CN1024806C - Amino-functional compounds as builder/dispersants in detergent compositions - Google Patents

Abstract

Amino-functional compounds are economically prepared by reacting maleic anhydride with alcohols to form a maleate 'half-ester' or fumarate 'half-ester' which is combined with certain amines, most preferably aspartate or glutamate, under conditions selected to avoid hydrolysis. At low molecular weights, the compounds herein are useful detergency builders; at progressively higher molecular weights within a specific range, combined builder/dispersant and typical dispersant properties emerge. Processes for preparing the compounds and useful detergent compositions containing them are described.

Description

Amino-functional compounds as builder/dispersants in detergent compositions

The present invention relates in detergent composition, can be used as the compound of synergistic agent, synergy/dispersion agent and/or dispersion agent.These compounds liquid with granular heavy dirty laundry detergent composition in particularly useful.

Can be known in the prior art as the composition of synergistic agent, dispersion agent or sequestering agent, it has chemical constitution widely.For example, can be referring to work " Angew.Chem.Internat.Edit., " the 14th such as Berth, 1975,94-102 page or leaf.The user of commercially available washing composition admits the operability of these materials in cloth-washing detergent.It is difficult with " synergistic agent ", " dispersion agent " or " sequestering agent " this class noun these compounds being sorted out, also have some arbitrariness, because the compound disclosed in many prior aries has the different combination of these useful qualitys, and become commercialized widely and be applied to different purposes, comprise the control of boiler scale and water softening etc.However, brainstrust thinks that some nouns have reflected that these compounds are in qualitative real difference so in the prior art, for example, some compound is obviously preferably as synergistic agent when high consumption, and other compounds such as polyacrylate then are preferably as dispersion agent when low consumption.For example, see P.Zini work " being the homopolymer of base-material and multipolymer additive with the acrylic acid or the like ", " Seifen-Oele-Fette-Wachse ", 113,1987, the 45-48 page or leaf and 187-189 pages or leaves as washing composition.Therefore the exploration that has the novel substance required composite behaviour of this generic attribute, economic cheap is continuing always, and is the simple operation of laundering of textile fabrics to their the most effective test of effectiveness.

Recently disclosed relevant document comprises: the United States Patent (USP) 4,021,359 of Schwab, the United States Patent (USP) 4,680,339 of (being published on May 3rd, 1977) and Fong, (being published on July 14th, 1987).Also can be referring to people such as Abe work " oiling " (Japanese) 35(11): the 937-944 page or leaf, 1986, and people such as Tanchuk shows " Ukr.Khim.Zh " (the Russian edition), and 43(7), 1977 years, the 733-8 page or leaf.In addition, can be referring to people's such as Picciola " α of N-alkyl and aralkyl D, L-aspartic acid-and β-acid amides ", " Il Farmaco " 24(11), 1969, the 938-945 pages or leaves; People such as Laliberte work " improvement of N-alkyl-aspartic acid synthetic ", " Can.J.Chem. " 40, (1962), 163-165 page or leaf; People's such as Zilkha " N-alkyl-aspartic acid and N ²Synthesizing of-alkyl-α-l-asparagine ", " J.Org.Chem. " 24(1959), pp.1096-1098.Schwab has proposed some compounds, comprises the water-soluble salt of the partial ester of maleic anhydride and polyvalent alcohol (comprising three hydroxyls at least), and their chelating calcium ions also block its precipitating action, play the effect of washing composition synergistic agent.Fong has set forth the building-up process of the water-soluble carboxyl fluidized polymer with random multiple amido polymer chain link.People such as Tanchuk have set forth some N-(beta-hydroxyethyl) monoesters of aspartic acid, they are by butene dioic acid monoesters and thanomin reaction and obtain.

People such as Abe set forth by (malolactonate) ring-opening polymerization of maloyl lactone acid benzyl ester polymaleic acid and by the DL-toxilic acid in methyl-sulphoxide direct polymerization and the difference of polymaleic acid.And the washing composition synergy effectiveness of polymaleic acid and the test-results of biological degradability have been reported.

Chemical to maleic anhydride had been done comprehensive commentary, referring to " maleic anhydride ", and B.C.Trvedi and B.M.Culbertson work, Plenum publishes, New York, nineteen eighty-two, this book is a bibliography at this.Need scale operation for the detergent for washing clothes chemical, this compound quantitatively is to satisfy.The patent of Trivedi and Culbertson and above mentioned Schwab all indicates, and the reaction of maleic anhydride and alcohol is known in the prior art.Yet these compounds obviously were not explored by the reaction of the further functionalization of mode that the present invention proposes.

As from aforementioned that see and learnt that from the amount of literature data that relates to washing composition people are proceeding to improve the research of synergistic agent and dispersion agent.Especially, these researchs will help to obtain some from can be biodegradable and the synergistic agent and/or the dispersion agent of calm facile feedstock production.

The invention provides a new class synergistic agent/dispersant material, to satisfy the needs of these aspects.

The present invention includes and have general formula and be the compound of (MAO) nE, wherein n is from 1 to about 2500 integer; M is H or salifiable positively charged ion (preferably sodium ion); A selects from following groups: 2-(secondary substituted-amino)-and 4-ketobutyric acid alkali, three grades of substituted-aminos of 2-()-4-ketobutyric acid alkali, 3-(secondary substituted-amino)-4-ketobutyric acid alkali and three grades of substituted-aminos of 3-()-4-ketobutyric acid alkali.O is and the oxygen of E with covalent bonds; E is specific organic moiety, and specific definition is seen below.

" secondary substituted-amino " used herein reaches " three grades of substituted-aminos " speech is in order to emphasizing containing secondary or tertiary amine base/part in the ketobutyric acid salt radical derivative wherein, and usually, getting rid of one-level amino (is H ₂N-) the ketobutyric acid alkali of Qu Daiing.Thereby compound of the present invention is that the amino oxygen that replaces is for butyrates based compound rather than H ₂The ketobutyric acid salt based compound that N-replaces.

The material of best type provided herein comprises the such compound or the mixture of these compound isomers, and A wherein partly is selected from

OC(O) HCH C(L) ₂(O) C-or OC(O) CH ₂C(L) H(O) C-or their mixture.Herein, if when L is alcohol amido, L is the part that comprises single secondary amino or tertiary amine base, and n is greater than 1.

More generally, the A part can be in the following isomery formula any:

Herein, the four carbon atom on the ketobutyric acid alkali chain is numbered, suc as formula shown in.L partly comprises one or more secondary amino or tertiary amine base, its amino nitrogen-atoms and carbon atom C that goes up ²Or C ³Bonding forms nitrogen-carbon bond.

In the isomer formula of A, Z is typically hydrogen, alkyl or other neutral does not have chemical active radical, and it is just in order to fill up this valence link position.As mentioned above, preferably Z is H and A partly is the substituent of L on 2, suc as formula shown in:

As further pointing out in detail in the back, major part is C preferably ²-L replaces, C ³A part and a spot of C that-H replaces ²-H replaces, C ³The isomer mixture of the A part that-L replaces requires to be still effectively to purpose proposed by the invention, and the compound of preparation gained can directly be used as dispersion agent or synergistic agent.

According to the definition of the A that provides above part, when M is univalent cation, formula (MAO) but the nE imagery be expressed as general structural formula, to 2 position isomers, have as shown in the formula

And to 3 position isomers, have as shown in the formula

Generally, E can be a molecular weight ranges from being about 15 to 170,000 monomer or polymer part.The E part can be charged or non-charged.When it was charged body, E was typically negatively charged ion, and energy and salt-forming cation, associated mutually as sodium, potassium, tetraalkyl ammonia or similar positively charged ion.Generally, E can comprise one or more heteroatomss, as S(sulphur) or N(nitrogen).Yet, E preferably one only comprise C and H basically, or comprise the non-charged body of C, H and O.

Generally, E partly has n covalent linkage connecting point position, by means of n ester bond, partly is connected with above-mentioned (MAO) n.Like this, in any compound (MAO) nE, the formation of each ester bond all is that the MA part forms by oxygen and E covalent bonds in n ester bond.

When using as dispersion agent, the molecular weight of the E part among compound (MAO) nE is about 200 to 15,000 and is advisable; And when making synergistic agent and using, the molecular weight of E part then is about from 15 to 15,000 and is advisable.Useful especially herein compound is that those A wherein partly have formula

OC(O) HCH C(L) ₂(O) compound of C-, L can be from being selected from following one group of group in the formula: aspartic acid alkali, L-glutamic acid alkali, glycine alkali, alcohol amido, Beta-alanine alkali, taurine alkali, aminoethyl, sulfuric acid alkali, L-Ala alkali, sarkosine alkali, N-methyl ethanol amino, Iminodiacetate base, 6-aminocaprolc acid alkali, N-methylaspartic acid alkali and diethanolamino etc. are (referring to back L ^1-14Structural formula).L is that aspartic acid alkali, L-glutamic acid alkali, sarkosine alkali, glycine alkali or alcohol amido etc. are better, and preferably aspartic acid alkali or L-glutamic acid alkali.

E chooses alkyl,-oxyl, poly-alkyl or poly--oxyl preferably, and their mixture, in the optimum weight scope that their molecular weight should be pointed in the above.Structurally, preferably E part further to be characterized as general formula be the thing of dehydroxylation wholly or in part of the alcohols of EOH; Cite a plain example, if EOH is a methyl alcohol, then E structurally is characterized as a methyl.In fact, E is that the dehydroxylation product of alcohols is on the structure viewpoint, rather than from the angle of preparation.From preparing and on mechanism, when the preparation The compounds of this invention, what generally include is esterification rather than decarboxylation reaction.Like this, the E definition structurally any particular procedure used with preparing this compound has nothing to do.

Can provide the suitable alcoholic of this E part to select: polyvinyl alcohol, sorb (sugar) alcohol, tetramethylolmethane, starch, dibasic alcohol such as ethylene glycol, propylene glycol, monohydroxy-alcohol such as methyl alcohol, ethanol, propyl alcohol and butanols from following compounds.Yet E can also be from polyol derivative other various straight chains or side chain, for example can be from sucrose, oligose, Beta-methyl glucoside and dibasic alcohol such as C ₂-C ₆Alkylene dihydric alcohol etc. derive.

Generally, the alcohols of Shi Heing is that class that can obtain in a large number commercial.In the oligose type slightly some special alcohol can adopt M-138, " Fructus Hordei Germinatus (malto) oligosaccharide mixture ", other suitable oligosaccharides of (Pfanstiehl Laboratories Inc. company product) can be made from W-Gum.

Generally, low molecular weight substance herein is specially adapted to the synergistic agent as washing composition.For example, in compound of the present invention, n wherein is that l and E select following groups for use, can have the function of washing composition synergistic agent, and these groups have: methyl, ethyl, propyl group, butyl, 1.2-ethylidene, diethylidene, propylidene, butylidene and hexylidene.

Generally, this high molecular (n is typically from 4 to about 2500 greater than 1) material is particularly suitable for as dispersion agent, or in detergent composition, it can be used as dispersion agent and synergistic agent simultaneously.

A good especially dispersion agent/synergist compound herein is a random copolymers, and the basic repeating segment that it contains is

M is a sodium in the formula, and A has

OC(O) HCH C(L) ₂(O) C-, L are the aspartic acid alkali.Also may there be selectable repeating segment.Selectable preferably repeating segment can be selected from following:

And their mixture.Typically, this random copolymers contains the basic repeating segment of about 0.1 to 0.95 molar fraction

And molecular weight is being about 635 to 50,000.

The present invention also comprises the method for making these compounds.For example, aforesaid random copolymers preferably is to obtain easily: with (ⅰ) the Vinyl Acetate Copolymer reaction with excessive maleic anhydride and hydrolysis, the mean polymerisation degree of Vinyl Acetate Copolymer is about 10 to 1500, be about 15 to 150 then better, be more preferably the height hydrolysis in advance of this Vinyl Acetate Copolymer is changed into polyvinyl alcohol, calculate with molecular fraction, degree of hydrolysis is preferably at about 70mol% to 95mol%.

The reaction product in (ⅰ) step is the half ester of butene dioic acid, this half ester and aspartic acid are reacted in as (ⅱ) alkaline aqueous medium in step, its reaction product is a random copolymers as mentioned above, and it is the most useful dispersion agent/synergistic agent in washing composition is used.Dense sodium carbonate/bicarbonate alkalescence buffering reaction medium is used for the reaction of (ⅱ) step, and then its competing reaction is that hydrolysis is just controlled, so that desired product has high productive rate.

The present invention also comprises the composition of washing composition, and it contains the general tensio-active agent that clean ability is arranged, SYNTHETIC OPTICAL WHITNER, enzyme and similar substance, and typical prescription accounts for about 0.1% to 35%(weight for compound of the present invention).

The percentage ratio of indication, ratio and umber are all calculated by weight otherwise indicated herein.

The present invention includes as shown in the formula simple low-molecular weight compound

In the simplest compound, E is alkyl, alkoxyl group alkylidene group or alkyl (poly-(alkylidene oxide)); For example methyl, ethyl, propyl group, butyl or as CH ₃OCH ₂CH ₂-Ji.

Generally, the L base can be connected in C ²Or C ³, having formed structure like this is the isomer mixture of I a and I b compound.In such mixture, generalized case is that the L base of major part (for example, about 80mol%) is connected in C ²On, a describes as I; Remaining is connected in C ³On, for structure I b, account for 0 to 20mol%.In the structural formula of back, in II-IX and XI-X VI, will represent the position that these two kinds interchangeable L replace with symbol ", " and " * "; Preferably or main 2 replace isomer structures, promptly the congener of I a will be depicted as, and more a spot of isomer partly can be envisioned as the congener of I b.

Herein, the L base of Shi Heing usually can be selected from following groups:

Top L ¹-L ¹⁴Any is all applicable to structural formula I a and I b in the group.

When E was a polyol derivative, its structural formula was rather complicated.Therein, the L of the replacement of institute's secondary of describing or three grades of substituted-aminos is connected on the E matrix above more than one.For example, at synergistic agent:

In the following formula, E is represented as CH ₂CH ₂, be (MAO) nE if use the given general formula in front, then n is 2.In addition, when E partly is when being obtained by the material that is similar to the tetramethylolmethane structure, compound of the present invention has following formula:

Composition of the present invention also can be replaced by the part of tetramethylolmethane and make, and they comprise the mixture of compound (III) and following formula: compound:

Composition of the present invention can obtain by laxative remedy equally, promptly partly replaces those groups that link to each other with quaternary carbon atom among any of formula III, (IV), (V) and (VI) with hydroxy methylene.New constituent in any one such composition can represent that this formula comprises the substituent of structure formula III to (VI) and hydroxy methylene with the general formula VII:

Herein, a is 0,1,2 or 3; B is 0,1,2, or 3; C is 1,2,3 or 4, and a+b+c=4.

Other exemplary compounds comprises that E partly has the compound of similar sorbyl alcohol structure herein; This compound can be represented by enough following formulas (Fisher projection formula):

E can also derive and obtains from the many alkylol cpds of ring-type; Like this, compound of the present invention can be, for example M

A

The α of-replacement-or Beta-methyl glucoside derivative; A representational α-derivative has following formula:

As top given structure (IV) to (VII), (OH) base of some alternative AM base or butene dioic acid salt half ester base (i.e. (C(O) CHCHCO ₂ Na

)) new compound may be present in and comprise among the compound compositions shown in formula (VIII) or the formula (X), particularly used compound (VIII) or (X) are not through under the situation of chemical purification, and be especially true.

When E was the group of a simple homopolymer type, compound of the present invention was an oligomer type or polymer-type.What for example, replaced by structure (IX) group fully is that the homopolymer of matrix can be expressed as with the polyvinyl alcohol:

In the case, the end group of homopolymer will be common PVA end group, used initiator and terminator when it is decided by that PVA is synthetic.

Common oligopolymer or multipolymer with basic (MAO) chain link also can prepare.They may be simple multipolymers, also may be ter-polymers, quadripolymer or its analogue.The unregulated polymer that makes according to the present invention generally includes the chain link of the formula (XI) that is taken as basic chain link; Herein, an interesting specific multipolymer can be represented with following chain link:

In the formula, exist a unit unitary with b " head is to tail " and " tail enemy's " different arrangements simultaneously.

Also comprise suc as formula represented random oligopolymer or the polymkeric substance of (X III)-(X V) herein:

Complicated oligopolymer or polymkeric substance can obtain, and promptly add hydrosulphite, allow it be attempted by on the C chain link in a part of formula (X IV), produce following structure:

The adding of vitriol (Sulfate) in this case will help being added in C ^*On the carbon atom of position.

In (X V), basic repeating segment (a) is the selectable chain link complementation of (b)-(e) with footnote, C " and C in formula (X III) ^*With reaching C with C ' ^*Same mode is defined; Sulfonation is at C like this ^*Be preferably on the position.

Better polymerization thing type compound of the present invention with the link units that comprises amino, alcohol radical and acetate base composition is shown in the following formula:

The difference that these unitary " head is to tails " reach " tail enemy " is arranged and is also included.The value that unit (a+b+d) adds together generally is about 100.One preferably embodiment be, a is 60 or higher, b be about 25 and d be about 15.

In all in front formulas, sodium cation can be substituted by other positively charged ion, particularly by H ⁺Or other water-soluble cationic such as positively charged ions such as potassium, ammonium substitute.

Details as Follows states round relevant with preferable embodiment of the present invention:

As mentioned above, preferably use not charged basically E part oligomer type or polymer-type herein.Will get rid of E especially is the charged polyanion body of any height as the derivative of polyacrylate, and this is different with the required how pure radical derivative of describing at this.

Have been found that the charged caused situation of L part is to be different from the charged caused situation of E part.Therefore, should select charged L part as L preferably ¹-L ³, L ⁵-L ⁹And L ¹¹-L ¹³(see before and state structure), they and L ⁴, L ¹⁰And L ¹⁴Be different.

Therefore, to the selection of one group of compound being used for detergent for washing clothes synergistic agent and dispersion agent especially, should carry out round the compound of general formula for (MAO) nE.Wherein n is 1 to about 2500 integer, and M is H or salt-forming cation; A can be selected from following one group of group: 2-(secondary substituted-amino)-4-ketobutyric acid alkali, its general formula is

OC(O) HCH C(L) ₂(O) C-, L is a secondary amino in the formula; Three grades of substituted-aminos of 2-()-and 4-ketobutyric acid alkali, its general formula is

OC(O) HCH C(L) ₂(O) C-, L is a tertiary amine base in the formula; 3-(secondary substituted-amino)-and 4-ketobutyric acid alkali, its general formula is

OC(O) CH ₂C(L) C-H(O), L is a secondary amino in the formula; Three grades of substituted-aminos of 3-()-and 4-ketobutyric acid alkali, its general formula is

OC(O) CH ₂C(L) C-H(O), in the formula L be a tertiary amine base, and composition thereof.E is a non-basically charged body, and its molecular weight is about 15 to 170,000; The E that this place is referred to partly has the contact of several covalent linkage, so as with (MAO) n part keyed jointing mutually; Described E part is formed by C and H or by C, H and O basically; When L herein was a secondary amino, it can be selected from following groups: aspartic acid alkali, L-glutamic acid alkali, glycine alkali, Beta-alanine alkali, taurine alkali, aminoethyl sulfuric acid alkali, L-Ala alkali and 6-aminocaprolc acid alkali; When described L was a tertiary amine base, L can be from being selected from following groups: sarkosine alkali, imino-diacetic acetate base and N-methylaspartic acid alkali.

Particularly under the situation that is used for dispersion agent, the Sauerstoffatom of or a considerable amount of covalent bondings is preferably arranged in E, and preferably use cheap and water-soluble salt-forming cation (as sodium cation or potassium cationic) safety.Like this, the present invention has determined the compound that this is useful, and wherein said salt-forming cation M is a water-soluble cationic, and described A partly has formula and is OC(O) HCH C(L) ₂(O) C-, described E part is basically by C, H and O forms and molecular weight is about 45 to 15,000.The lower molecular weight limits of E in these compounds is will be consistent with the situation that wherein has at least one Sauerstoffatom.

In application, be a long felt need for a considerable amount of charged MAO parts as dispersion agent.Like this, n to each E part, has at least three MAO then better preferably greater than 1.Yet when obtaining best effect as dispersion agent, n preferably is no more than 250.Like this, this compound that the present invention has, wherein M is a sodium; N is about 3 to 250, and the molecular weight of described E part then is about 45 to 15,000, and it is structural to be characterised in that it is that it contains dihydroxyl or the polyhydroxy-alcohol product of dehydroxylation wholly or in part.

Put it briefly, here preferable dihydroxyl of Shi Yonging or polyhydroxy-alcohol can be selected from following alcohol:

(ⅰ) polyvinyl alcohol;

(ⅱ) tetramethylolmethane;

(ⅲ) carbohydrate of from monose, disaccharides, oligose and polysaccharide, selecting;

(ⅳ) glucoside of selecting from monohydroxy-alcohol glucoside and dibasic alcohol glucoside;

(ⅴ) from C ₂-C ₆The alkylene dihydric alcohol that chooses in the alkylene dihydric alcohol;

(ⅵ) sorbyl alcohol; And

(ⅶ) said mixture.

Suitable carbohydrate can be enumerated as maltose, lactose, sucrose, Fructus Hordei Germinatus-oligomeric sugar and starch.

The glucoside that is fit to can be enumerated as α-Jia Jiputanggan, ethylidene binary alcohol glucoside and propylidene dibasic alcohol glucoside.

About the polyvinyl alcohol as the formation thing of E, particularly from the angle of decentralized compound, the professional will assert the implication of its " degree of hydrolysis " in general sense.More precisely, no matter whether this polyvinyl alcohol really is through the methyl alcohol alcoholysis by Vinyl Acetate Copolymer, " degree of hydrolysis " this useful term all is measuring of a basic-OH base content, with the content of hydrolysising group not such as the acetate groups that is different from such as exists sometimes.This term is that polyvinyl alcohol manufacturer adopts.The degree of hydrolysis of best as used herein polyvinyl alcohol sample is 70% or higher.Corresponding compounds especially is applicable in the detergent composition compound that the dispersion agent/synergistic agent as dispersion agent or combination uses, and wherein the structure of E part and its be from alcohol, particularly degree of hydrolysis be about 70% or the derivative of higher polyvinyl alcohol consistent.

The professional thinks degree of hydrolysis naturally less than 100% polyvinyl alcohol, its vinyl alcohol link units and vinyl acetate between to for plastic link units generally will be randomly or block ground distribute.When it participated in the compound of the present invention, the polymer architecture of this entire compound was subjected to the influence of this distribution naturally.

At one preferably in the embodiment, used compound is derived from polyvinyl alcohol, thereby it is made up of random copolymers basically.The molecular weight of this random copolymers preferably is about 635 to 50,000, is about 4950 to 49500 then better.The molecular weight of entire compound is decided by that the molecular weight of used polyvinyl alcohol and the relative proportion of A part are its molar fraction.Preferably this compound is a random copolymers, and it contains has an appointment 0.1 to about 0.95 molar fraction, more preferably contains the following formula repeating segment of about 0.60 to 0.95 molar fraction:

M is a sodium herein, and A is

OC(O) HCH C(L) ₂(O) C-.L is a charged body that accords with aforementioned definitions, and preferably it is selected from aspartic acid alkali, L-glutamic acid alkali, glycine alkali, taurine alkali, sarkosine alkali and imino-diacetic acetate base.

With regard to the preparation method; such compound can contain amino reactant one by above-mentioned polyvinyl alcohol and maleic anhydride and one and react and make, and wherein contains amino reactant and can select aspartic acid, L-glutamic acid, glycine, taurine, sarkosine, imino-diacetic acetic acid or their water-soluble salt for use.

This method is special a bit, and it preferably includes the following step:

(ⅰ) with above-mentioned polyvinyl alcohol and maleic anhydride reaction, produce the maleic acid semi-ester of described polyvinyl alcohol;

(ⅱ) with the maleic acid semi-ester of gained with contain amino reactant reaction.

In these method stepss, importantly step (ⅱ) is carried out in aqueous media, and the control that its basicity adds with carbonate buffer agent to this, will further be described below.

To a very effective method of completing steps (ⅰ) be with the mixture of polyvinyl alcohol and maleic anhydride with make the tetrahydrofuran (THF) of solvent and the acetate catalyst one of a significant quantity reacts, but require that the content of tetrahydrofuran (THF) is no more than about 5% to 20% of total amount in the said mixture.This reaction makes the maleic acid semi-ester of above-mentioned polyvinyl alcohol, and with it purification, then step (ⅰ) is promptly accused and finished.The method of purifying is its extracting to be gone into the lower floor of tetrahydrofuran (THF)/water mixture, and the volume/volume ratio that this mixture has tetrahydrofuran (THF) and water is about 1/2 to 1/12.

The method for preparing compound of the present invention

The first step

In detail, the general available two-step approach of the production of The compounds of this invention is finished.The first step of this method is generally the reaction of maleic anhydride and hydroxy-containing compounds, to obtain maleic acid semi-ester.Typical hydroxy-containing compounds (alcohol) is polyvinyl alcohol, tetramethylolmethane, tripentaerythritol, sorbyl alcohol, 1, ammediol, ethanol, Virahol, propyl carbinol and the methyl alcohol in addition of less usefulness.

Preferably adopt any that has been included in the alcohol cited in aforementioned (ⅰ)-(ⅶ) class.

The first step reaction can with or carry out without catalyzer.Generally, can adopt for example basic catalyst such as yellow soda ash or sodium-acetate.In general solvent to this reaction not necessarily because hydroxy-containing compounds is dissolved in maleic anhydride usually or by maleic anhydride institute swelling.When adopting solvent, should select those solvents that is suitable for swelling or dissolving hydroxy-containing compounds for use, this kind solvent such as tetrahydrofuran (THF), diox and dimethyl formamide etc., they are gratifying.

Select the required temperature of reaction of the first step reaction will depend on the space environment of these hydroxyls.Usually, the esterification of secondary alcohol needs higher temperature of reaction than the esterification of primary alconol.Generally,, be reflected in the tetrahydrofuran (THF), under its reflux temperature (about 65 ℃), carry out just enough for the most of primary and secondary hydroxyls of esterification.When not having solvent, the temperature that reaction needed is higher, usually at about 80 ℃ and 120 ℃, the degree of esterification that reaction reached in the time of just reaching with solvent.

The maleic anhydride consumption that reacts required is decided by

(a) hydroxyl is primary hydroxyl or secondary hydroxyl;

(b) required gamma value; And

(c) whether use solvent.

If hydroxyl is a primary hydroxyl, having used solvent and temperature of reaction is 65 ℃ or higher, and then hydroxyl is generally 1: 1 to the mol ratio of maleic anhydride, can make the above hydroxyl of 60 molecular fractions esterified.Under same condition, the excessive maleic anhydride that secondary alcohol then need be up to 2: 1 and the mol ratio of hydroxyl just can reach same degree of esterification.If only need lower gamma value, then available maleic anhydride in shortage is to the mol ratio of hydroxyl, and uses solvent in reaction usually.

When carrying out under being reflected at the condition that does not have solvent, needing the mol ratio of excessive maleic anhydride to hydroxyl under the normal circumstances, is a fluid so that make the gained reaction mixture.

When using solvent, used quantity of solvent will make hydroxy-containing compounds swelling or dissolving at least.Usually, solvent load is about 5% to 60% of reaction mixture weight, is preferably 5% to 20%.What make us feeling surprised is that low solvent load can cause good esterification yied.

When hydroxy-containing compounds during by solvent height swelling, the order that reactant adds is very important.Therefore, the order below usually adopting is better: at first maleic anhydride and catalyzer are dissolved in the solvent, heat this solution to 50 ℃, add hydroxy-containing compounds then.In the process that adds, the hydroxy-containing compounds partial esterification avoids the viscosity of reaction system to become too high.

The first step reaction and product ordinary representation thereof are in following:

Wherein the X VII is typical maleic acid semi-ester, and it is included in C ¹And C ^*Between two keys along or trans two kinds of configurations.The link units that reaches more than 80% can be by functionalization, and for example in the X VII, n ' and n " are respectively the marks that is higher than 0.8 times and is lower than 0.2 times total polymerization degree.Still keeping other link units, the link units of coming, promptly as deriving from vinyl acetate between to for plastic

This first step building-up reactions will be further described with non-sex-limited example 1-V in the back.

Following patent and patent documentation (listing in this as a reference) further describe the first step reaction that is used to prepare compound of the present invention.The initial compounds maleic acid semi-ester of second step reaction that the compound of being discussed in these documents all is suitable for being discussed below.These documents have the United States Patent (USP) issue on May 3rd, 4,021,359,1977 of Schwab; Soviet Union's journal article " Vysokmol.Soedin., " Ser.B., 1976,18(11) volume, 856-8 page or leaf, people such as Korshak; Japanese document JP 85/1480, transfers Japanese Shokubai, and on January 10th, 1985 is open; JP 79/20093, Yoshitake, and on September 13rd, 1979 is open; JP 77/85353, transfers Kuraray KK, and on July 15th, 1977 is open; JP 78/52443, transfers Kuraray KK, and on April 28th, 1978 is open; JP 84/36331, transfers Nippon Oils and Fats KK, and on February 29th, 1984 is open; JP 78/27119, transfers Kuraray KK, and on March 7th, 1978 is open; JP 77/59083, transfers Kuraray KK, and on May 20th, 1977 is open; JP 77/94481, transfers Kuraray KK, and on August 5th, 1977 is open; JP 77/94482, transfers Kuraray KK, and on August 5th, 1977 is open.

The maleic acid semi-ester that the first step is reacted gained is used for specific second step (the present invention's a part itself) reaction, then can obtain compound of the present invention.

Second step

The second synthetic step of compound of the present invention exists a huge technical difficult problem.If (these contain amino reactant generally is water miscible for half ester discussed above and specific amine or amino acid reaction; Face reaction (ⅰ) as follows), then to the necessary water solvent system of this reaction, because amine or amino acid solubleness in common organic solvents is very little.Yet the use of water solvent system causes various competing reactions unavoidably, for example the ester hydrolysis reaction of maleic acid semi-ester reactant or 2-amino-4-ketobutyric acid salt based products generation ester hydrolysis reaction.

The used method of the present invention can overcome esterolytic problem, and makes that reaction (ⅰ) has reduced its reversed reaction (ⅱ) smoothly simultaneously and obtains 2-amino-4-ketobutyric acid salt based compound with high productive rate in second step

The reaction of the 2nd step

Used typical reactant is

(a) specific amine or amino acid, general formula is L ¹H to L ¹⁴H;

(b) sodium hydroxide (being preferably the aqueous solution);

(e) water (solvent);

(d) maleic acid semi-ester of the first step reaction gained;

(e) yellow soda ash.

Typical step comprises:

(ⅰ) mix (a) and (b) and (c);

(ⅱ) cool off this mixture, generally be chilled to 0 °-10 ℃;

(ⅲ) add (d);

(ⅳ) progressively heating is no more than 100 ℃ to temperature.Be typically approximately to 80 ℃, preferably be no more than about 65 ℃, make (d) scatter or dissolve;

(ⅴ) attemperation makes and is lower than about 50 ℃;

(ⅵ) add (e); And

(ⅶ) reaction mixture is reacted down in the temperature (" temperature of reaction ") usually above environment, typical temperature is about 20 ℃ to 80 ℃, this is decided by the temperature one basicity relation that the back will go through, and just obtains product (reaction times generally is to be about 1 to 24 hour).

Above (a) and amount (b) can select by stechiometry.The compound of the present invention that obtains with this step can directly make the component as washing composition after preparation, or is further purified processing before using.

Generally, above reactant (a) in the step be a water dispersible or water miscible amine or amino acid, it has an amino at least, when its when protonated, its pKa is approximately less than 11.This amino must be primary amino or secondary amino group (because it is respectively parahelium product or the uncle's ammonia product that was used to prepare second step), and does not have big spatial obstacle.Amine or amino acid with spatial obstacle to a certain degree can also use, as long as it is reflected under the rational speed and can carries out.Generally, amino acid one speech comprises aminocarboxylic acid, amidosulphuric acid and thionamic acid.

Generally, when reactant (a) was not amine but amino acid derivative, reactant (a) can use its water-soluble cationic salt that is neutralized wholly or in part.Clear for describing, for example, based on above-mentioned L ⁷The suitable change of the best reactant (a) of group has comprised L ⁷H salt, i.e. aminoethyl sodium sulfate salt and free aminoethyl sulfuric acid.For simplicity, this reactant can be labeled as " aminoethyl sulfuric acid alkali " simply.Other preferably reactant (a) be formula L ¹H to L ⁶The sodium salt of H and formula L ⁸H is to formula L ¹⁴The sodium salt of H also comprises their corresponding free acids.

In addition, the selection of reactant, order that material adds and temperature controlling etc., all as implied above, to obtaining chemical combination material desire of the present invention good productive rate is arranged by the reaction of second step, below listed controlled variable be particularly important:

(ⅰ) basicity;

(ⅱ) shock absorption; And

(ⅲ) water-content.

In each parameter, the control of basicity is most important in the above; Specific shock absorption can provide the method for basicity control, and the control of water-content is very important.

Generally, high basicity is adopted in the reaction of second step.When high density, pH is not the observed value of a strictness, but an index, basicity generally is about 10 more than or equal to pH.Yet,, only can cause the hydrolysis of ester with high basicity as above-mentioned.

For fear of hydrolysis reaction, in alkaline reaction mixture, merge and adopt NaOH/Na ₂CO ₃(in the presence of acid organic reagent, carbonate-buffered with bicarbonate system is established basicity/buffer system, is by NaOH at the autochthonous inorganic salt promptly, Na ₂CO ₃And NaHCO ₃Form, this will remain discuss to be estimated).Under a simple situation, be about to amine, as thanomin (1mol) and maleic acid semi-ester (1mol) reaction, the NaOH of available about 0.1mol, the Na of the about 0.5mol of usefulness again ₂CO ₃Like this, NaOH/Na ₂CO ₃Total consumption can calculate according to whole neutralizing acids and the needs that provide reaction to carry out required excessive basicity.When amine itself is an a-amino acid, for example be aspartic acid (1mol), the Na of the NaOH of available about 2.6mol and about 0.5mol then ₂CO ₃In a word, the calculating of these consumptions be according in fully and the acid of butene dioic acid part, in and the H of 2mol in the aspartic acid ⁺And provide the 0.6mol excess base to draw.Big excessive alkali needs because in the aspartic acid ammonium ammonium have high pKa value (～9.7, by contrast the ammonium of thanomin have only～9.0).Under the situation of beta-amino acids (1mol), the consumption of NaOH (1.1mol) and Na ₂CO ₃The compute classes of consumption (0.5mol) like the situation of above-mentioned thanomin, and consider carboxyl in the amino acid.Clearly, in this step, suppose that following way is suitable, promptly selects NaOH/Na ₂CO ₃Ratio, generally should accord with the size of the pKa value of ammonium in the amine, also will be according to the mole number of the total acid carboxylate salt that from two possible sources (maleic acid semi-ester and acid aminocarboxylate), comes.

In general, also can be with other buffer system, as long as they can play the efficient buffer effect in the similar pH scope of above-mentioned hydroxide hydrochlorate/supercarbonate.

In the second step reaction, also can adopt the reactant (a) of aqueous solution middle and high concentration and (d).This two component is calculated by its sodium salt together, and the two weight concentration scope altogether is account for reaction mixture weight about 30% to 60%, preferably about 40% to 55%.

The reaction of second step also has the problem that basicity-temperature relation will match, and as obtaining optimum, is to carry out preferably it.Thereby higher basicity and lower temperature match and can react effectively, and on the contrary, lower basicity cooperates higher temperature of reaction that second group of optimized reaction conditions is provided.To the aspartic acid system, low reaction temperatures optimum condition and high reaction temperature optimum condition are described in down:

Aspartic acid butene dioic acid half Na ₂CO ₃NaOH

T ℃ of mole number ester mole number mole number mole number

37℃ 1 1 0.5 2.6

(seeing top explanation)

64℃ 1 1 0.71 1.8

(second group of optimum condition)

Needn't also can guess for this amine L by means of theory ^1-14Among the H each also exists similar optimum condition.At typical temperature and NaOH/Na ₂CO ₃In the scope of using, these conditions are to be easy to determine.

General step (the first step)

1A. the reaction product of maleic anhydride and hydroxyl reactant alcohol is loaded onto mechanical stirrer on a 500ml flask with three necks,round bottom that claimed weight, condenser and gas eduction tube, add tetrahydrofuran (THF) (20ml), maleic anhydride (68.99 grams, 0.704mol) and sodium-acetate (0.0288 gram, 0.000352mol).Reaction mixture is heated to 50 ℃ in oil bath in argon gas atmosphere.Hydroxyl reactant (its add-on is for being enough to obtain the hydroxyl of 0.352mol) joins in the reaction mixture under stirring fast, and the joining day is 5 minutes.Then, oil bath temperature rises to 65 ℃, and reaction mixture approximately remained under this temperature about 6 to 24 hours, obtains the settled solution of product.Its degree of esterification is measured with the method for step 1C.Then solvent is removed from reaction mixture, obtained resinoid solid product.

Looking particular case 1B. purify can be undertaken by following method.This method is particularly useful for the situation that the hydroxyl reactant is a polyvinyl alcohol.

To remove excessive maleic anhydride in the product that make among the step 1A, this product under agitation can be dissolved in tetrahydrofuran (THF) (100ml), then gained solution is poured in the long-pending water of triploid.In most of the cases, the volume/volume of this tetrahydrofuran (THF)/water is than approximately from 1/2 to 1/12.This just obtains a two-phase liquid mixture.Desired product is in bottom (phase), and surplus or free toxilic acid are stayed upper strata (phase).Tell bottom, lyophilize.Measure its ester content with the method for step 1E.

1C. maleic acid semi-ester Determination on content

With the sidewall and the condenser of THF flushing used round-bottomed flask in step 1A, so that the maleic anhydride refunds that comes up distilling is in reaction mixture.Flask together with wherein reaction mixture weighing, is obtained the weight of reaction mixture with the difference of its weight.Weigh up the five equilibrium (～250 milligrams) in the mixture, with the phenol red sodium hydroxide titration of doing indicator with 0.1N.Suppose the loss that does not have reactant in reaction process, then maleic acid semi-ester content can be calculated as follows:

Q ₁The mole number of used maleic anhydride in the every gram reaction mixture of mole number=2(of maleic acid semi-ester in=every gram reaction mixture)-(mole number of the residual acid of representing by every gram reaction mixture that titration records), because the mole number of hydroxyl in the used hydroxyl reactant among the known response 1A is so can predict the average esterification degree of sample.Calculate with molecular fraction, this gamma value can above the Q of gained ₁Mole number divided by hydroxyl in the hydroxyl reactant in every gram reaction mixture calculates and gets.

1D.1A or the mensuration of 1B product total acidity

Get the product of first-class 1A or 1B and use 0.1N NaOH titration, just can obtain numerical value Q to phenol red terminal point ₂The mole number of acidic group in=every gram maleic acid semi-ester.

1E. maleic acid semi-ester Determination on content in the 1A product of purifying

On a 25ml three neck round-bottomed flasks, load onto stirring rod, condenser and gas eduction tube, add (～30mg) the first-class half ester product of 1B step by step of weighing.(10.0ml 1.0mmol), heats reaction mixture oil bath with 100 ℃ under argon gas the sodium hydroxide of adding 0.1N, reacts 30 minutes, makes whole ester complete hydrolysis.Reaction mixture is chilled to room temperature, uses 0.1N salt acidometric titration to phenol red terminal point.The titre of every gram reaction mixture and Q ₂The difference of (1D is measured in step) promptly provides Q ₁(molar weight of ester units in the 1A product of every gram purifying)

With top said step, the hydroxyl reactant that the column selection of according to the form below institute is specific, just can carry out the first step of synthetic method:

The selected hydroxyl reactant of example

1 ethanol

2 Virahols

3 tetramethylolmethanes

4 sorbyl alcohols

5 polyvinyl alcohol

2A. amido functional group reactant (a) adds in step 1A or the 1B product in the time of 37 ℃

Select to have measured Q ₁Value (with step 1C or 1E) and Q ₂The step 1A of value (using step 1D) or the product Y of 1B gram, its weight of getting is to make it can obtain the maleic acid semi-ester group of 0.017mol.Gas introduction tube is housed and has to add in the 25ml flask with three necks,round bottom of mechanical stirring device at one and contain amino reactant (0.017mol), water (2.5 gram) and contain 40%(weight) aqueous solution of sodium hydroxide.When containing amino reactant and being aspartic acid, the weight (W) of this NaOH solution of 40% is when selected:

W＝ 40/0.4 ｛（0.6×0.017）+（Q ₂×Y）+（2×0.017）-（2×0.0085）｝

When containing amino reactant and being sarkosine or glycine, it is when selected:

W＝ 40/0.4 ｛（0.6×0.017）+（Q ₂×Y）+（1×0.017）-（2×0.0085）｝

When containing amino reactant and being thanomin, it is when selected:

W＝ 40/0.4 ｛（0.6×0.017）+（Q ₂×Y）-（2×0.0085）｝。

Flask is placed on ice bath internal cooling reaction mixture, under agitation once adds the product of Y gram step 1A or 1B.With 37 ℃ oil bath heating, typical case is the suspension that obtains a milk shape to reaction flask under violent stirring.(0.807 gram 0.0085mol), avoid producing too much foam slowly to add yellow soda ash then.Reaction mixture kept 4 hours in 37 ℃ of oil baths, was chilled to room temperature, and with isopyknic water dilution.The pH value of regulating this solution with 0.1N sulfuric acid is 7, and lyophilize is to obtaining a white solid.In addition, can also not regulate its pH value, and adopt purification step (referring to the 2C or the 2D of back).

The product of synthetic method the first step gained can prepare compound of the present invention with the method 2A of above-mentioned step:

The product of step 2A

Step 1A or 1B step 2A product

The product of example contains the structure type of amino reactant

The product aspartic acid L of 6 examples 1 ¹I a that replaces and I b mix

Compound is based on isomer I a

The product sarkosine I of 7 examples 1, L ⁹

The product glycine I of 8 examples 1, L ³

The product thanomin I of 9 examples 1, L ⁴

The product aspartic acid I of 10 examples 2, L ¹

The product aspartic acid III of 11 examples 3, L ¹

The product aspartic acid VIII of 12 examples 4, L ¹

The product aspartic acid XI of 13 examples 5, L ¹

The product sarkosine XI of 14 examples 5, L ⁹

The product glycine XI of 15 examples 5, L ³

The product thanomin XI of 16 examples 5, L ⁴

Example 17

Three mouthfuls of round-bottomed flasks of 500ml that weighed toward one and that stirring rod, condenser and gas eduction tube be housed add tetrahydrofuran (THF) (125ml), maleic anhydride (68.99 grams, 0.704mol) and sodium-acetate (0.0288 restrains, 0.000352mol).Reaction mixture is heated to 50 ℃ under argon atmospher, in the oil bath.(trade mark is GOHSENOL, Japanese Gohsei company product, polymerization degree ≈ 100,87% hydrolysis to add polyvinyl alcohol lentamente.20.0 gram, hydroxyl 0.352mol).Oil bath temperature rises to 65 ℃ then, and reaction mixture kept 28 hours under this temperature, obtains an amber solution.The gamma value of polyvinyl alcohol 1C set by step is determined as 79%.From reaction mixture, remove solvent, obtain an arborescens solid product (97.7 gram), press laxative remedy its purifying.

The arborescens product stirred down at room temperature be dissolved in tetrahydrofuran (THF) (100ml), this solution is poured in the intensively stirred water (500ml), obtains a two-phase liquid.The product of wanting in lower floor's liquid phase, and the residue or free toxilic acid stay in the upper phase.Subnatant is separated out, removes tetrahydrofuran (THF), obtain the cream-coloured liquid of a heavy-gravity (68.0 gram).This liquid is mixed with water (50ml), and lyophilize then obtains beige solid, 42.3 grams; ¹H NMR analyzes (with 3-trimethyl silicane-2,2,3,3-d ₄-propionic acid sodium salt is a reference substance), the wide multiplet of δ 1.3-2.5(), the wide multiplet of δ 4.5-5.4() and, δ 5.9-6.5(multiplet).Solid that this is cream-coloured and aspartic acid can react by laxative remedy:

At first cream-coloured solid is used step 1E and its Q of 1D assay determination respectively ₁And Q ₂Value gets Q ₁=0.00681 mole of maleic acid semi-ester base/every gram solid; Q ₂=0.006876 mole of acidic group/every gram solid.The amount that provides the beige solid of 0.017mol maleic acid semi-ester group can be calculated as follows:

$\mathrm{Y\; =}\frac{\mathrm{0.017}}{Q_1}\mathrm{=\; 2.5}$

To a 25ml flask with three necks,round bottom that gas introduction tube and mechanical stirring device be housed add aspartic acid (2.27 grams, 0.017mol), deuterium-oxide (2.5 gram) and 40% deuterium aqueous solution of sodium oxide, the weight of NaOD solution is:

W=41/0.4 { (0.6 * 0.017)+(0.006876 * 2.5)+(2 * 0.017)-(2 * 0.0085) }=4.54 gram

Flask is placed on the ice bath with reaction mixture, the cream-coloured maleic acid semi-ester solids of 2.5 grams, one five equilibrium are under agitation once added in the flask.

Under agitation with 37 ℃ of oil bath heating, (0.900 gram 0.0085mol) slowly adds reaction flask, avoids producing a large amount of foams with yellow soda ash then.Reaction mixture kept 4 hours in 37 ℃ of oil baths, and with isopyknic water dilution, the pH of this solution is 9.81 then.Regulate the pH to 7.0 of this solution then with 0.1N sulfuric acid, lyophilize is to obtaining a white solid (5.8 gram).This solid is further purified (in step 2D discussion, as follows) with gel permeation chromatography.

This white solid (0.92 gram) is dissolved in the 10ml water, this solution is loaded into 2.5 * 95cm BIOGEL P2(Bio Rad company) in the post or be loaded in the polyacrylamide gel of equivalent, be to carry out wash-out in 12-16ml/ hour with the flow velocity, about 15.5 hours is to carry out wash-out 8 hours in 25-35ml/ hour at flow velocity then.The wash-out fraction of the product of wanting is 250-400ml, and impurity wash-out fraction is 400-470ml.With this 250-400ml fraction lyophilize to obtaining white solid: 0.3 the gram; ¹H NMR(is with the 3-(trimethyl silicane)-2,2,3,3-d ₄-propionic acid sodium salt is a reference substance) the wide multiplet of δ 1.3-2.1(), the wide multiplet of δ 2.5-3.1() and, the wide multiplet of δ 3.5-4.0(), the wide multiplet of δ 4.7-5.3(); Ultimate analysis: C, 38.57%; H, 4.58%; N, 3.32%.

Example 18

Add tetrahydrofuran (THF) (170ml) to the 1000ml flask with three necks,round bottom that mechanical stirrer, condenser and gas eduction tube are housed of having weighed, maleic anhydride (493.8 grams, 5.04mol) and sodium-acetate (0.225 restrains, 0.0027mol).This mixture is heated to 50 ℃ and dissolves until maleic anhydride in oil bath under argon gas.Add polyvinyl alcohol (GOHSENOL, Japanese Gohsei company, polymerization degree ≌ 100,87% hydrolysis, 150.0 grams, hydroxyl 2.63mol), about 3 minutes of joining day.Oil bath temperature rises to 65 ℃, and reaction mixture kept 25 hours under this temperature, obtains an amber viscous solution.The gamma value of polyvinyl alcohol is measured as 97% with step 1C method.

Under agitation pour the reaction mixture (about 700ml) of top gained in the intensively stirred 10 ℃ water (2000ml), obtain two-phase liquid.After stirring in the time of 25 ℃ 1 hour, allow it two be separated.Desired product is in the bottom liquid phase, and excessive or free toxilic acid is stayed upper phase.Bottom liquid phase (about 500ml) is branched away and is diluted with fresh tetrahydrofuran (THF) (800ml).The solution that obtains is poured in the fresh water (1400ml) and 25 ℃ of violent stirring 1 hour, and lower floor's liquid phase pours in four 9 " * 15 " glass baking basins to liquid depth and is about 1cm, places in the stink cupboard evaporation 18 hours.With gained arborescens thing in a vacuum 25 ℃ place 48 hours to remove residual solvent, obtain hard glass foams.It is bored mill, obtain linen powder (272 gram). ¹H NMR(is with the 3-(trimethyl silicane)-2,2,3,3-d ₄Propionic acid sodium salt is a reference substance) the wide multiplet of δ 1.3-2.5(), the wide multiplet of δ 4.5-5.4() and, δ 5.9-6.5(multiplet).This solid is reacted with aspartic acid as follows:

At first analyze the Q of this solids respectively with step 1E and 1D ₁And Q ₂Value: Q ₁=0.00602 mole of maleic acid semi-ester base/every gram solid, Q ₂=0.00595 mole of acidic group/every gram solid.Can provide the amount of solid of 0.244 mole of maleic acid semi-ester base to be calculated as follows:

$\mathrm{Y\; =}\frac{\mathrm{0.244}}{Q_1}\mathrm{=\; 40.5}$

The aspartic acid salts solution can make with this quadrat method: (45.3 grams 0.341mol) in water (50 gram), add water (62.8 gram) solution of the sodium hydroxide of 50%W/W to the dissolving aspartic acid.This solution is chilled to about 0 ℃.The amount of used sodium hydroxide is based on down column count:

W＝ 40/0.5 ｛（0.6×0.340）+（0.00595×40.5）+（2×0.340）-（2×0.170）｝

=62.8 grams

In device has the 500ml flask with three necks,round bottom of inlet mouth, mechanical stirrer and two feed hoppers, in the time of 0 ℃, mix " Y " gram maleic acid semi-ester solid (40.5 grams, 0.244mol) and aspartic acid salts solution (158.1 gram), two kinds of materials are to add from two funnels respectively in batches, big this identical and adding simultaneously of every batch amount lasts about 15 minutes.Reaction mixture is mixed by violent stirring, obtains a butyraceous heavy-gravity and steeps liquid more.Reactor is warmed to about 37 ℃ in oil bath, (18.0 grams 0.17mol), avoid too much foam to generate slowly to add yellow soda ash.Reaction mixture in oil bath, keep 37 ℃ 4 hours, be chilled to envrionment temperature, with the dilution of equal-volume water, the pH of this solution is 9.81 then.The method of product available step 2B is purified.If desire is purified it and use without the method for 2B set by step, then with regulating its pH to 7.0 with 1.0N sulfuric acid, lyophilize and obtain white solid (136 gram) then.This material can be used as suitable random copolymers without further purifying, and can be used as the dispersion agent in the cloth-washing detergent prescription, and its consumption is about 0.1% to 10%, and the back will further describe it.Such prescription has comprised the tensio-active agent of washing composition, does not need to comprise any common dispersion agents such as for example polyacrylate again.

2B. the purifying of step 2A product

The thick product of poly-hydroxy thing deutero-can simply be purified with sedimentary method from the aqueous solution.For example, polyvinyl alcohol derivative can be about at 2.4 o'clock at pH and precipitates.

Usually, impure impurity, such as toxilic acid, FUMARIC ACID TECH GRADE and the initial residue that contains amino reactant etc. can be poured crude product in solution (for the firm preparation person before the pH regulator to 7) in the methyl alcohol (generally being 3 to 6 times volume) into and just can remove.Concentrate this and have the solution of impurity, desired product just is precipitated out.Yet the impurity of some amount still can be present in the precipitation, and this precipitation can further be purified, and being about to it soluble in waterly becomes a 50%(weight) solution, be poured in the methyl alcohol then.Desired product is precipitated out.This process can repeat to make several times impurity further to remove from desired product.

2C. the step of another purification also may be utilized.Use gel permeation chromatography, come each component in the separate reacted mixture according to the difference of molecular weight.When the room temperature, can carry out classification with one 2.5 * 100cm ALTEX post.Elutriant can detect with WATERS R403 type refractive index detector, and the flow velocity of elutriant can be kept with MASTER FLEX peristaltic pump, and used gel generally is about 150 grams of BIO GEL P-2(), the void volume of post is about 150ml.

The product of about 0.5 gram step 2A is dissolved in the 5ml water, and gained solution is loaded in the post and makes it and is about wash-out under 12-15ml/ hour the condition at flow velocity.The order of component wash-out depends on its molecular weight, and high-molecular weight component elder generation wash-out goes out, and wash-out goes out after the low-molecular-weight component.After gpc purified, the mode that compound of the present invention just can be common characterized with NMR spectrum, ultimate analysis and similar means.

Detergent composition

Compound of the present invention is effective dispersion agent, particularly for clay, Magnesium Silicate q-agent and Calcium Pyrophosphate.They can be used for detergent for washing clothes as dispersion agent or with the synergistic agent of high consumption as detergent for washing clothes with low consumption.

No matter compound of the present invention is mainly as dispersion agent or mainly as synergistic agent, and its content in laundry detergent composition all can change in very wide scope.The The compounds of this invention of preparation gained can directly join in the detergent for washing clothes, its consumption approximately can account for final composition weight 0.1 to 35% or higher, preferable consumption is about and accounts for the about 0.1% to 6% of laundry detergent composition weight when making dispersion agent and using, and when making synergistic agent and using its preferable consumption general about 6% to 35%.

During only with one tensio-active agent, it may be very simple describing, yet the composition of preferable detergent for washing clothes described herein but is a more complicated.For example, when these compounds during as dispersion agent, are generally used at least one tensio-active agent and at least one common washing composition synergistic agent, the latter preferably do not have phosphoric acid salt or with the synergistic agent of pyrophosphate salt form.

A kind of like this composition of essentially no polyacrylic acid dipersant can be produced and use, and is particularly advantageous.

In when washing preparation laundry, generally to take safeguard procedures directly to contact with used concentrated acid formula concentrated base, especially in preparation employing comparatively high temps to avoid compound of the present invention.General herein laundry detergent formulations comprises composite particle of phosphoric acid salt and the composite particle of no phosphoric acid salt (preferable), contains the composite particle of pyrophosphate salt, no phosphoric acid salt compositional liquor and European no phosphoric acid salt particle.Referring to following patent and application for patent, list as a reference entirely in this.

Polyacrylate component in the detergent for washing clothes that the The compounds of this invention of preparing can replace making usually simply (with the consumption of dispersion agent) or replace its boosting components (with the consumption of synergistic agent), and outstanding effect is arranged.

Particularly, the disclosed preparation work that will help washing composition below:

The tensio-active agent of washing composition:

To comprise organic surface active agent (" tensio-active agent ") in the detergent composition of the present invention, to obtain using upward related common cleaning function with these materials.

Useful herein detergent surfactant comprises known synthetic anionic, non-ionic type, both sexes are (acid-basicity) and tensio-active agent amphoteric ion type.This wherein typically has the α-sulfonate of alkylbenzene sulfonate, alkyl and sulfated alkyl ether, paraffin hydrocarbyl sulfonate, alkylene sulfonate, amine oxide, lipid acid and the pure and mild ethoxylated alkylphenol of α-sulfonate, alkylglycoside, ethoxylation of fatty acid ester, and the like material.These are all known in the washing composition prior art.Generally, such detergent surfactant all comprises C ₉-C ₁₈Alkyl, what the anionic detergent tensio-active agent was used is the salt of their sodium, potassium or triethanol ammonium.Standard data text is listed these typical detergent surfactants in detail as McCutCheon ' s Index.In current each based composition, C ₁₁-C ₁₄Alkylbenzene sulfonate, C ₁₂-C ₁₈The paraffin hydrocarbyl sulfonate, C ₁₁-C ₁₈Alkyl-sulphate and C ₁₁-C ₁₈Sulfated alkyl ether is good especially.

Useful herein tensio-active agent also has water-soluble soap class, for example, and the common cocounut oil of having known in the prior art or the soda soap or the potash soap of butter.Unsaturated soap such as alkyl soap also can use, and particularly use on liquid formulations.Saturated or unsaturated C ₉-C ₁₆The hydrocarbyl succinic hydrochlorate also is effectively.

It is few to 1% to as many as 98% that surface active agent composition can account for used detergent composition, and this gets due to used specific surfactant and desired effect.Generally, it is about 5% to 60% that its composition comprises, preferable about tensio-active agent of 60% to 30%.Adopt anionic as alkylbenzene sulfonate, alkyl-sulphate and paraffinic base sulfonate etc. and C ₉-C ₁₆The surfactant mixtures of ethoxylated alcohol, remove simultaneously for washing that various dirts and iron rust are preferably on the fabric.

Generally, anionic, combinations-of surfactants cationic and non-ionic type are got up to use.Such combination, or the just combination of the tensio-active agent of anionic and non-ionic type are preferably for the composition of liquid washing agent.Such tensio-active agent often with the form utilization of acid, is neutralized when liquid detergent composition is prepared.Be used for liquid detergent composition preferably aniorfic surfactant comprise linear alkylbenzene sulfonate, alkyl-sulphate and alkyl ethoxylated sulfate.Nonionic surface active agent comprises many ethoxylations of alkyl alcohols preferably.

The detergent surfactant that aniorfic surfactant is used for doing granular detergent composition is more satisfactory.Aniorfic surfactant comprises linear alkylbenzene sulfonate and alkyl-sulphate preferably.Particularly useful in the application that is combined in detergent granules of anionic detergent tensio-active agent and non-ionic detergent tensio-active agent.

The additive of washing composition: detergent composition can comprise other interpolation component, and they help to improve clenaing effect.For example, comprise enzyme in the laundry detergent composition, to increase them to the ability that various dirts and iron rust are disposed simultaneously by washing, this is extraordinary.In the prior art and in commercially available liquid and detergent granules, amylase and proteolytic enzyme are applicable to that the fact of washing composition is well-known.The general consumption of commercial enzyme for detergent (the preferably mixture of amylase and proteolytic enzyme) is 0.001% to 2% in existing composition, or higher.

In addition, except that the interpolation component of having said, composition also comprises various suitable other batching that typically is used for commodity, so that the advantage on aesthstic or the additional product performance to be provided.Typical batching comprises pH regulator agent, spices, dyestuff, SYNTHETIC OPTICAL WHITNER, whitening agent, polyester scale remover, fabric softener, solubility promoter and gel control agent, freeze-thaw stablizer, sterilant, sanitas, soap bubble control agent, bleach-activating agent or the like.

Other detergent additives: the detergent composition of full formula also may comprise various metal ion chelation agents, as amine sequestrant and phosphine acid salt chelator, and as diethylidene three ammonia pentacetates, alkylidene amino phosphonate such as ethylidene diamino tetra methylene phosphonic acid salt, or the like.The disclosed Smectite clay of clay softening agent such as prior art, and they also can be used softening washing to be provided and to remove remollescent advantage simultaneously with the composition of amine and quaternary ammonium compound.The typical amounts of additional synergistic agent is 5-50%.Such material comprises 1-10 micron zeolite A, 2,2 '-the oxo disuccinate, tartrate, mono succinate salt and two salt, Citrate trianion, C ₈-C ₁₄Hydrocarbyl succinic hydrochlorate, tripoly phosphate sodium STPP, pyrophosphate salt, carbonate, or the like.Inorganic salt such as sal epsom also can be included.

In washing and the fabric laundry method removed, in washing pool during laundering of textile fabrics, the general consumption of laundry detergent composition is about 0.10% to 2.5%, and typical pH is 7-11.Fabric and scouring agent composition can be stirred together during laundry, temperature can be 5 ℃ of boiling points to water, and this will obtain good washing effect, preferably wash under about 35 ℃ to 80 ℃ temperature.

Following abbreviation will be used for later example:

The LAS linear alkylbenzene sulphonic acid, it has C ₁₂, C ₁₁-C ₁₂Or C ₁₃Alkyl chain

AS C _12-20Alcohol sulfate, for example ox ester alcohol sodium sulfate (Sodium tallow

alcohol sulfate）

NI has the 6-7 mole by the C of ethoxylation ₁₂-C ₁₃Or C ₁₄-C ₁₅Primary alconol;

Dobanol or Neodol

Q ₁C _12-14Base trimethylammonium chlorination (or bromination) ammonium

Q ₂Two C _16-18The base alkyl dimethyl ammonium chloride

A ₁Two tallow methylamines or distearyl methylamine

White bentonite/the polynite of BENT; Particulate, cation exchange capacity 50-110meq/

100g

The STPP tripoly phosphate sodium STPP

The ORTHO sodium orthophosphate

The PYRO trisodium phosphate

The NTA nitrilotriacetic acid(NTA)

Z ₄A zeolite 4A, the 1-10 micron

The CARBONATE anhydrous sodium carbonate

The SILICATE water glass, Na ₂O: SiO ₂Than being 1.6: 1; Solid

ODS 2,2 '-oxo disuccinic acid tetra-na salt

TMS/TDS tartrate monosuccinic acid salt and tartrate disuccinic acid salt mixture,

Weight ratio is 80/20 or 85/15, sodium-salt form

The ACR1 polyacrylic acid, molecular-weight average is about 4500, sodium salt.

Toxilic acid/acrylic copolymer of 3: 7 of ACR2, molecular-weight average are approximately

60,000-70,000, sodium salt.

MgSO ₄Sal epsom, anhydrous

Na ₂SO ₄Sodium sulfate, anhydrous

Sequestrant (being used interchangeably):

EDDS S, the amino disuccinic acid of S-ethylene

EDTMP ethylene amino four (methylene phosphonic acid)

DETPMP diethylidene triamino five (methylene phosphonic acid)

DTPA diethylidene triamino five (acetic acid)

The CMC Xylo-Mucine

PB ₄Four water sodium perborate

PB ₁Monohydrate sodium stannate

The tetra-acetylated ethylene diamine of TAED

NOBS nonanoyl oxo benzene sulfonic acid sodium salt

INOBS 3,5,5-trimethyl acetyl base oxo benzene sulfonic acid sodium salt

SRP ethylene glycol or 1, the linear copolymer of 2-propylene glycol and dimethyl terephthalate (DMT),

Preferably low-molecular-weight (according to appointment 25,000 or lower), have sulfonated

Group

In demand selectable batching also comprises albumen (hydrolysis) enzyme (Alcalase, Maxatase, Savinase, Amylase { Termamyl }) and whitening agent (DMS/CBS, for example 4,4 '-two (2-morpholinoes-4-anilino-5-triazinyl-6-amino-stilbene)-2: 2 '-disulfonic acid disodium salt.）。Rest part comprises water and some amounts of additives such as spices in the composition, polysiloxane/silicon-dioxide or soap class, for example, and the tallow fatty acid froth suppressor, the polyoxygenated ethylidene glycol, as PEG-8000, and the water solubility promoter, as toluenesulfonic acid sodium salt.

Example 19

A B C D E F

LAS 7.4 14.8 0 7.4 0 7.4

TAS 7.4 0 0 7.4 14.8 7.4

NI 1.5 0 14.8 1.5 0 1.5

Carbonate 17.3 17.3 17.3 17.3 17.3 17.3

Silicate 4.7 4.7 4.7 4.7 4.7 4.7

Z ₄A 24.0 24.0 24.0 24.0 24.0 24.0

Example 17 products 0.1 0.1 2345

All the other: add water to 100 100 100 100 100 100

G H I J K L

LAS 7.4 0 7.4 7.4 7.4 7.4

TAS 7.4 14.8 7.4 7.4 7.4 7.4

NI 1.5 0 1.5 1.5 1.5 1.5

Carbonate 17.3 17.3 17.3 17.3 17.3 17.3

Silicate 4.7 4.7 4.7 4.7 4.7 4.7

Z ₄A 24.0 24.0 24.0 10 5 0

Example 17 products 67 10 15 20 30

All the other: add water to 100 100 100 100 100 100

Each row from A to L add each additive formulations by the weight percentage shown in the last table, and the product of example 17 adds at last under each situation, is made into aqueous mixture.Prepare each solution with tap water.Further dilute above each solution with same tap water (hardness is 12grains/gallon), the content that makes every kind of solution in the wash trough is 1,500ppm.Fabric adds wherein, and washing operation is made at stirring-type detergency test machine Terg-O-Tometer(U.S.Testing Co. at 125 °F (52 ℃)) in carry out.

Example 17 products in alternative each row of example 6-16 and each product of 18.

Example 20

The liquid detergent composition that home laundry is used is as follows:

Composition weight, %

C ₁₄-C ₁₅Alkyl polyethoxye (2.5) vitriolate of tartar 8.3

C ₁₂-C ₁₄Alkyl-dimethyl amine oxide 3.3

Potassium toluene sulfonate 5.0

Monoethanolamine 2.3

The TMS/TDS triethanolamine salt, 85/15 TMS/TDS 15.0

1,2-dihydroxyl-3,5-benzene disulfonic acid sodium 1.5

Example 17 products 1.5

Composition weight, %

Excess: adding distil water to 100

Add each component and mixing continuously together, obtain above-mentioned composition.

Replace example 17 products with example 18 products, obtain same result.

Example 21

Home laundry washes the agent composition by liquid and makes with mixing following batching:

C ₁₃Alkyl benzene sulphonate (ABS) 8.0%

Trolamine-COCOalkyl ether Sulfate 8.0

C ₁₄-C ₁₅Alcohol ethoxylate-7 5.0

C _12-13The alkyl monocarboxylate 5.0

Example 17 products 5.0

Diethylidene triamino pentamethylene phosphonic acids 0.8

Polyacrylic acid (molecular-weight average: about 5000) 0.8

Trolamine 2.0

Ethanol 8.6

1,2-propylene glycol 3.0

Maxatase enzyme (2.0Au/g activity) 0.7

Distilled water, spices, pH7.6 buffer reagent

And other configuration 100

The following preparation of the granular detergent composition of example 22-39: at first prepare a powdered composition of doing the basis, promptly mix all components (but the Dobanol 45E7 that wherein exists, except SYNTHETIC OPTICAL WHITNER, bleach-activating agent, enzyme, soap bubble inhibitor, phosphoric acid salt and the carbonate), in an amalgamator, stir into the water soup compound at 55 ℃, wherein moisture about 35%.Then water slurry is about 330 ℃ of following spraying dryings in the gas feed temperature, obtains base materials powder shape particulate.With the bleach-activating agent that wherein exists with as the TAE of tackiness agent ₂₅Mix, by one radially forcing machine (be described in United States Patent (USP) 4,399,049, people such as Gray, deliver August 16 nineteen eighty-three, is hereby incorporated by reference data) be extruded into extended " noodles ".Then the powder composition of bleach-activating agent " noodles ", SYNTHETIC OPTICAL WHITNER, enzyme, soap bubble inhibitor, phosphoric acid salt and carbonate and base-material is done and mixed, Dobanol 45E7 is sprayed in the mixture of gained with spray method.At last, the form of compound of the present invention after with lyophilize added with dry mix.

22 23 24 25 26 27 28

LAS 6.0 8.0 6.0 6.0 6.0 6.0 7.0

TAS 2.5 0.0 2.5 2.5 2.5 2.5 1.0

NI 5.5 4.0 5.5 5.5 5.5 5.5 0.0

Q ₁- - - - - - 1.5

Q ₂- - - - - - 0.5

A ₁- - - - - - 3.0

BENT - - - - - - 5.0

STPP - - - - - - 24.0

PYRO - - - - - - -

NTA - - - - - - -

Z ₄A 21.0 20.0 18.0 21.0 21.0 21.0 -

CARB 10.0 15.0 15.0 12.0 10.0 10.0 3.0

SIL 3.0 5.0 10.0 6.0 3.0 3.0 3.0

ODS - - - - 4.0 - -

TMS/TDS - - - - - 2.0 -

ACR1 - - - 3.0 - 1.0 -

ACR2 - - - - 2.0 - -

MgSO ₄0.4 0.4 0.4 0.4 0.4 0.4 0.4

Na ₂SO ₄11.0 11.0 11.0 11.0 11.0 11.0 11.0

Sequestrant 0.3 0.3 0.3 0.3 0.3 0.3 0.3

CMC 0.7 0.7 0.7 0.7 0.7 0.7 1.0

PB ₄- 24.0 - 24.0 - - 24.0

PB ₁12.0 - 11.0 - 11.0 11.0 -

TAED 1.5 2.0 - - - - -

NOBS - - - 2.0 - - -

INOBS - - 2.0 - 2.0 2.0 -

SRP 1.0 - - - - - -

Example 17 products 4.0 5.0 5.0 2.0 1.0 1.0 1.0

H ₂O and some a small amount of compositions-to 100-

29 30 31 32 33 34 35

LAS 12.0 4.1 7.4 4.0 11.0 12.0 16.0

TAS 7.0 6.4 7.4 6.4 11.0 6.0 -

NI 0.8 6.4 1.2 0.3 1.0 1.0 -

Q ₁- - - - - - -

Q ₂- - - - - - 5.0

A ₁- - - - - - -

BENT - - - - - - 6.0

STPP - 5.6 25.0 39.4 - - 28.0

PYRO - 22.4 5.9 - - - -

NTA - - - - - - 3.0

Z ₄A 29.0 - - - 27.0 10.0 -

CARB 17.0 12.2 16.8 12.0 17.0 15.0 12.0

SIL 2.5 6.0 4.7 5.5 2.0 2.0 6.0

ODS - - - - - - -

TMS/TDS - - - - - - -

ACR1 6.0 - - - - - -

ACR2 - - - - - - -

MgSO ₄2.0 - - - - - -

Na ₂SO ₄15.0 20.0 10.0 7.0 20.0 20.0 24.0

Sequestrant 1.0-0.4----

CMC - - - - - - -

PB ₄15.0 5.0 5.0 - - - -

PB ₁4.0 - - - - - -

TAED 3.0 2.0 - - - - -

NOBS - - 8.0 - - - -

INOBS 1.0 - - - - - -

SRP 1.0 - - - - - -

Example 17 products 4.0 4.0 4.0 3.0 6.0 10.0 2.0

H ₂O and other a small amount of compositions-to 100-

36 37 38 39

LAS 6.0 6.0 14.0 -

TAS 3.0 3.0 - -

NI 6.0 6.0 - 12.0

CARB 10.0 7.0 - -

SIL 7.0 3.0 - -

Na ₂SO ₄15.0 20.0 20.0 20.0

PB ₄18.0 10.0 10.0 2.0

TAED 2.0 2.0 2.0 2.0

Example 17 products 20.0 25.0 30.0 15.0

H ₂O and other a small amount of compositions-to 100-

Example 40

One of this case description comprises a high proportion of useful especially compound of the present invention in interior actual composition, and these compounds can be without further purifying as the dispersion agent in the laundry detergent composition.Preferable polyhydroxy-alcohol used herein is a glucoside.Said composition can be made by starch, ethylene glycol, maleic anhydride and D.L-aspartic acid.At first ethylene glycol and starch are reacted by the method for known technology in the presence of sulfuric acid and obtain single and two monoethylene glycol glucosides.Referring at this F.H.Otey as bibliography, F.L.Bennett, B.L.Zagoren and C.L.Mehltretter work " Ind.End.Chem.Prod.Res.Develop. ", 4,224 pages, nineteen sixty-five.Method with general step 1A, with single/pair-mixture of glycol glucoside and maleic anhydride reaction, the 3.3mol maleic anhydride is used in every mole of starch unit (dextrose anhydrous) in the glucoside mixture, obtain the maleic acid semi-ester of glucoside mixture, characterize it with the method for step 1D and 1E.The result who obtains according to these steps: Q ₁=7.41 * 10 ^-3Mol maleic acid semi-ester/every gram sample, Q ₂=6.59 * 10 ^-3Mol acid/every gram sample.

Maleic acid semi-ester and aspartic acid reaction (by general step 2A) with the glucoside mixture promptly obtain product composition.

The structure of each compound of the present invention (in fact, it is decided by main molecule in stable product composition chemically) is similar in appearance to fairly simple, the represented methyl glucoside of front formula (X).Point out that the comparison difference is: MA-replaces (M=Na, A=-OC(O) C(L) HCH herein ₂(O) C-, wherein L is L ', i.e. the aspartic acid alkali) not typically utterly completely; Certainly, methyl is non-existent, because E partly is a unit based on oxidation ethylidene oxygen-starch (Oxyethegleneoxy-Starch) (with the new compound form of ethylene glycol-α-D-glucoside and ethylene glycol-β-D glucoside) herein; Or a unit (with the form of ethylene glycol bisthioglycolate glucoside, this is best) based on starch-oxidation ethylidene oxygen-starch.In this special case, the n value in the compound general formula of the present invention is 5-8.

Preferably with the composition imagery, operator can go to consult at this people such as Otey " I﹠amp as reference; EC Product Research and Development ", nineteen sixty-five, the 4th, 228 pages of given structure iron.Though more complicated, this structure iron represented before carrying out functionalization with maleic anhydride and aspartic acid with the mode in the example of the present invention exist known by the derive structure of the initial glucoside mixture that comes of starch and ethylene glycol.Obtain a high-quality of in the scouring agent product, using and cheap dispersion agent, promptly use the front defined-OA

Part reaches the compound for great majority band-OH part gained in the formula of people such as Otey statement, is can obtain effectively for this example.

Claims (8)

1, a kind of laundry detergent composition, comprise that 1% to 98% is selected from negatively charged ion, nonionic, the detergent surfactant of cats product and its mixture, optional 0.001% to 2% is selected from the enzyme of amylase, proteolytic enzyme and composition thereof, and optional 5% to 50% is selected from 2,2 '-the oxo disuccinate, tartrate, single-and two-succinate, Citrate trianion, C ₈-C ₁₄The additional synergistic agent of hydrocarbyl succinic hydrochlorate, tripoly phosphate sodium STPP, pyrophosphate salt, anti-its mixture of carbonate, it is characterized in that comprising 0.1% to 35% random copolymers dispersion agent, this copolymer dispersant molecular weight is about 635-50000 and the repeating unit represented that comprises about 0.10-0.95 molar fraction:

Wherein M is a sodium, and A is---OC (O) C (L) HCH ₂(O) C--, L are selected from aspartic acid alkali, L-glutamic acid alkali, glycine alkali, taurine alkali, sarkosine alkali and imino-diacetic acetate base.

2, the laundry detergent composition of claim 1 also contains the additional synergistic agent of one or more non-polymers and does not in fact contain polyacrylate.

3, the laundry detergent composition of claim 2, wherein, detergent surfactant is that 5%-60% and random copolymers dispersion agent are 0.1%-10%.

4, the laundry detergent composition of claim 3, wherein, the molecular weight of random copolymers dispersion agent is 4950-49500, the have an appointment repeating unit represented of 0.60-0.95 molar fraction of this dispersion agent;

5, the laundry detergent composition of claim 4, wherein, the amount of detergent surfactant is that the amount of 6%-30% and random copolymers dispersion agent is 1%-10%.

6, a kind of fabric cleaning process of washing fabric commonly used in the washing pool that is included in is characterized in that comprising and uses claim 1,2,3,4 or 5 laundry detergent composition, and this method is carried out in the hand washing mode.

7, the fabric cleaning process of claim 6, wherein, said fabric is in essence by cotton, polyester, knitted fabrics or cloth that polyacrylonitrile or its blend are made.

8, the fabric cleaning process of claim 6, this method is carried out in family commonly used automatic washing machine under the temperature that routine is selected.