compound as claimed in claim 1, wherein said 10 compound is lauric/myristic amido monosodium 3-hydroxypropyl phosphobetaine.

11. A compound as claimed in claim 1, wherein said compound is lauric/myristic amido disodium 3-hydroxypropyl phosphobetaine.