CN117715949A - Polycarboxylic acid (salt) containing ester bond and method for producing same - Google Patents

Polycarboxylic acid (salt) containing ester bond and method for producing same Download PDF

Info

Publication number
CN117715949A
CN117715949A CN202280052691.2A CN202280052691A CN117715949A CN 117715949 A CN117715949 A CN 117715949A CN 202280052691 A CN202280052691 A CN 202280052691A CN 117715949 A CN117715949 A CN 117715949A
Authority
CN
China
Prior art keywords
salt
acid
polycarboxylic acid
ester bond
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280052691.2A
Other languages
Chinese (zh)
Inventor
山口繁
富家嘉一
伊藤良太
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Priority claimed from PCT/JP2022/028620 external-priority patent/WO2023008367A1/en
Publication of CN117715949A publication Critical patent/CN117715949A/en
Pending legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a polycarboxylic acid (salt) containing ester bond with excellent biodegradability and alkali decomposition change rate, a manufacturing method thereof and a detergent composition containing the polycarboxylic acid (salt) containing ester bond. The present invention relates to a polycarboxylic acid (salt) containing an ester bond, which has a structural unit derived from an ester group in the main chain, a carboxylic acid (salt) in the side chain, and a carboxylic acid (salt) in the beta-or gamma-position of the carbonyl carbon of the ester group.

Description

Polycarboxylic acid (salt) containing ester bond and method for producing same
Technical Field
The present invention relates to an ester bond-containing polycarboxylic acid (salt) excellent in biodegradability and alkali degradability, a process for producing the same, and a detergent composition containing the same.
Background
Conventionally, polyacrylic acid or a copolymer of acrylic acid and maleic acid has been used as a detergent builder with low cost and high performance. In recent years, a polymer used as a builder for a detergent has been demanded to be a water-soluble polymer having a low environmental load, and to have a builder action and biodegradability.
For example, patent document 1 discloses a vinyl acetate/acrylic acid/maleic anhydride copolymer.
Further, patent document 2 discloses a copolymer composed of 2-methylene-1, 3-dioxepane and acrylic acid.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 4-311706
Patent document 2: japanese patent laid-open No. 2000-38595
Disclosure of Invention
Problems to be solved by the invention
Further, the present inventors have found through studies so far that when a homopolymer of acrylic acid or a copolymer with another comonomer such as maleic acid is used in a detergent composition, the detergent composition has excellent recontamination preventing ability.
However, the copolymers described in patent document 1 and patent document 2 have the following problems: the biodegradability is insufficient, and there is room for improvement in the recontamination prevention ability.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an ester bond-containing polycarboxylic acid (salt) having a structural unit derived from an ester group in a main chain, a carboxyl group in a side chain, and a carboxylic acid (salt) at the β -position or γ -position of a carbonyl carbon of the ester group, a method for producing the same, and a detergent composition containing the ester bond-containing polycarboxylic acid (salt).
Means for solving the problems
As a result of further studies, the present inventors have found that when a polycarboxylic acid (salt) containing an ester bond, which has a structural unit derived from an ester group in the main chain, a carboxyl group in the side chain, and a carboxylic acid (salt) in the β -position or γ -position of the carbonyl carbon of the ester group, is used as a detergent composition, biodegradability and alkali decomposition change rate are excellent, and have completed the present invention.
That is, the present invention relates to an ester bond-containing polycarboxylic acid (salt) having a structural unit derived from an ester group in the main chain, a carboxylic acid (salt) in the side chain, and a carboxylic acid (salt) in the β -or γ -position of the carbonyl carbon of the ester group.
The ester bond-containing polycarboxylic acid (salt) preferably has a change rate of alkali decomposition of 10% or more.
The ester bond-containing polycarboxylic acid (salt) preferably has biodegradability of 20% or more.
In addition, the present invention relates to a detergent composition comprising the ester bond-containing polycarboxylic acid (salt) of the present invention.
The present invention also relates to a method for producing a polycarboxylic acid (salt) containing an ester bond, comprising: a step of reacting a compound having an unsaturated double bond and an acid anhydride group with a compound having two or more hydroxyl groups; and a step of reacting the double bond of the product of the above step.
The present invention also relates to a method for producing a polycarboxylic acid (salt) containing an ester bond, comprising: and a step of reacting a compound having three or more carboxylic acids (salts) or an anhydride thereof with a compound having two or more hydroxyl groups.
Effects of the invention
According to the present invention, it is possible to provide an ester bond-containing polycarboxylic acid (salt) excellent in biodegradability and alkali decomposition rate of change, a process for producing the same, and a detergent composition containing the ester bond-containing polycarboxylic acid (salt).
Drawings
FIG. 1 is a proton NMR spectrum of polycarboxylic acid (4) containing an ester bond obtained in example 4. The peak of 3.6 to 4.3ppm is considered to be the peak of hydrogen bound to carbon adjacent to the ester bond.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The following description of the preferred embodiments is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
In the following description, "%" means "% by mass", and "parts" means "parts by mass", and "a to B" in the expression range means a to B and below unless otherwise specified. In the present invention, "(meth) acrylate" means "acrylate" or "methacrylate", and "(meth) acrylic acid" means "acrylic acid" or "methacrylic acid".
[ polycarboxylic acid (salt) containing ester bond ]
The ester bond-containing polycarboxylic acid (salt) of the present embodiment has the following substituents and structural units 1) to 3).
1) Having structural units derived from ester groups in the main chain
2) Having carboxylic acids (salts) in side chains
3) Having carboxylic acids (salts) in the beta-or gamma-position of the carbonyl carbon of the ester group of the main chain
The ester groups present in the backbone may be generally represented by the chemical formula "-c=o-O-" or "-COO-". By providing two or more of these bonds in the main chain of the polymer, the polycarboxylic acid (salt) containing an ester bond is discharged as a detergent composition into a river or the like in a state of being contained in the detergent composition or the like, and then the compound having a low molecular weight can be biodegraded by hydrolysis or hydrolysis of the ester bond present in the main chain, which contributes to reduction of environmental load.
The structural unit derived from an ester group in 1) above refers to a structure represented by "-c=o—o-" or "-COO-".
The polycarboxylic acid (salt) containing an ester bond of the present invention has a polycarboxylic acid (salt) structure in which two or more carboxylic acids (salts) are present in a side chain.
The carboxylic acid (salt) may also be denoted as "-COOM". M is a hydrogen atom, an alkali metal atom or an ammonium group, more preferably a hydrogen atom, sodium or potassium, still more preferably a hydrogen atom or sodium.
In an example of the structure of the ester bond-containing polycarboxylic acid (salt) of the present invention, the structure of the ester group of the main chain and the carboxylic acid (salt) moiety located at the β or γ position of the carbonyl carbon of the ester group of the main chain may be represented by the following general formula (1).
[ chemical 1]
In the general formula (1), a, b, c, d is a substituent group containing carbon atoms at the α -position, the β -position, the γ -position and the δ -position from the carbonyl carbon of the ester group. a is selected from methylene (-CH) 2 (-), -CHOH-group, methine group ]>CH-). b is selected from methylene (-CH) 2 (-) and methine ]>CH-)、-CR 1 COOH (M) -group. c is selected from single bond, methylene (-CH) 2 -)、-CR 1 COOH (M) -group. d is a single bond or-CR 1 COOH (M) -group. R is R 1 The same or different, and represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom or an ammonium group. m represents a positive integer of 1 or more.
In the production of the ester bond-containing polycarboxylic acid (salt) of the present invention, when a dicarboxylic acid compound such as acrylic acid and maleic acid (anhydride) is used for copolymerization, the carboxylic acid (salt) is bonded to the β -and δ -positions in the above general formula (1). When polymerization is carried out using two or more dicarboxylic acid (anhydride) compounds having a double bond such as maleic acid (anhydride) and itaconic acid (anhydride), carboxylic acid (salt) is bonded at the γ position.
The structural unit derived from the ether bond constituting the ester bond can be represented by the following general formula (2).
[ chemical 2]
In the general formula (2), R 2 A substituent having two bonds and having 2 to 10 carbon atoms, and n represents a positive integer of 1 or more.
R as in the general formula (2) 2 Specific examples of (C) include-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CHCH 3 CH 2 -、-CHCH 3 CH 2 CH 2 -、-CH 2 CHCH 3 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 -an isostearic or linear chain substituent with two bonds, -CH 2 CH 2 OCH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -or the like, a chain-like substituent having two bonds containing an ether bond, a cyclic substituent having two bonds having 3 to 10 carbon atoms, -CH 2 CH(OH)CH 2 -、-CH 2 CH(OH)CH 2 CH 2 -、-CH 2 CH 2 CH(OH)CH 2 CH 2 -、-CH 2 CH(OH)CH 2 CH 2 CH 2 CH 2 -and the like having a hydroxyl group, a chain-like substituent having two bonds, and the like. From the viewpoints of biodegradability and alkali decomposition change rate, it is preferable that the-CH derived from ethylene glycol 2 CH 2 -base, -CH derived from glycerol 2 CHOHCH 2 -a radical.
Examples of the polymer of the polycarboxylic acid (salt) containing an ester bond of the present invention include polymers having a structure represented by the following general formula (3) as a repeating unit.
[ chemical 3]
In the general formula (3), a 1 、a 2 The same or different, and a is the same as a of the general formula (1). b 1 、b 2 The same or different, and b is the same as b in the general formula (1). c 1 、c 2 Identical or different, respectively withC of the general formula (1) is the same. d, d 1 、d 2 The same or different, d is the same as d of the general formula (1). R is R 2 R with the general formula (2) 2 The same applies. p represents a positive integer of 1 or more.
Specifically, an example of the structure of the polymer of the polycarboxylic acid (salt) containing an ester bond of the present invention can be represented by the following general formula (4).
[ chemical 4]
R in the general formula (4) 2 The same or different, and the same as the above general formula (2). R is R 3 Identical or different, selected from methylene, -CHCH 3 -a radical. R is R 4 Represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic group, two R' s 4 At least one of them is a hydrogen atom, an alkali metal atom or an ammonium group. In addition, x represents a positive integer of 1 or more.
R as the general formula (4) 4 Examples of the organic group (c) include 1-valent organic groups obtained by removing one hydroxyl group from a compound having a hydroxyl group. Examples of the compound having a hydroxyl group include a compound having two or more hydroxyl groups of the present invention described below.
Having two R in the structure represented by the general formula (4) 4 The polycarboxylic acid (salt) containing an ester bond having a structure represented by the following general formula (4-1), each of which is a hydrogen atom, can be obtained, for example, by reacting maleic anhydride with ethylene glycol, and then polymerizing a double bond derived from maleic anhydride or the like by radical reaction.
[ chemical 5]
R in the general formula (4-1) 2 、R 3 X is the same as the general formula (4).
Specifically, another example of the structure of the polymer of the polycarboxylic acid (salt) containing an ester bond of the present invention can be represented by the following general formula (5).
[ chemical 6]
R in the general formula (5) 2 The same as the above general formula (2). R is R 4 In the same manner as in the above general formula (4), 5R 4 At least one of which is a hydrogen atom, an alkali metal atom or an ammonium group. R is R 5 Is methylene. y represents a positive integer of 1 or more.
R in the structure represented by the general formula (5) 4 The polycarboxylic acid (salt) containing an ester bond having a structure represented by the following general formula (5-1) in which all the hydrogen atoms are present is obtained, for example, by reacting maleic anhydride with ethylene glycol, and then polymerizing acrylic acid with a double bond derived from maleic anhydride by radical reaction or the like.
[ chemical 7]
R in the general formula (5-1) 2 、R 5 Y is the same as in formula (5).
Specifically, an example of a further structure of the polymer of the polycarboxylic acid (salt) containing an ester bond of the present invention can be represented by the following general formula (6).
[ chemical 8]
R in the general formula (6) 2 The same as the above general formula (2). R is R 4 As in the above formula (4), two R' s 4 At least one of them is a hydrogen atom, an alkali metal atom, or an ammonium group. R is R 6 Is methylene. z represents a positive integer of 1 or more.
Having two R in the structure represented by the general formula (6) 4 The polycarboxylic acid (salt) having an ester bond and having a structure represented by the following general formula (6-1) each having a hydrogen atom can be produced, for example, by reacting itaconic anhydride with glycerolAfter the oil reaction, a double bond derived from itaconic anhydride is polymerized by radical reaction or the like. In addition, in the case of itaconic anhydride, a homopolymer can be produced, and therefore, when the polycarboxylic acid (salt) polymer containing an ester bond of the present invention is synthesized using itaconic anhydride as a raw material, not only a linear polymer but also a branched polymer is produced.
[ chemical 9]
R in the general formula (6-1) 2 、R 6 Z is the same as the general formula (6).
As another example of the structure of the polymer of the polycarboxylic acid (salt) containing an ester bond of the present invention, there is a polymer having a structure represented by the following general formula (7) in addition to any one of the above general formulae (4) to (6).
[ chemical 10]
R in the general formula (7) 2 The same as the above general formula (2). R is R 4 The same as in the above general formula (4). R is R 7 Is an organic group. q represents a positive integer of 1 or more.
R as the general formula (7) 7 Examples of the organic group (C) include a C1-4 hydrocarbon group having 2-valent hydrocarbon groups and a method in which one or more of the hydrogen atoms of the C1-4 hydrocarbon group are hydroxyl groups or-COOR groups 4 Radical (R) 4 The same as the above general formula (4).
The polycarboxylic acid (salt) having an ester bond having a structure represented by the general formula (7) can be obtained, for example, by reacting maleic anhydride, ethylene glycol and citric acid, and then polymerizing a double bond derived from maleic anhydride by a radical reaction or the like. In this case, the resulting polycarboxylic acid (salt) containing an ester bond has a structure represented by the above-mentioned general formula (4-1) in addition to the structure represented by the general formula (7).
Specifically, another example of the polymer of the polycarboxylic acid (salt) containing an ester bond of the present invention is a polymer having a structure represented by the following general formula (8) as a repeating unit.
[ chemical 11]
R in the general formula (8) 2 The same as the above general formula (2). R is R 8 Represents an oligomer group obtained by removing two or more carboxylic acid (salt) groups from an oligomer of a compound having an unsaturated double bond and a carboxylic acid (salt) group, wherein R is a group represented by 8 The beta-or gamma-position of the bonded carbonyl carbon has a carboxylic acid (salt). r represents a positive integer of 1 or more.
R 8 The oligomer group represented may be one from which three or more carboxylic acid (salt) groups are removed, and in this case, the carboxylic acid (salt) group-removed site is referred to as-COO-R 2 The linking group represented by OCO-is bonded to a plurality of other oligomer groups. At R 8 In the case where the oligomer group represented is a 2-valent oligomer group from which only two carboxylic acid (salt) groups have been removed, the carboxylic acid (salt) groups have been removed at the site via-COO-R 2 -the OCO-group is bonded to only two other oligomer groups.
At R 8 In the case where the oligomer group represented is an n-valent group from which n (n is an integer of 3 or more) carboxylic acid (salt) groups are removed, the n sites from which the carboxylic acid (salt) groups are removed are located via-COO-R 2 -OCO-groups are bonded to other n oligomer groups.
The polycarboxylic acid (salt) having an ester bond having a structure represented by the general formula (8) can be obtained, for example, by using an oligomer of a compound having an unsaturated double bond and a carboxylic acid (salt) group as a compound having three or more carboxylic acids (salts) and reacting the oligomer with a compound having two or more hydroxyl groups.
As the compound having an unsaturated double bond and a carboxylic acid (salt) group, a compound having two or more hydroxyl groups, the compounds described later can be used.
[ physical Properties of ester bond-containing polycarboxylic acid (salt) ]
The polycarboxylic acid (salt) containing an ester bond of the present invention is a water-soluble polymer. The water-solubility means that the ester bond-containing polycarboxylic acid (salt) of the present invention is dissolved in 100 parts by mass of pure water at normal temperature and normal pressure by 1 part by mass or more. The ester bond-containing polycarboxylic acid (salt) of the present invention can be suitably used as a detergent builder, a detergent, a water treatment agent, a dispersant, a fiber treatment agent, a scale inhibitor (scale inhibitor), a cement additive, a metal ion blocking agent, a thickener, various binders, and the like by exhibiting water solubility.
The ester bond-containing polycarboxylic acid (salt) of the present invention has no problem in terms of biodegradability and alkali decomposition rate change even if the weight average molecular weight is low in the order of oligomer, but when used as a builder for a detergent composition, the weight average molecular weight is preferably 600 or more.
The lower limit of the weight average molecular weight of the ester bond-containing polycarboxylic acid (salt) of the present invention is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, and still more preferably 3000 or more for the purpose of improving the Ca ion capturing ability. The upper limit of the weight average molecular weight of the ester bond-containing polycarboxylic acid (salt) of the present invention is not particularly limited, and may be 1000000 or less, or 200000 or less. For the purpose of improving biodegradability, the molecular weight is preferably 80000 or less, more preferably 10000 or less, and still more preferably 3000 or less.
The weight average molecular weight of the ester bond-containing polycarboxylic acid (salt) of the present invention is preferably 1000 to 1000000, more preferably 1500 to 200000, still more preferably 1500 to 80000, particularly preferably 3000 to 10000.
In the present invention, the weight average molecular weight is a measurement value obtained by GPC (gel permeation chromatography), and can be measured by the apparatus and measurement conditions described in examples described below.
The acid value of the ester bond-containing polycarboxylic acid (salt) of the present invention is preferably 50mg (KOH)/kg or more. More preferably 100mg (KOH)/kg or more, still more preferably 300mg (KOH)/kg or more.
When the acid value is within the above range, calcium in tap water can be captured when the detergent is added thereto, and the detergency of the detergent can be improved.
The hydroxyl value of the ester bond-containing polycarboxylic acid (salt) of the present invention is preferably 5mg (KOH)/kg or more. More preferably 10mg (KOH)/kg or more, still more preferably 50mg (KOH)/kg or more. When the hydroxyl value is in the above range, dispersibility in high hardness water and compatibility with a surfactant are improved.
The biodegradability of the ester bond-containing polycarboxylic acid (salt) of the present invention can be measured by the biodegradability test described later, and the higher the biodegradability, the more the environmental load of polluted water after washing can be reduced in the case where the ester bond-containing polycarboxylic acid (salt) of the present invention is used in a detergent composition, and is therefore preferable. The biodegradability is preferably 10% or more, more preferably 20% or more, further preferably 50% or more, and most preferably 60% or more.
The alkali decomposition rate of the ester bond-containing polycarboxylic acid (salt) of the present invention can be measured by the alkali decomposition rate test described later, and it is preferable that the higher the alkali decomposition rate, the higher the efficiency of removing the ester bond-containing polycarboxylic acid (salt) of the present invention by alkali washing. The alkali decomposition rate of change is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more.
The Ca-capturing ability of the ester bond-containing polycarboxylic acid (salt) of the present invention can be measured by the Ca-capturing ability test described later. By improving the Ca capturing ability, inactivation/insolubilization of the surfactant due to Ca ions can be prevented, the cleaning ability can be greatly improved, or the amount of the surfactant can be greatly reduced when the composition is added to a detergent.
[ polycarboxylic acid (salt) composition containing ester bond ]
The ester group-containing polycarboxylic acid (salt) composition of the present invention contains the ester group-containing polycarboxylic acid (salt) of the present invention. The ester group-containing polycarboxylic acid (salt) composition of the present invention may contain components other than the ester group-containing polycarboxylic acid (salt) of the present invention.
The ester group-containing polycarboxylic acid (salt) composition of the present invention is not particularly limited, and preferably contains 0.1 mass% to 100 mass% with respect to 100 mass parts of the ester group-containing polycarboxylic acid (salt) composition of the present invention. More preferably, the content is 1% by mass or more and 99.5% by mass or less.
The ester group-containing polycarboxylic acid (salt) composition of the present invention may contain an ester compound of an unsaturated dicarboxylic acid and a compound having two or more hydroxyl groups (hereinafter also referred to as "ester bond-containing carboxylic acid (salt)"). The content of the ester bond-containing carboxylic acid (salt) in the ester group-containing polycarboxylic acid (salt) composition of the present invention is preferably 20 mass% or less, more preferably 10 mass% or less, relative to 100 mass% of the total of the ester group-containing polycarboxylic acid (salt) and the ester bond-containing carboxylic acid (salt) contained in the ester group-containing polycarboxylic acid (salt) composition of the present invention. When the amount is within the above range, the recontamination preventing ability of the ester group-containing polycarboxylic acid (salt) composition of the present invention tends to be improved.
The term "carboxylic acid (salt) containing an ester bond" refers to a substance which is an esterified product of an unsaturated dicarboxylic acid and a compound having two or more hydroxyl groups and which does not undergo polymerization reaction.
[ method for producing ester bond-containing polycarboxylic acid (salt) ]
The method for producing the ester bond-containing polycarboxylic acid (salt) of the present invention is not particularly limited, and the following method is preferably exemplified: method (I), comprising: a step (A) of reacting a compound having an unsaturated double bond and an acid anhydride group with a compound having two or more hydroxyl groups; and (B) reacting the double bond of the product of the above steps; method (II), comprising: and (C) reacting a compound having three or more carboxylic acids (salts) or an anhydride thereof with a compound having two or more hydroxyl groups.
As a more preferable production method, a method in which the reaction in the step (a) or the step (C) includes an esterification reaction, for example, can be exemplified: a method in which 1) an esterification step of reacting a compound having an unsaturated double bond and an acid anhydride group with a compound having two or more hydroxyl groups, and 2) a step of reacting the double bond of the product obtained in the esterification step are sequentially performed; a method comprising a step of esterifying a compound having three or more carboxylic acids (salts) or an anhydride thereof with a compound having two or more hydroxyl groups.
The step (a) may be a step of reacting only a compound having an unsaturated double bond and an acid anhydride group with a compound having two or more hydroxyl groups, and compounds other than these may be used. Examples of the compounds other than these include compounds having three or more carboxylic acids (salts) described later.
The compound having an unsaturated double bond and an acid anhydride group of the present invention is not particularly limited as long as it has a double bond and an acid anhydride group, and examples thereof include maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, trimellitic anhydride, and the like. Among these, one or more selected from maleic anhydride and itaconic anhydride is preferable from the viewpoint of high reaction rate in the esterification step with a compound having two or more hydroxyl groups.
The compound having three or more carboxylic acid (salt) groups of the present invention is not particularly limited as long as it has three or more carboxylic acid (salt) groups. Examples thereof include oligomers of one or more compounds selected from the group consisting of compounds having an unsaturated double bond (more preferably, a radically polymerizable unsaturated double bond) and a carboxylic acid (salt) group, such as acrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyleneglutaric acid, and methylenemalonic acid; an oligomer of one or more compounds selected from the group consisting of anionic polymerizable carboxylic acid (salt) groups such as glyoxylic acid and methylenemalonic acid; citric acid, 1,3, 5-pentanetetracarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid, trimellitic acid, pyromellitic acid, salts thereof, and the like. Among these, 1,2,3, 4-butanetetracarboxylic acid is preferable in terms of high reaction rate in the esterification step with a compound having two or more hydroxyl groups; oligomers of one or more compounds selected from the group consisting of maleic acid and itaconic acid, and salts and anhydrides thereof; etc.
The oligomer may be obtained by, for example, using an ester compound corresponding to a compound having a carboxylic acid (salt) group as a raw material, preparing an oligomer, and then hydrolyzing with a base, or adding a strong acid or the like as needed to convert the oligomer into an acid-type carboxyl group, and the like.
The acid anhydride of the compound having three or more carboxylic acids (salts) of the present invention is not particularly limited as long as the compound is hydrolyzed to give a substance having three or more carboxylic acid (salt) groups, and examples thereof include 1,3, 5-pentanetetracarboxylic acid anhydride, 1,2,3, 4-butanetetracarboxylic acid dianhydride, 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid tricarboxylic acid anhydride, trimellitic anhydride, pyromellitic dianhydride, and the like. Among these, 1,2,3, 4-butanetetracarboxylic acid dianhydride is preferable from the viewpoint of high reaction rate in the esterification step with a compound having two or more hydroxyl groups.
The compound having three or more carboxylic acids (salts) of the present invention more preferably contains four or more carboxyl groups, from the viewpoint of improving the carboxylic acid density in the ester group-containing polycarboxylic acid (salt) and maintaining high calcium chelating ability and carbon black dispersibility.
The compound having two or more hydroxyl groups of the present invention is not particularly limited as long as it has two or more hydroxyl groups, and may have three or four hydroxyl groups. Specific examples thereof include branched or straight chain compounds such as ethylene glycol, propane-1, 3-diol, butane-1, 4-diol, heptane-1, 5-diol, hexane-1, 6-diol, propylene glycol, 1, 3-butanediol, 1, 4-pentanediol, diethanolamine and the like, chain compounds containing an ether bond such as diethylene glycol, triethylene glycol, tetraethylene glycol and the like, chain cyclic compounds having 3 to 10 carbon atoms such as cyclohexanediol and the like, glycerin, 1,2, 4-butanetriol, pentane-1, 3, 5-triol, 1,2, 6-hexanetriol and HO-CH 2 CH 2 CH(OH)CH 2 CH 2 CH 2 And chain compounds having three or more hydroxyl groups such as-OH. From the viewpoints of biodegradability and alkali decomposition rate of change, at least one selected from ethylene glycol and glycerin is preferable.
< esterification conditions >
In the case of carrying out the esterification reaction of the compound having an unsaturated double bond and an acid anhydride group of the present invention with the compound having two or more hydroxyl groups, the mixing ratio of the two is not particularly limited, and the reaction may be carried out in an arbitrary ratio. In order to increase the weight average molecular weight of the polymer obtained from the esterification reaction, it is preferable to perform the esterification reaction after feeding the polymer in a state where the molar ratio of the acid anhydride groups to the hydroxyl groups of the two compounds is approximately equimolar.
In the case of performing the esterification reaction using a compound having a carboxylic acid (salt) other than the compound having an unsaturated double bond and an acid anhydride group, it is preferable to perform the esterification reaction after charging in a state where the molar ratio of the total molar number of the acid anhydride group of the compound having an unsaturated double bond and an acid anhydride group and the carboxyl group of the compound having a carboxylic acid (salt) other than the compound is approximately equal to the molar ratio of the hydroxyl group.
In the step (a), the ratio of the compound having two or more hydroxyl groups to the compound having an unsaturated double bond and an acid anhydride group is not particularly limited, but in the case of a compound having two hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 0.5 to 2.0 moles, more preferably 0.7 to 1.5 moles, based on 1 mole of the compound having an unsaturated double bond and an acid anhydride group.
In the case of a compound having three hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 0.8 to 3 moles, more preferably 1.0 to 2.2 moles.
In the case of a compound having four or more hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 1.0 to 4.0 moles, more preferably 1.4 to 3.0 moles.
In the above case, the biodegradability and alkali decomposition rate of the polycarboxylic acid (salt) containing an ester bond tend to be improved.
In the case of performing an esterification reaction using a compound having a carboxylic acid (salt) other than the compound having an unsaturated double bond and an acid anhydride group, the number of moles of the hydroxyl groups contained in the compound having two hydroxyl groups is preferably 0.5 to 2.0 moles, more preferably 0.7 to 1.5 moles, relative to the total number of moles of the compound having an unsaturated double bond and an acid anhydride group and the carboxyl groups of the compound having a carboxylic acid (salt) other than the compound. In the case of a compound having three hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 0.8 to 3 moles, more preferably 1.0 to 2.2 moles. In the case of a compound having four or more hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 1.0 to 4.0 moles, more preferably 1.4 to 3.0 moles.
When the esterification reaction is carried out using a compound having a carboxylic acid (salt) other than the compound having an unsaturated double bond and an acid anhydride group, the compound having a carboxylic acid (salt) other than the compound having a carboxylic acid (salt) is preferably used in such a ratio that the number of moles of the carboxylic acid groups of the compound having a carboxylic acid (salt) other than the compound is 0.1 to 7.0 moles relative to 1 mole of the compound having an unsaturated double bond and an acid anhydride group. The molar amount of the carboxyl group in the other carboxylic acid (salt) -containing compound is more preferably 0.2 to 5.0 mol, and still more preferably 0.3 to 3.0 mol, based on 1 mol of the unsaturated double bond-and acid anhydride group-containing compound.
In the step (C), the ratio of the compound having two or more hydroxyl groups to the compound having three or more carboxylic acids (salts) or the acid anhydride thereof is not particularly limited, but in the case of the compound having two hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 0.5 to 2.0 moles, more preferably 0.8 to 1.5 moles, with respect to 1 mole of the compound having three or more carboxylic acids (salts) or the acid anhydride thereof. In the case of a compound having three hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 0.8 to 3 moles, more preferably 1.0 to 2.2 moles. In the case of a compound having four or more hydroxyl groups, the number of moles of hydroxyl groups contained is preferably 1.0 to 4.0 moles, more preferably 1.4 to 3.0 moles.
In the above case, the biodegradability and alkali decomposition rate of the polycarboxylic acid (salt) containing an ester bond tend to be improved.
The reaction temperature in the step (A) or the step (C) is not particularly limited, but is preferably 25℃or higher, more preferably 50℃or higher, and still more preferably 75℃or higher. The temperature is preferably 200℃or lower, more preferably 160℃or lower, and still more preferably 150℃or lower.
The reaction temperature is preferably 25 to 200 ℃, more preferably 50 to 160 ℃, and even more preferably 75 to 150 ℃.
The same applies to the case where the esterification reaction is carried out in the step (a).
In the above case, the biodegradability and alkali decomposition rate of the polycarboxylic acid (salt) containing an ester bond tend to be improved.
In the case where the reaction in the step (a) or the step (C) includes an esterification reaction, a known esterification catalyst or an esterification enzyme may be used. Examples of the esterification catalyst include titanium-based esterification catalysts and tin-based esterification catalysts.
< polymerization conditions >
The product obtained by the esterification reaction of the compound having an unsaturated double bond and an acid anhydride group of the present invention with the compound having two or more hydroxyl groups (hereinafter also referred to as an esterified product) is subjected to polymerization in the next step. In this case, other polymerizable monomers may be used.
As the other polymerizable monomer, specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, allyl alcohol, prenyl alcohol, allyl alcohol EO adduct, prenyl alcohol EO adduct, acrylamide, sodium acrylamide propane sulfonate, sodium 2-hydroxy-3-allyloxy propane sulfonate, hydroxyethyl acrylate, hydroxyethyl methacrylate, and the like are preferably used.
In the case of reacting the esterified product of the present invention with another polymerizable monomer, the ratio of the product obtained by the esterification reaction of the compound having an unsaturated double bond and an acid anhydride group of the present invention with the compound having two or more hydroxyl groups to the other polymerizable monomer is not particularly limited, and the product may be polymerized in any ratio. When the molar ratio of the other polymerizable monomer is increased, the weight average molecular weight of the resulting polycarboxylic acid (salt) containing an ester bond of the present invention tends to be increased. On the other hand, if the proportion of the other polymerizable monomer is increased, biodegradability tends to be lowered.
The ratio of the esterified product of the present invention to other polymerizable monomer is not particularly limited, and examples thereof include: a method of using 0.05 to 5.0 moles of another polymerizable monomer, a method of using 0.1 to 3.0 moles of another polymerizable monomer, a method of using 0.2 to 2.0 moles of another polymerizable monomer, and the like based on 1 mole of the esterified product of the present invention.
In addition, a compound having a hydroxyl group may be added at the time of polymerization. Thus, the polymerization reaction proceeds, and the esterification reaction between the carboxylic acid (salt) and the hydroxyl group of the obtained polymer proceeds. Examples of the compound having a hydroxyl group include the above-mentioned compound having two or more hydroxyl groups.
When the compound having a hydroxyl group is added during the polymerization reaction, the ratio of the compound having a hydroxyl group to be added is preferably 0.05 to 2.0 mol based on 1 mol of the esterified product of the present invention. More preferably, 0.08 to 1.5 mol, and still more preferably 0.1 to 1.3 mol.
< polymerization initiator >
As the polymerization initiator used in the above production method, a commonly used polymerization initiator can be used. Specifically, there can be suitably mentioned: hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azo compounds such as 2,2' -azobis (2-amidinopropane) hydrochloride, 4' -azobis-4-cyanovaleric acid, azobisisobutyronitrile, and 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, and cumene hydroperoxide. Among these polymerization initiators, hydrogen peroxide, persulfates, 2 '-azobis (2-amidinopropane) hydrochloride are preferred, and persulfates, 2' -azobis (2-amidinopropane) hydrochloride are more preferred. These polymerization initiators may be used alone or in combination of two or more.
For the purpose of improving the polymerizability and reducing the residual initiator, the polymerization initiator is preferably used in an amount of 0.5 to 60 wt%, more preferably 1.0 to 50 wt%, and still more preferably 2.0 to 30 wt% based on the product obtained by the esterification reaction of the compound having an unsaturated double bond and an acid anhydride group of the present invention with the compound having two or more hydroxyl groups.
In the above production method, an accelerator such as a moire salt may be used together with the polymerization initiator.
When a moire salt is used, for the purpose of improving polymerizability, it is preferable to use 0.002 to 0.05 wt%, more preferably 0.003 to 0.04 wt%, based on the product obtained by the esterification reaction of the compound having an unsaturated double bond and an acid anhydride group of the present invention with the compound having two or more hydroxyl groups.
< polymerization conditions >
In the above production method, the polymerization temperature is appropriately determined according to the polymerization method, solvent, polymerization initiator, and the like used, and is preferably 25 ℃ or higher. More preferably 50℃or higher, still more preferably 60℃or higher, and particularly preferably 80℃or higher. Further, the temperature is preferably 200℃or lower. More preferably not higher than 150℃and still more preferably not higher than 120℃and particularly preferably not higher than 110 ℃.
The polymerization temperature is preferably 25 to 200 ℃, more preferably 50 to 150 ℃, still more preferably 60 to 120 ℃, particularly preferably 80 to 110 ℃.
The polymerization temperature does not always have to be kept substantially constant during the polymerization reaction, and for example, the polymerization may be started from room temperature, the temperature may be raised to a set temperature for a suitable temperature raising time or a suitable temperature raising rate, and then the set temperature may be maintained, or the temperature may be changed (raised or lowered) with time during the polymerization reaction according to a method of dropping the monomer component, the initiator, or the like. The polymerization temperature refers to the temperature of the reaction solution of the polymerization reaction. The method and means for measuring and controlling the polymerization temperature may be any suitable method and means. For example, measurement may be performed by using a commonly used device.
The pressure during polymerization in the above production method is not particularly limited, and any suitable pressure may be used. For example, the pressure may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.
The atmosphere in the reaction system may be directly in an air atmosphere or an inert gas atmosphere may be used. In the case where the atmosphere in the reaction system is an inert gas atmosphere, for example, the reaction system may be replaced with an inert gas such as nitrogen before the polymerization is started. Thus, the atmosphere gas (e.g., oxygen or the like) in the reaction system is dissolved in the liquid phase and functions as a polymerization inhibitor.
In the above production method, a curing step may be provided after the addition of all the raw materials is completed, in order to increase the polymerization rate or the like.
In the above production method, the polymerization time is not particularly limited, and is preferably 20 to 420 minutes.
< production of oligomer >
The compound having three or more carboxylic acids (salts) or the acid anhydride thereof used in the step (C) is not particularly limited, and an oligomer of one or more compounds selected from compounds having an unsaturated double bond and a carboxylic acid (salt) group may be used.
The oligomer of one or more compounds selected from the group consisting of compounds having an unsaturated double bond and a carboxylic acid (salt) group (hereinafter also referred to as the oligomer of the present invention) used in the step (C) is not particularly limited, and can be produced by, for example, the following method.
As a raw material of the oligomer of the present invention, for example, one or more compounds selected from the group consisting of compounds having an unsaturated double bond and a carboxylic acid (salt) group, such as acrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyleneglutaric acid, and methylenemalonic acid, are preferably used.
The oligomer of the present invention may use monomers other than the compound having an unsaturated double bond and a carboxylic acid (salt) group as a raw material, if necessary.
The other monomer is not particularly limited, and examples thereof may include: hydroxy-containing monomers such as allyl alcohol, methallyl alcohol, prenyl alcohol, hydroxyethyl acrylate, and hydroxyethyl methacrylate; monomers having a structure in which an alkylene oxide is added to the hydroxyl group-containing monomer include ethylene oxide adducts of methallyl alcohol and ethylene oxide adducts of prenyl alcohol; amide group-containing monomers such as acrylamide and N-vinylpyrrolidone; sulfonic acid (salt) -group-containing monomers such as sodium acrylamide propane sulfonate and sodium 2-hydroxy-3-allyloxy propane sulfonate; hydrophobic group-containing monomers such as ethyl acrylate and isobornyl acrylate; etc.
The proportion of the compound having an unsaturated double bond and a carboxylic acid (salt) group to be used in the oligomer of the present invention is not particularly limited, but may be any proportion, and is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, still more preferably 80 to 100 mass%.
The oligomer of the present invention is preferably produced by polymerizing a compound having an unsaturated double bond and a carboxylic acid (salt) group with other monomers as needed in the presence of a polymerization initiator. As the polymerization initiator, the polymerization initiator exemplified in the item < polymerization initiator > described above can be exemplified.
The polymerization temperature conditions and pressure conditions in the production of the oligomer of the present invention are the same as those described in the item < polymerization conditions >.
The oligomer of the present invention may be produced by adding all the raw materials to a reactor at once, or by adding all or a part of the raw materials sequentially or continuously.
In order to increase the polymerization rate, the oligomer of the present invention may be provided with a curing step.
In the above production method, the polymerization time is not particularly limited, and is preferably 20 to 420 minutes.
[ use of ester bond-containing polycarboxylic acid (salt) ]
The ester bond-containing polycarboxylic acid (salt) of the present invention can be suitably used in detergent builders, detergents, water treatment agents, dispersants, fiber treatment agents, scale inhibitors (scale inhibitors), cement additives, metal ion blocking agents, thickeners, various binders, and the like. Among them, the detergent composition can be preferably used as a detergent builder, a detergent, a water treatment agent, or a dispersant.
The present invention also relates to a detergent builder, a detergent, a water treatment agent, or a dispersant containing the ester bond-containing polycarboxylic acid (salt) of the present invention or the ester bond-containing polycarboxylic acid (salt) produced by the production method of the present invention as an essential component.
< detergent builder and detergent composition >
The detergent builder of the present invention plays a role of preventing reattachment of dirt to laundry or the like during washing. The copolymer (polycarboxylic acid (salt) containing ester bond) of the present invention can strongly disperse the soil by the charge repulsion of the carboxyl group, and can prevent reattachment to the laundry by dispersing the peeled soil, thereby further improving whiteness of the white laundry and greatly improving the added value of the detergent. In addition, the ability to disperse zeolite used in a powder detergent is high, and the effect as a dispersant in the production of a detergent powder is also high.
The detergent builder of the present invention can be suitably used as a liquid detergent builder, in view of excellent compatibility with a surfactant and that the resulting detergent is a highly concentrated liquid detergent. By making the compatibility with the surfactant excellent, the transparency is good when used in a liquid detergent, and the problem of separation of the liquid detergent due to turbidity can be prevented. In addition, by making the compatibility excellent, a highly concentrated liquid detergent can be produced, and the cleaning ability of the liquid detergent can be improved. The detergent builder of the present invention exhibits excellent thickening effect when blended in a liquid detergent. Therefore, sagging and the like at the time of use are suppressed, and the operability is excellent.
The detergent builder of the present invention has excellent anti-redeposition ability, and is excellent in detergent performance and stability, and is hardly reduced in performance during long-term storage and is excellent in detergent performance and stability, which are excellent in quality such as precipitation of impurities during low-temperature storage.
The above-mentioned cleaning ability can be judged by the cleaning rate. The cleaning rate can be determined by the following method.
(evaluation method of cleaning Rate)
As a sample, an artificial contaminated cloth was used. As the artificially contaminated cloth, a cloth (STC GC "clay soil", EMPA164 "grass soil", EMPA106 "carbon black/mineral oil soil") obtained by Scientific Service company was used, and whiteness was measured by reflectance in advance. For the reflectance measurement, a colorimeter model ND-1001DP (manufactured by Nippon electric color industry Co., ltd.) or the like can be used.
Hard water was prepared by adding pure water to 1.47g of calcium chloride dihydrate (0.74 g in the case of using EMPA106 as a sample) to prepare 10 kg.
Pure water was added to 4.8g of sodium laureth sulfate (AES), 0.6g of polyoxyethylene lauryl ether (AE), 0.6g of sodium borate, 0.9g of citric acid and 2.4g of propylene glycol to give 80g of total. After adjusting the pH to 8.2 with an aqueous sodium hydroxide solution, pure water was added to give 100g of a total amount, and an aqueous surfactant solution was prepared.
The shaking type scale remover was set at 27℃and 1000mL of hard water, 5mL of an aqueous polymer solution (concentration: 0.50% (concentration: 0.60% in the case of using EMPA106 as a sample)) 5mL of an aqueous surfactant solution, 5.4g of artificially contaminated cloth and 5.4g of white cloth or only 10.8g of artificially contaminated cloth were added to the tank, and stirred at 100rpm for 10 minutes.
The artificially contaminated cloth and the white cloth were taken out of the pot, and the water was wrung out by hand. 1000mL of hard water was added to the tank, and the artificially contaminated cloth and white cloth, which had been wrung out of the water, were added to the tank and stirred at 100rpm for 2 minutes. The artificially contaminated cloth and the white cloth were taken out from the pot, and after the water was wrung out by hand, a cloth mat was provided on the artificially contaminated cloth, and the cloth mat was dried while extending the wrinkles by an iron. And measuring whiteness of the dried artificially contaminated cloth by using a colorimeter through reflectivity.
The cleaning rate (%) was determined from the values measured by the following methods and the following formulas.
Cleaning force (%) =
(whiteness of artificially contaminated cloth after washing-whiteness of artificially contaminated cloth before washing)/(whiteness of raw white cloth of artificially contaminated cloth (EMPA 221) whiteness of artificially contaminated cloth-whiteness of artificially contaminated cloth before washing) ×100
The detergent builder, detergent, water treatment agent or dispersant comprising a composition containing an ester bond-containing polycarboxylic acid (salt) having a cleaning rate of 7.3% or more when EMPA164 is used or 17.4% or more when EMPA106 is used is also one of the present invention.
In such a detergent builder, detergent, water treatment agent or dispersant which is a composition containing an ester bond-containing polycarboxylic acid (salt), it is preferable to satisfy both of these characteristics, that is, the cleaning rate when the EMPA164 is used and the cleaning rate when the EMPA106 is used.
The cleaning rate when the EMPA164 is used is preferably 7.4% or more.
The cleaning rate when EMPA106 is used is preferably 17.5% or more. More preferably 17.6% or more.
The artificially contaminated cloths EMPA164 and 106 used in the measurement of the above-mentioned cleaning rate refer to a standard sample for a soil test in which a certain amount of soil is adhered to the cloth, EMPA164 is a standard sample in which grass soil is adhered to a white cotton cloth (EMPA 221), and EMPA106 is a standard sample in which carbon black and mineral oil soil are adhered to a white cotton cloth (EMPA 221).
The other components and blending ratios other than the ester bond-containing polycarboxylic acid (salt) in the detergent builder described above can be appropriately used within a range not impairing the operational effects of the present invention, based on various components and blending ratios which have been conventionally known to be usable in detergent builders.
The above-mentioned detergent may be a powder detergent or a liquid detergent, and is preferably a liquid detergent in view of excellent solubility of the ester bond-containing polycarboxylic acid (salt) and the liquid detergent.
In the above-mentioned detergents, additives commonly used for detergents may be used in addition to the polycarboxylic acid (salt) containing an ester bond. As the above-mentioned additives, for example, a surfactant, an alkaline builder, a chelate builder, a redeposition inhibitor such as sodium carboxymethyl cellulose for preventing redeposition of a contaminant, a scale inhibitor such as benzotriazole, ethylene-thiourea, a detergent, a color-cross preventing agent, a softener, an alkaline substance for pH adjustment, a perfume, a solubilizing agent, a fluorescent agent, a colorant, a foaming agent, a foam stabilizer, a polish, a bactericide, a bleaching agent, a bleaching aid, an enzyme, a dye, a solvent, and the like are suitable. In the case of a powder detergent, zeolite is preferably blended.
When used in the above-mentioned detergent, the ester bond-containing polycarboxylic acid (salt) of the present invention is preferably added in an amount of 0.1 to 20% by mass relative to 100% by mass of the detergent. If the amount is less than 0.1% by mass, the detergency of the detergent may be insufficient, and if it exceeds 20% by mass, the detergent may be uneconomical.
The above-mentioned detergents include detergents for specific applications such as synthetic detergents for household detergents, industrial detergents for fiber industry and the like, hard surface cleaning detergents, and bleaching detergents in which the action of one of the components is enhanced.
The surfactant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and one or two or more of these surfactants may be used.
In the case of using two or more kinds, it is preferable to include an anionic surfactant and a nonionic surfactant therein. In this case, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more relative to 100% by mass of the total surfactant. More preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
As the above anionic surfactants, alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α -olefin sulfonate, α -sulfo fatty acid or ester salt, alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate or salt thereof, alkenyl phosphate or salt thereof, and the like are suitable. The alkyl group and alkenyl group in the anionic surfactant may have a branched chain of an alkyl group such as a methyl group.
As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl dialcoholate, fatty acid monoglyceride, alkylamine oxide, and the like are suitable. The alkyl group and alkenyl group in the nonionic surfactant may have a branched chain of an alkyl group such as a methyl group.
As the cationic surfactant, quaternary ammonium salts and the like are suitable.
As the above-mentioned amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable.
The alkyl group and alkenyl group in the cationic surfactant and amphoteric surfactant may have a branched chain of an alkyl group such as a methyl group.
The mixing ratio of the surfactant is usually preferably 10 to 60% by mass relative to 100% by mass of the liquid detergent. More preferably 15 to 50 mass%, still more preferably 20 to 45 mass%, particularly preferably 25 to 40 mass%. When the mixing ratio of the surfactant is less than 10% by mass, sufficient detergency may not be exhibited, and when it exceeds 60% by mass, economical efficiency may be lowered.
When two or more surfactants are used, the total blending ratio of the two or more surfactants is preferably as described above.
The mixing ratio of the builder for liquid detergents is usually preferably 0.1 to 20% by mass relative to 100% by mass of the liquid detergent. More preferably, the content is 0.2 to 15 mass%, still more preferably 0.3 to 10 mass%, particularly preferably 0.4 to 8 mass%, and most preferably 0.5 to 5 mass%. If the mixing ratio of the liquid detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 20% by mass, economical efficiency may be lowered.
The water content of the liquid detergent is usually preferably 0.1 to 75% by mass relative to 100% by mass of the liquid detergent. More preferably 0.2 to 70 mass%, still more preferably 0.5 to 65 mass%, particularly preferably 0.7 to 60 mass%, still more preferably 1 to 55 mass%, and most preferably 1.5 to 50 mass%.
The liquid detergent preferably has a kaolin turbidity of 200mg/L or less. More preferably 150mg/L or less, still more preferably 120mg/L or less, particularly preferably 100mg/L or less, and most preferably 50mg/L or less.
In addition, the change (difference) in turbidity of kaolin in the case where the ester bond-containing polycarboxylic acid (salt) of the present invention is added to a liquid detergent and in the case where it is not added is preferably 500mg/L or less. More preferably 400mg/L or less, still more preferably 300mg/L or less, particularly preferably 200mg/L or less, and most preferably 100mg/L or less. The kaolin turbidity can be measured by the following method.
(method for measuring turbidity of Kaolin)
After a sample (liquid detergent) was put into a 50mm square cuvette having a thickness of 10mm and stirred uniformly, the turbidity (kaolin turbidity: mg/L) at 25℃was measured by using NDH2000 (trade name, turbidity meter) manufactured by Nippon electric color Co., ltd.
As enzymes that can be blended in the detergent of the present invention, proteases, lipases, cellulases and the like are suitable. Among them, proteases, alkaline lipases and alkaline cellulases having high activity in alkaline washing solutions are preferred.
The amount of the enzyme to be added is preferably 5% by mass or less relative to 100% by mass of the detergent. If the amount exceeds 5% by mass, the detergency will not be improved, and the economical efficiency may be lowered.
As the above alkaline builder, silicate, carbonate, sulfate, etc. are suitable.
As the above chelate builder, diglycolic acid, hydroxycarboxylic acid, EDTA (ethylenediamine tetraacetic acid), DTPA (diethylenetriamine pentaacetic acid), citric acid, MGDA (methylglycine diacetic acid), HIDS (hydroxyiminodiacetic acid) and the like are suitable. Water-soluble polycarboxylic acid polymers may be used.
The above-mentioned detergent can be a detergent which is excellent in dispersibility, is less likely to cause deterioration in performance during long-term storage and precipitation of impurities during low-temperature storage, and has extremely high quality and excellent stability.
< Water treatment agent >
The compound of the present invention (the ester bond-containing polycarboxylic acid (salt) of the present invention) can be used for a water treatment agent. In the water treatment agent, a polyphosphate, a phosphonate, an anticorrosive agent, a mucus control agent, a chelating agent may be used as other compounding agents as needed.
The above water treatment agent is useful for scale control in cooling water circulation systems, boiler water circulation systems, sea water desalination apparatuses, pulp digestion tanks, black liquor concentration tanks, and the like. In addition, any suitable water-soluble polymer may be contained within a range that does not affect the performance or effect.
< fiber treatment agent >
The compounds of the present invention may be used in fiber treatment agents. The fiber treatment agent comprises at least one selected from the group consisting of a coloring agent, a peroxide, and a surfactant, and the polymer (or polymer composition) of the present invention.
The content of the compound of the present invention in the fiber treating agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treating agent. In addition, any suitable water-soluble compound may be contained within a range that does not affect the performance or effect.
In the following, a blending example of the fiber treating agent of the embodiment is shown. The fiber treating agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of the coloring agent, peroxide and surfactant include those commonly used for fiber-treating agents.
Regarding the compounding ratio of the ester bond-containing polycarboxylic acid (salt) of the present invention and at least one selected from the group consisting of a coloring agent, a peroxide and a surfactant, for example, in order to improve whiteness, color unevenness, and color fastness of a fiber, it is preferable to use a composition in which at least one selected from the group consisting of a coloring agent, a peroxide and a surfactant is compounded in a ratio of 0.1 to 100 parts by weight relative to 1 part by weight of the compound of the present invention as a fiber-treating agent in terms of pure matter of the fiber-treating agent.
Any suitable fiber may be used as the fiber for which the above-mentioned fiber treatment agent can be used. Examples thereof include cellulose fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semisynthetic fibers such as rayon, and fabrics and blends thereof.
When the above-mentioned fiber-treating agent is used in the refining step, the compound of the present invention is preferably blended with an alkaline agent and a surfactant. In the case of application to the bleaching step, the compound of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor of an alkaline bleaching agent are preferably blended.
< inorganic pigment dispersant >
The compounds of the present invention can be used in inorganic pigment dispersants. In the inorganic pigment dispersant, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used as other compounding agents as required.
The content of the compound of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight based on the whole inorganic pigment dispersant. In addition, any suitable water-soluble compound may be contained within a range that does not affect the performance or effect.
The above inorganic pigment dispersant can exhibit good performance as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating. For example, by adding an inorganic pigment dispersant to an inorganic pigment in a small amount and dispersing the inorganic pigment dispersant in water, a high-concentration inorganic pigment slurry such as a high-concentration calcium carbonate slurry having a low viscosity and high fluidity and excellent stability of these properties over time can be produced.
In the case where the above-mentioned inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant to be used is preferably 0.05 to 2.0 parts by weight relative to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant is within the above range, a sufficient dispersing effect can be obtained, and an effect matching the amount added can be obtained, which is economically advantageous.
Examples
< biodegradability test >
The biodegradability test of the resulting polycarboxylic acid (salt) containing an ester bond was carried out in accordance with OECD 301F.
(1) Preparation of the culture medium:
stock solutions A to D were prepared as follows.
And (3) solution A: in a 50ml sample bottle, potassium dihydrogen phosphate (KH) 2 PO 4 ) 0.850g of dipotassium hydrogen phosphate (K) 2 HPO 4 ) 2.175g of disodium hydrogen phosphate dodecahydrate (Na 2 HPO 4 ·12H 2 O) 6.7217g, ammonium chloride (NH) 4 Cl) 0.050g, dissolved in an appropriate amount of water, transferred to a 100ml measuring flask, and then added with water to the reticle.
And (2) liquid B: calcium chloride dihydrate (CaCl) 2 ·2H 2 O) 3.640g was dissolved in an appropriate amount of water, transferred to a 100ml measuring flask, and then added with water to the reticle.
And C, liquid: magnesium sulfate heptahydrate (MgSO) 4 ·7H 2 O) 2.250g was dissolved in an appropriate amount of water, transferred to a 100ml measuring flask, and then water was added to the reticle.
And D, liquid: iron (III) chloride hexahydrate (FeCl) 3 ·6H 2 O) 0.025g was dissolved in an appropriate amount of water, and after transferring to a 100ml measuring flask, water was added to the reticle.
The above-mentioned stock solutions A to D were adjusted to 25℃and 10ml of A was added to a 1L measuring flask by a full pipette and diluted with about 800ml of water. Then, 1ml of B, C, D was added to each of the above-described samples by a full pipette, and diluted to the mark with water adjusted to 25 ℃. The above culture medium was prepared in a plurality of portions in accordance with the amount required for the test. The prepared medium was transferred to a 5L beaker and mixed, and bubbling was performed for 1 hour or more while stirring.
(2) And (3) preparation of a sludge solution:
the sludge used in the biodegradability test was obtained from a sewage treatment plant under the south blowing field. First, the concentration of sludge obtained by the following method was measured. The obtained sludge was bubbled while stirring, 5ml was collected by a total pipette, and suction filtration was performed by using filter paper. 5 pieces of filter paper thus obtained were prepared, and after drying at 105℃for 1 hour by a dryer, the concentration of sludge was calculated from the average value of the weight reduction of these 5 pieces. The sludge was diluted with the above-prepared culture medium to prepare a 1000ppm sludge solution.
(3) Preparation of aqueous polymer solution:
The polymer obtained in example was diluted with pure water to obtain a 2 mass% aqueous polymer solution. As a standard substance, sodium benzoate was diluted with pure water to obtain a 2 mass% sodium benzoate aqueous solution.
BOD test:
in the measurement of BOD, a pressure sensor type BOD measuring instrument is used. After 144.75g of the above-prepared medium was weighed into a French flask, 0.75g of a 2% aqueous polymer solution was added. For blank measurement, 0.75g of pure water was added, and for standard measurement, 0.75g of 2% aqueous sodium benzoate solution was added. Then, the pH of the solution was measured, and the pH was adjusted by using a 0.1M aqueous hydrochloric acid solution so that the pH of the solution became 7.4.+ -. 0.2. Then, 4.5ml of a 1000ppm sludge solution was added as a test solution. After adding the stirrer to the frank flask, the stirrer was stirred in CO 2 CO is added into the absorbent retainer 2 1.8g of absorbent (YABASHI LIME) was set up to install BOD sensor. The BOD sensor-mounted French flask was stirred in a constant temperature bath at 24℃and the BOD value was calculated from the pressure sensor.
Calculation of the decomposition rate:
the theoretical oxygen demand (ppm) of the polymer was calculated, and the decomposition rate was calculated from the difference between the BOD value measured by the blank and the BOD value measured by the polycarboxylic acid (salt) containing an ester bond. The degradation rate 28 days after the start of the test was taken as the biodegradation rate.
Decomposition rate (%) = (biochemical oxygen demand from polymer)/(theoretical oxygen demand from polymer) ×100
< alkali decomposition Change Rate >
The pH of the ester group-containing polymer (ester bond-containing polycarboxylic acid (salt)) was set to 13 or more, 48% NaOH was added thereto, and the mixture was heated at 90℃for 5 hours to effect alkali decomposition. The weight average molecular weight before and after the alkali decomposition was measured under the following weight average molecular weight conditions, and the change rate was used as the alkali decomposition change rate.
Change rate of alkali decomposition (%) = (weight average molecular weight before alkali decomposition-weight average molecular weight after alkali decomposition)/(weight average molecular weight before alkali decomposition) ×100
< conditions for weight average molecular weight measurement >
The device comprises: HLC-8320GPC manufactured by Tosoh Co., ltd
A detector: RI (RI)
Column: tsk-gelG-3000SWXL X2
Column temperature: 40 DEG C
Flow rate: 0.5mL/min.
Calibration curve: american Polymer Standards polyacrylic acid standard
Eluent: 80mM phosphate buffer
< conditions for measurement of Capacity for Ca >
As a standard calcium ion solution for calibration curves, 50g of an aqueous solution of 0.01mol/L, 0.001mol/L and 0.0001mol/L was prepared using calcium chloride dihydrate, the pH was adjusted to a range of 9.5 to 10.5 with a 1.0% NaOH aqueous solution, 1mL of a 4mol/L aqueous potassium chloride solution (hereinafter abbreviated as 4M-KCl aqueous solution) was further added, and the mixture was sufficiently stirred using a magnetic stirrer to prepare a sample solution for calibration curves. In addition, as a standard calcium ion solution for test, the same calcium chloride dihydrate was used to prepare an aqueous solution of 0.001mol/L in a desired amount (50 g per sample).
Next, a test sample (polycarboxylic acid (salt) containing an ester bond) in terms of a solid content of 10mg was weighed in a 100mL beaker, 50g of the above-mentioned calcium ion standard solution for test was added thereto, and the mixture was sufficiently stirred by a magnetic stirrer. Then, as in the case of the calibration curve sample, the pH was adjusted to a range of 9.5 to 10.5 with a 1.0% aqueous sodium hydroxide solution, and 1mL of a 4M-KCl aqueous solution was added to prepare a test sample solution.
The thus prepared calibration curve sample solution and test sample solution were measured using a titration apparatus COM-1700 manufactured by Pingzhou Kogyo Co., ltd. By using an Orion 9720BNWP Sure-Flow calcium composite electrode manufactured by Thermo Fisher Scientific Co., ltd. A calibration curve of the molar concentration of Ca ions is prepared from the measured values of the sample liquid for calibration curve, and the molar concentration of Ca ions in the sample liquid is calculated from the measured values of the sample liquid for test using the calibration curve. The Ca capturing ability was calculated by the following calculation formula.
Ca Capture ability of sample solution
= (0.001-Ca ion molar concentration (mol/L) of sample)/0.01X100X 50/1000X 1000
< mud dispersibility test >
(1) Preparation of Glycine buffer (600 g was prepared by adding pure water to 67.56g of glycine, 52.60g of sodium chloride, and 5.00g of 48% sodium hydroxide).
(2) Preparation of buffer for dispersion (Ca/Mg=3/1 mol 100ppm in test solution) (1000 g was prepared by adding pure water to 60g of glycine buffer, 0.123g of calcium chloride dihydrate, and 0.056g of magnesium chloride hydrate).
(3) An aqueous solution of a polycarboxylic acid containing an ester bond was prepared.
(4) To a test tube, 0.3g of JIS11 clay, 27.0g of glycine buffer (2) and 3.0 g of an ester bond-containing polycarboxylic acid 0.10% aqueous solution (3) were added, and capped.
(5) After releasing the clay deposited on the bottom, the test tube was turned upside down 60 times.
(6) The cover of the test tube was removed, the upper part was covered with a preservative film, and the test tube was left to stand in a stable place for 20 hours.
(7) A5 cm portion of the upper part of a 5cc test tube was collected, and ABS (absorbance) was measured by UV380nm as a value for the mud dispersibility test.
The higher the value of the mud dispersibility test, the higher the mud dispersibility and the higher the mud scale cleaning power.
< carbon Black dispersibility test >
(1) An aqueous 5.0% solution of a polycarboxylic acid containing an ester bond was prepared.
(2) Into a test tube, 0.1g of Mitsubishi chemical carbon black #10 was charged 9g of ion-exchanged water and 1.0g of an ester bond-containing polycarboxylic acid 5.0% aqueous solution of (1), followed by capping.
(3) After releasing the carbon black deposited on the bottom, the test tube was turned upside down 60 times.
(4) The cover of the test tube was removed, the upper part was covered with a preservative film, and the test tube was left to stand in a stable place for 4 hours.
(5) The dispersion after standing was observed, and the dispersion was judged based on the following criteria.
Reference of
Well dispersed: excellent (L.) Excellent
To a certain extent disperse: (V)
Almost undispersed: x-shaped glass tube
The better the dispersibility of the carbon black, the higher the detergency of the composite soil containing the oil soil.
< conditions for NMR measurement >
The measurement was carried out under the following conditions 1 H-NMR。
Device name: varian VNMS 600
Measurement conditions:
nuclear species: 1 H
resonance frequency: 600MHz
Signal acquisition time: 3.4 seconds
Delay time: 5 seconds
Cumulative number of times: 128 times
Solvent: d (D) 2 O
Sample concentration: 10 percent of
The measurement data were dried under reduced pressure, dried, and then dissolved in a measurement solvent to measure the data.
Example 1 ]
(esterification step)
90 parts of ethylene glycol and 213.3 parts of maleic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 2L and a reflux condenser, and the mixture was heated to 120℃with stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the completion of the esterification step, 150 parts of pure water was charged, and 90 parts of a 15% aqueous sodium persulfate solution and 150 parts of a 35% aqueous hydrogen peroxide solution were continuously added dropwise at constant speed through separate charging lines for 60 minutes while stirring under reflux at a boiling point (about 105 to 101 ℃). Then, curing was performed under boiling reflux for 60 minutes. After curing, the temperature was lowered to obtain a polycarboxylic acid (1) containing an ester bond in a solid content of 44%.
The molecular weight of the obtained ester group-containing polycarboxylic acid (1) was measured by aqueous GPC, and the Ca capturing ability, biodegradability (according to OECD 301F) and molecular weight change after alkali decomposition were measured, and are shown in Table 1.
Example 2 ]
(esterification step)
90 parts of ethylene glycol and 284.4 parts of maleic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 2L and provided with a stirrer and a reflux condenser, and the mixture was heated to 120℃while stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the esterification step was completed, 120 parts of pure water was charged, and 60 parts of a 15% aqueous sodium persulfate solution, 150 parts of a 35% aqueous hydrogen peroxide solution, and 42 parts of an 80% aqueous acrylic acid solution were continuously added dropwise at constant speed through separate charging lines for 60 minutes while stirring under reflux at a boiling point (about 105 to 101 ℃). Then, curing was performed under boiling reflux for 60 minutes. After curing, the temperature was lowered to obtain polycarboxylic acid (2) containing an ester bond in a solid content of 55%.
Physical properties were measured in the same manner as in example 1, and the results are shown in table 1.
Example 3 ]
(esterification step)
90 parts of ethylene glycol and 284.4 parts of maleic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 2L and provided with a stirrer and a reflux condenser, and the mixture was heated to 120℃while stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the esterification step was completed, 60 parts of a 15% aqueous sodium persulfate solution, 210 parts of a 35% aqueous hydrogen peroxide solution, and 42 parts of an 80% aqueous acrylic acid solution were continuously added dropwise at a constant rate through separate feed lines for 60 minutes while stirring under reflux at a boiling point (about 105 to 101 ℃). Then, curing was performed under boiling reflux for 60 minutes. After aging, the temperature was lowered, and 300 parts of pure water was added to obtain a polycarboxylic acid (3) containing an ester bond in an amount of 42% in solid content.
Physical properties were measured in the same manner as in example 1, and the results are shown in table 1.
Example 4 ]
(esterification step)
90 parts of ethylene glycol and 284.4 parts of maleic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 2L and provided with a stirrer and a reflux condenser, and the mixture was heated to 120℃while stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the esterification step was completed, 60 parts of a 15% aqueous sodium persulfate solution, 210 parts of a 35% aqueous hydrogen peroxide solution, and 84 parts of an 80% aqueous acrylic acid solution were continuously added dropwise at constant speed through separate feed lines for 60 minutes while stirring under reflux at a boiling point (about 105 to 101 ℃). Then, curing was performed under boiling reflux for 60 minutes. After aging, the temperature was lowered, and 150 parts of pure water was added to obtain a polycarboxylic acid (4) containing an ester bond in a solid content of 50%. The proton NMR spectrum of the obtained polycarboxylic acid (4) containing an ester bond is shown in FIG. 1.
Physical properties were measured in the same manner as in example 1, and the results are shown in table 1.
Example 5 ]
(esterification step)
90 parts of glycerin and 219 parts of itaconic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 2L and provided with a stirrer and a reflux condenser, and the mixture was heated to 70 ℃ while stirring, and then heated and stirred at 70 ℃ for 60 minutes.
(polymerization step)
After the completion of the esterification step, 300 parts of pure water was charged, and 39 parts of a 10% aqueous sodium persulfate solution and 97.5 parts of a 10% aqueous sodium bisulfite solution were continuously added dropwise at constant speed through separate charging lines for 60 minutes while stirring at 95 ℃. Then, curing was performed under boiling reflux for 60 minutes. After curing, the temperature was lowered to obtain a polycarboxylic acid (5) containing an ester bond in an amount of 42% of the solid content.
Physical properties were measured in the same manner as in example 1, and the results are shown in table 1.
Example 6 ]
(esterification step)
90 parts of ethylene glycol and 150 parts of itaconic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 2L and provided with a stirrer and a reflux condenser, and the mixture was heated to 120℃with stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the completion of the esterification step, 600 parts of pure water was charged, and 60 parts of a 15% aqueous sodium persulfate solution and 210 parts of a 30% aqueous sodium bisulfite solution were continuously added dropwise at constant speed through separate charging lines for 60 minutes while stirring at 95 ℃. Then, curing was performed under boiling reflux for 60 minutes. After aging, the temperature was lowered, and 300g of pure water was charged to obtain a polycarboxylic acid (6) containing an ester bond in an amount of 27% in solid content.
Physical properties were measured in the same manner as in example 1, and the results are shown in table 1.
TABLE 1
Rate of change of alkali decomposition: (molecular weight before decomposition-molecular weight after alkali decomposition)/molecular weight before decomposition X100
The alkali decomposition is carried out as follows: the polycarboxylic acid containing an ester group of each example was brought to pH13 by adding NaOH, and heat-treated at 100℃for 3 hours.
Ca capturing ability: ca amount (as CaCO) captured by 1g of polymer solid content 3 Is calculated in terms of mg quantity of (2)
Mud dispersibility test: the ability to disperse the mud was measured. The higher the number, the higher the dispersing ability, and the higher the cleaning power of the mud scale when added to the detergent.
Comparative example
As comparative examples, physical properties were measured using sodium polyacrylate (comparative polycarboxylic acid (C-1)) having a molecular weight of 2500 in the same manner as in example 1, and are shown in Table 2.
TABLE 2
Example 7 ]
(esterification step)
35 parts of ethylene glycol and 94.8 parts of maleic anhydride were charged into a reaction vessel made of SUS316L having a capacity of 1L and provided with a stirrer and a reflux condenser, and the mixture was heated to 120℃while stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the esterification step was completed, 2 parts of a 1.8% aqueous solution of a Moire salt was charged, and 12 parts of diethanolamine, 70 parts of a 35% aqueous solution of hydrogen peroxide, and 28 parts of an 80% aqueous solution of acrylic acid were continuously added dropwise at constant speed through separate charging lines for 120 minutes while stirring under reflux at a boiling point (about 120 to 135 ℃). Then, curing was performed under boiling reflux for 30 minutes. After curing, the temperature was lowered to obtain a polycarboxylic acid (7) containing an ester bond in a solid content of 44%.
The molecular weight of the obtained ester group-containing polycarboxylic acid (7) was measured by aqueous GPC, and the Ca capturing ability, biodegradability (according to OECD 301F) and molecular weight change after alkali decomposition were measured, and are shown in Table 3.
In addition, the Ca-capturing ability of the ester group-containing polycarboxylic acid (7) was evaluated, and as a result, 160mgCaCO was obtained 3 And/g, the biodegradability (according to OECD 301F) was evaluated, as a result of which it was 55%.
Example 8 ]
(esterification step)
21.7 parts of ethylene glycol, 66.4 parts of maleic anhydride, and 10.5 parts of SOFTANOL 60 (a secondary alcohol EO6 mol adduct, manufactured by Nippon catalyst Co., ltd.) were charged into a reaction vessel made of SUS316L having a capacity of 1L and a reflux condenser, and the mixture was heated to 120℃with stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the esterification step was completed, 1.4 parts of 1.8% aqueous solution of a Moire salt was charged, and 16.8 parts of diethanolamine, 56 parts of 35% aqueous solution of hydrogen peroxide, and 19.6 parts of 80% aqueous solution of acrylic acid were continuously added dropwise at a constant rate through separate charging lines for 120 minutes while stirring under reflux at a boiling point (about 120 to 135 ℃). Then, curing was performed under boiling reflux for 30 minutes. After aging, the temperature was lowered, and 300 parts of pure water was added to obtain a polycarboxylic acid (8) containing an ester bond in an amount of 42% in solid content.
Physical properties were measured in the same manner as in example 1, and the results are shown in Table 3.
Example 9 ]
(esterification step)
To a reaction vessel made of SUS316L having a capacity of 2L and equipped with a stirrer and a Dean-Stark tube for dehydration, 34.3 parts of ethylene glycol, 164 parts of 1,2,3, 4-butanetetracarboxylic acid dianhydride, 2.26 parts of 70% aqueous p-toluenesulfonic acid solution, and 300 parts of water were charged. The temperature was raised while stirring, dehydration was performed, and after the internal temperature reached 150 ℃, heating and stirring were continued for 60 minutes.
(neutralization step)
After the completion of the esterification step, the temperature was lowered to 60 ℃, 87.5 parts of sodium carbonate was dissolved in 374 parts of pure water, and the resultant solution was poured in all, stirred for 30 minutes, and then nitrogen bubbling was performed at a flow rate of 100 mL/min to obtain polycarboxylic acid (9) containing an ester bond in a solid content of 40%.
The molecular weight of the obtained polycarboxylic acid (number) containing an ester group was measured by aqueous GPC, and the Ca capturing ability, biodegradability (according to OECD 301F) and molecular weight change after alkali decomposition were measured, and are shown in Table 3.
Example 10 ]
(polymerization step)
125 parts of water, 155 parts of maleic acid, and 70.2 parts of a 0.1% Moire salt water solution were added to a reaction vessel made of SUS316L having a capacity of 2L and provided with a stirrer and a reflux condenser, and the temperature was raised to 100℃while stirring. 129 parts of 35% hydrogen peroxide and 20.6 parts of water were mixed together and the mixture was dropped into the autoclave at a constant rate of 4 hours while maintaining the temperature. After the completion of the dropwise addition, the mixture was aged for 30 minutes and then cooled to room temperature.
(esterification step)
16.6 parts of the entire reaction solution and ethylene glycol were added to a reaction vessel made of SUS316L having a capacity of 2L and equipped with a stirrer and a Dean-Stark tube for dehydration, and the mixture was heated while stirring to dehydrate, and after the internal temperature reached 150 ℃, the heating and stirring was continued for 60 minutes.
(neutralization step)
After the completion of the esterification step, the temperature was lowered to 60 ℃, 70.6 parts of sodium carbonate was dissolved in 387 parts of pure water, and the resultant solution was poured in all, stirred for 30 minutes, and then nitrogen bubbling was performed at a flow rate of 100 mL/min to obtain polycarboxylic acid (10) containing an ester bond in a solid content of 40%.
The molecular weight of the obtained polycarboxylic acid (number) containing an ester group was measured by aqueous GPC, and the Ca capturing ability, biodegradability (according to OECD 301F) and molecular weight change after alkali decomposition were measured, and are shown in Table 3.
In addition, regarding the polycarboxylic acid (10) having an ester group, biodegradability (according to OECD 301F) was evaluated, and as a result, it was 22%.
Example 11 ]
(polymerization step)
102 parts of water, 131 parts of itaconic acid, and 70.1 parts of a 0.1% Moire salt water solution were added to a reaction vessel made of SUS316L having a capacity of 2L and a reflux condenser, and the mixture was stirred and heated to 100 ℃. While maintaining the temperature, 197 parts of 35% hydrogen peroxide was added dropwise to the autoclave at constant speed over 4 hours. After the completion of the dropwise addition, the mixture was aged for 30 minutes and then cooled to room temperature.
(esterification step)
To a reaction vessel made of SUS316L having a capacity of 2L and equipped with a stirrer and a Dean-Stark tube for dehydration, 21.3 parts of ethylene glycol and 2.60 parts of 70% aqueous p-toluenesulfonic acid were added, and the mixture was stirred while heating up, dehydrated, and heated and stirred for 60 minutes after the internal temperature reached 150 ℃.
(neutralization step)
After the completion of the esterification step, the temperature was lowered to 60 ℃, 53.3 parts of sodium carbonate was dissolved in 379 parts of pure water, all the obtained solution was poured into the reactor, and after stirring for 30 minutes, nitrogen bubbling was performed at a flow rate of 100 mL/min, to obtain polycarboxylic acid (11) containing an ester bond in a solid content of 40%.
The molecular weight of the obtained polycarboxylic acid (number) containing an ester group was measured by aqueous GPC, and the Ca capturing ability, biodegradability (according to OECD 301F) and molecular weight change after alkali decomposition were measured, and are shown in Table 3.
Example 12 ]
(esterification step)
30.0 parts of ethylene glycol, 94.8 parts of maleic anhydride and 20.0 parts of citric acid were charged into a reaction vessel made of SUS316L having a capacity of 1L and a reflux condenser, and the mixture was heated to 120℃with stirring, and then heated and stirred at 120℃for 60 minutes.
(polymerization step)
After the esterification step was completed, 2.0 parts of a 1.8% aqueous solution of a Moire salt was charged, and 25.0 parts of diethanolamine, 90 parts of a 35% aqueous solution of hydrogen peroxide, and 35 parts of a 80% aqueous solution of acrylic acid were continuously added dropwise at constant speed through separate charging lines for 120 minutes while stirring under reflux at a boiling point (about 110 to 135 ℃). Then, curing was performed under boiling reflux for 30 minutes. After aging, the temperature was lowered, and 300 parts of pure water was added to obtain a polycarboxylic acid (12) containing an ester bond in a solid content of 45%. Physical properties were measured in the same manner as in example 1, and the results are shown in Table 3.
TABLE 3
From the results of tables 1 and 2, it is understood that the ester bond-containing polycarboxylic acid of the present invention has a good alkali decomposition rate and biodegradability.
As is clear from the results shown in Table 3, the polycarboxylic acid containing an ester bond of the present invention has not only a good alkali decomposition rate but also good carbon black dispersibility.

Claims (6)

1. An ester bond-containing polycarboxylic acid (salt) having a structural unit derived from an ester group in the main chain,
having a carboxylic acid (salt) in a side chain,
the carbonyl carbon of the ester group has a carboxylic acid (salt) at the beta-or gamma-position.
2. The ester bond-containing polycarboxylic acid (salt) according to claim 1, wherein,
The alkali decomposition change rate is more than 10%.
3. The ester bond-containing polycarboxylic acid (salt) according to claim 1 or 2, wherein,
the biodegradability is 20% or more.
4. A detergent composition comprising the ester bond-containing polycarboxylic acid (salt) according to claim 1 to 3.
5. A method for producing an ester bond-containing polycarboxylic acid (salt), comprising:
a step of reacting a compound having an unsaturated double bond and an acid anhydride group with a compound having two or more hydroxyl groups; and
and a step of reacting the double bonds of the product of the above step.
6. A method for producing an ester bond-containing polycarboxylic acid (salt), comprising:
and a step of reacting a compound having three or more carboxylic acids (salts) or an anhydride thereof with a compound having two or more hydroxyl groups.
CN202280052691.2A 2021-07-27 2022-07-25 Polycarboxylic acid (salt) containing ester bond and method for producing same Pending CN117715949A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-122126 2021-07-27
JP2022-044810 2022-03-22
JP2022044810 2022-03-22
PCT/JP2022/028620 WO2023008367A1 (en) 2021-07-27 2022-07-25 Ester bond-containing polycarboxylic acid (salt) and method for producing same

Publications (1)

Publication Number Publication Date
CN117715949A true CN117715949A (en) 2024-03-15

Family

ID=90144788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280052691.2A Pending CN117715949A (en) 2021-07-27 2022-07-25 Polycarboxylic acid (salt) containing ester bond and method for producing same

Country Status (1)

Country Link
CN (1) CN117715949A (en)

Similar Documents

Publication Publication Date Title
JP5178008B2 (en) Amino group-containing water-soluble copolymer
AU625453B2 (en) Water soluble polymers for detergent compositions
AU660166B2 (en) Biodegradable polymers, process for preparation of such polymers, and compositions containing such polymers
CA2038332A1 (en) Preparation of homopolymers and copolymers of monoethylenically unsaturated dicarboxylic acids and use thereof
IE904217A1 (en) Biodegradable, water-soluble graft copolymers, compositions¹containing such copolymers, and methods of use of such¹copolymers
NZ242068A (en) Preparation of itaconic acid polymers, use in detergents and water treatment.
JP2007231261A (en) (meth)acrylic acid-based copolymer, method for producing the same and detergent composition using the same
JP2008303347A (en) Polyalkylene glycol-based compound, its production method and its usage
EP1741750A2 (en) Water-soluble amphoteric copolymer, production method thereof, and application thereof
EP1182217A2 (en) Novel water-soluble copolymer and its production process and use
JP4323700B2 (en) Novel water-soluble copolymer, its production method and use
JP5660905B2 (en) Polyalkyleneamine alkylene oxide copolymer
JP5117887B2 (en) Cationic copolymer and use thereof
CN117715949A (en) Polycarboxylic acid (salt) containing ester bond and method for producing same
JPH05239127A (en) Bio-degradable hydrophilic cross-linked polymer, its production and use of the cross-linked polymer
WO2023008367A1 (en) Ester bond-containing polycarboxylic acid (salt) and method for producing same
JP3917857B2 (en) Amino group-containing polymer, production method thereof, and use
EP1505091A1 (en) Water-soluble copolymer
JP4750935B2 (en) Water-soluble polymer composition and use thereof
IE904216A1 (en) Biodegradable, water-soluble polycarboxylic acid copolymers,¹compositions containing such copolymers and methods of use¹of such copolymers
WO2000059958A1 (en) Crosslinked copolymer of unsaturated carboxylic acid and process for producing the same, copolymer of unsaturated carboxylic acid, biodegradable builder, and detergent composition
JP2007262403A (en) Itaconic acid-based copolymer, method for producing the same and detergent composition using the same
JP2004091635A (en) Water-soluble polymer and its application
EP4172297A1 (en) Laundry detergent formulation with biodegradable antiredeposition agent
CN115362248A (en) Polymer composition suitable as anti-graying agent in detergent formulations

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication