TW201240937A - Phosphorus-containing (poly)alkylene glycol compound and polymer - Google Patents

Abstract

The present invention provides: a polymer which, when used in a cement composition or the like, exhibits higher-level water-reducing properties, workability and other performances and which is useful in various fields of application, particularly as a cement admixture; and a compound which makes it possible to manufacture such a polymer easily and efficiently and at a low cost. The present invention pertains to: a phosphorus-containing (poly)alkylene glycol compound having a structure wherein the terminal oxygen atom at at least one end of the (poly)alkylene glycol chain is bonded to a phosphorus atom with an organic residue therebetween, with the organic residue being bonded to the phosphorus atom by a phosphorus -carbon bond; and a phosphorus-containing (poly)alkylene glycol polymer which comprises a (poly)alkylene glycol chain and structural units derived from a vinyl monomer and which has a structure wherein the terminal oxygen atom at at least one end of the (poly)alkylene glycol chain is bonded to a phosphorus atom with an organic residue therebetween, with the organic residue being bonded to the phosphorus atom by a phosphorus -carbon bond, while the phosphorus atom is bonded to the main chain comprising the structural units derived from a vinyl monomer.

Description

201240937 VI. OBJECTS OF THE INVENTION · TECHNICAL FIELD The invention relates to a (poly)alkylene glycol-based compound and a 4 σ substance containing a phosphorus atom. More specifically, it is used as a soft segment for various applications such as an adhesive or a sealant represented by the use of a cement admixture, a use of a softening component, and a use as a lotion adjuvant. (♦) an alkylene glycol-based polymer, and a phosphorus-containing (poly)alkylene glycol-based compound suitable as a chain transfer agent for producing such a polymer. [Prior Art] A polymer containing a (poly)alkylene glycol chain (hereinafter also referred to as a (poly)alkylene glycol polymer) is rendered hydrophilic by appropriately adjusting its chain length or constituent alkylene oxide. Or a property such as hydrophobicity or steric repulsion, and is widely used as a soft segment in various applications such as an adhesive or a sealant, a softening component, and a lotion aid. In recent years, it has been added to cement paste. The use of cement admixtures in cement compositions such as mortars and concrete has been studied. Such a cement admixture is generally used as a water reducing agent and the like for the purpose of improving the fluidity of the cement composition and reducing the strength or durability of the cured product by reducing the water content of the cement composition. The water reducing agent has previously used a water reducing agent such as a naphthalene system, but since the (poly)alkylene glycol chain functions as a dispersing group for dispersing the cement particles by its steric repulsion, it functions as a water reducing effect. Further, a polycarboxylic acid-based water reducing agent containing a (poly)alkylene glycol chain has been re-disclosed, and it has recently been used as a high-performance ae water reducing agent. For example, it is disclosed that a polymer containing a (poly)alkylene glycol chain is known as 201240937. The following polymer: after having an acid having a double bond at both ends or at one end, decomposing the generated sulfur s group to obtain the terminal,竣^ ^ ^ is not 缒 or one end has a basis (4) (for example, refer to Patent Document 1); or as a decomposable water-soluble polymer in the auxiliary agent, the phase μ is auxiliary _ ώ. A polymer obtained by blocking or graft-polymerizing an ethylenically unsaturated monomer component, which is obtained by introducing a polyunsaturated compound into a poly-myster compound (for example, see Patent Document 2). Further, it is disclosed that a polymer having a (poly)-extended diol chain and a polymer derived from a constituent unit of an unsaturated monomer which is bonded to at least the terminal of the chain is 7 G later. Cement mixed agent and patent document 3) 〇 Furthermore, stick + ancient Λ 匕 匕 匕 quot 揭 揭 揭 揭 揭 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : A polymer having a multi-branched structure of a diol bond is useful as a cement admixture (for example, see Patent Document 4). Patent Document 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-65-145 SUMMARY OF INVENTION [Invention] The polymer containing a (poly)alkylene alcohol chain for use as a cement admixture as described above is disclosed as having a long history of broadcasting a know-how The sturdy, but still not able to achieve the level of performance that has recently been expected to be extremely high (cement dispersibility (water reduction) or enthalpy (4)). The dispersibility or retention of cement is an important element of 201240937 related to the handling of cement site operability or the strength of cement hardening. Therefore, it is necessary to realize these mud mixing agents, and it is also necessary to be simple and cement admixture. Compound. The water of the cement composition which is more excellent is efficiently produced at low cost. The present invention has been made in view of the above-mentioned status quo, and the cement is used at a higher level to provide a property which can be used for various purposes, such as water or workability. The combined use is particularly high in cement mixing and high... Polymers useful in M applications, and compounds which can be easily and efficiently produced at low cost. The inventors have mixed a cement which is excellent in properties such as cement dispersibility (water-reducing property) or m-retention property, or can be preferably used for the manufacture of such a poly-S material. In the various studies, it was found that the novel compound having the following structure has a (poly)alkylene glycol bond and the end of the (poly)alkylene glycol chain The oxygen atom is bonded to the phosphorus atom in the sub- cephalic acid or the sulphur residue, the residue of the genus (hereinafter referred to as the hypophosphite (salt) residue, via the organic residue, and the organic The residue is bonded to the phosphorus atom by a uni-carbon bond. Further, I see that the polymer having a mouthwash structure is excellent in cement dispersibility (water-reducing property) or a material having excellent properties and can be preferably used as a cement admixture having a (poly) chain in the main chain. An alkylene glycol chain and a structural unit derived from a vinyl monomer, and a terminal oxygen atom of at least one terminal of the (poly)alkylene glycol chain is bonded to a residue of a hypophosphorous acid or a salt thereof via an organic residue ( a phosphorus atom bonded to a subphosphorus I (salt) residue, and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond, and the phosphorus atom is bonded to a polymer containing a vinyl monomer unit The main chain. Further, it has been found that the above-mentioned compound has a function as a transfer agent for the chain polymerization of the radicals 5 201240937, and can be preferably polymerized by using the above compound as a bond transfer agent, and is excellent in properties such as retention of polymer properties obtained. Things. For the production of various polymers; if the use of a vinyl-based monomer component for free cement dispersibility (water-reducing) or a good use as a cement admixture is found: if used, it has the following structure: Multi-branched structure... As the above compound, a polymer obtained by using the compound as a chain transfer agent (i.e., having a multi-branched structure and a sigma-like substance) can exert a function on the cement composition or the like due to its steric repulsion. The soap has more water-reducing properties. The above structure is based on a compound having three or more active hydrogens, and three or more (poly)alkylene glycol chains are bonded, and the (poly)alkylene glycol chain, ^ ^ ^ The terminal oxygen atom at the other end of the bonding is bonded to the disc atom of the underdentation (salt) residue via the organic residue, and the hydrazine organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond. It has also been found that a poly(alkylene)-terminated diol-based compound having a specific structure as described above can be used not only as a chain transfer agent in the production of various polymers but also as a chain-transfer agent by using a far-chain transfer agent. Since the monomer component is aggregated to obtain a cement admixture having excellent properties, such a method is industrially very useful for hand & ' it can be easily and efficiently manufactured at low cost for use in cement admixtures. The above polymer is considered to be a satisfactory solution to the above problems. That is, the present invention is a (poly)alkylene glycol-based compound containing a phosphorus atom, which is a compound having a (iv) atom and a (poly)-extended diol chain, and has the following structure, which is (8) At least the terminal oxygen atom of the alcohol chain is bonded to the phosphorus atom via the organic residue, and the above organic residue is bonded to the above-mentioned 201240937 phosphorus atom by a phosphorus-carbon bond. Further, the present invention relates to a (poly)alkylene glycol-based polymer containing a phosphorus atom, which is required to have a polymer of a phosphorus atom and a (poly)alkylene glycol chain, and has the following structure. The terminal oxygen atom having at least one end of the (poly)-extended diol chain of the structural unit derived from the (poly)-extended diol bond and the ethylenic-based monomer is bonded to the scale atom via an organic residue, Further, the organic residue is bonded to the above-mentioned filler atom by a lin-carbon bond, and the phosphorus atom is bonded to the main chain of the structural unit derived from the vinyl monomer. The invention is described in detail below. Further, each of the preferred embodiments of the present invention described in the following two or more combinations is also a preferred shape of the present invention. <Polyalkylene-containing (poly)alkylene glycol-based compound> The atom-filled (poly)-forming diol-based condensed diol chain (PAG) of the present invention, derived from hypophosphite (salt) The structural part (gift), and the organic residue (γ) located between the two. The disc atom-containing (poly)-extended diol-based compound of the present invention may contain other structural sites as long as it has three structural sites. And ^ contains ; In the case of two or more such structural parts, the same may or may not be used. In the case of 11(=1), in the case of 11=1, it means that the diol is extended: : In the case of 'the case' refers to the performance of the smashing diol, which is the same as the r^ of the Π>1. From the following, the phosphorus-containing atom of the present invention is also referred to as a phosphorus PAG compound. Let "alcohol compound 201240937" (poly)alkylene glycol chain (PAG), only I loop # Λ, K /, to be composed of a lactide having a carbon number of 2 or more (polyepoxy) Preferably, the tetrakisole is preferably a carbon number of 2, more preferably a carbon number of 2 to 8 s., for example, ethene oxide, propylene oxide, butylene oxide.焓 焓, ο ϊ 技 么 么 乳 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J Ethane, epoxybutene, octylene oxide, etc. Further, dipentane ethylene oxide, two HHt xffi /, and already known as jade-lactated special fat c; An alicyclic epoxide such as oxetan, tetraziridine or tetradecylene epoxide; an aromatic epoxide such as epoxy phenyl b.-dioxalate, etc. The alkylene glycol chain (filled with G according to the present invention) is preferably used in the form of a (poly)alkylene glycol compound.

, although, for example, when used to make Huan, the corpse J, it is about the situation of the composition of the 盥 、 尸 尸 尸 尸 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ~8 Epoxy Ethylene = Ring Oxide (oxyl extension base) as the main body. More preferably, the body: "Γ, butyl butyl oxide and other carbon number 2 ~ 4 epoxy burning, and preferably epoxy blush as the main body. Here, the so-called r Φ from 2 boxes", Refers to the (poly)alkylene glycol chain (PAG): the majority of the two or more epoxy institutes. In the presence of the right .p W decane, all % oxyalkylene 1 〇〇 Mo 〇 / middle ear % means "% of the most extracted oxyethylene sulphur is used. The sub-f is preferably 5_G~/GG%. Thereby, the polymer (hereinafter also referred to as: 丨; 申二化合物, which is obtained by 60 mol% or more (1)) / has a more hydrophilic property. More preferably, it is preferably 7 〇 〇 〇. Above, especially good for 8〇 201240937 Moer. /. Above, it is preferably 90 mol% or more. In the case where the above (poly) stilbene diol chain (PAG) is composed of two or more types of epoxy marshalling, two or more kinds of epoxies may be randomly added, blocked, and alternately added. In the case of any of the above-mentioned (poly)alkylene glycol chains in the above-mentioned phosphorus-containing compound, the addition of the above-mentioned (poly)alkylene glycol chain may be the same or different. . ^, the above (poly) condensed diol chain (PAG), in the case of containing an alkylene oxide having 3 or more carbon atoms, can impart a certain degree of hydrophobicity to the above polymer (i), so the above polymer (i) When used in a cement admixture 2, the cement particles may have a number of structures (mesh) to reduce the stickiness or hard feeling of the cement composition. On the other hand, when the alkylene oxide having a carbon number of 3 or more is excessively introduced, the hydrophobicity of the polymer (i) becomes too high, and on the contrary, the performance of dispersing the cement particles is insufficient. Therefore, the content of the alkylene oxide having 3 or more carbon atoms based on 100% by mass of all the alkylene oxide is preferably 3 Å or less. More preferably, it is 25% by mass or less, further preferably 2% by mass or less, and particularly preferably 5% by mass or less. Further, depending on the application required for the above polymer (i), there is also a case where it is preferable to not contain an alkylene oxide having 3 or more carbon atoms. Here, the structural unit derived from the (poly)alkylene glycol chain represented by "PAG" and derived from "SHp" derived from hypophosphorous acid (salt) may be caused by the structure represented by "γ". Hydrolyzed and cut. When it is necessary to improve the hydrolysis resistance, it is preferred to introduce an alkyl group having a carbon number of 3 or more at the terminal of the (poly)alkylene glycol chain. Examples of the oxyalkylene group having 3 or more carbon atoms include an oxypropyl group, a urethane butyl group, an oxystyrene group, and an alkyl epoxy propyl ether residue. Among them, in terms of easiness of production, an oxypropyl group and an oxybutyl group are preferred. The amount of introduction of the above-mentioned oxyalkylene group having 3 or more carbon atoms is determined according to the required hydrolysis resistance, and the amount of introduction is preferably 50 mol% or more with respect to both ends of the (poly) glycerin chain. More preferably, it is more than 1% of the moles and preferably 1 50 moles. /. Above, it is especially good to be 2% or more. Further, in order to improve the hydrolyzability, it is preferred that the terminal of the above (poly)alkylene glycol chain (PAG) is a secondary alcohol residue. As long as it is used in the introduction of a secondary alcohol group at the end of the (poly)alkylene glycol chain, for example, as long as it is a (poly)alkylene glycol addition to the raw material of the (poly)alkylene glycol chain. The carbon number is 3 or more = the alkylene oxide can be used. In the addition reaction, in order to increase the introduction rate of the secondary alcohol group, it is preferred to use an alkali metal, an alkaline earth metal, and at least one selected from the group consisting of such oxides or oxychlorides. 1 帛 compound as a catalyst. More preferably, it is sodium hydroxide, potassium hydroxide, hydroxide #, calcium hydroxide, and it is preferably sodium hydroxide or potassium hydroxide. In order to prevent side reactions, the amount of the above-mentioned catalyst used in the addition reaction is preferably 50,000 ppm or less based on the amount of the compound containing the (8) extended diol chain. More preferably, it is 200,000 ppm or less, further preferably 10,000 psi or less, more preferably 10,000 ppm or less, still more preferably 5 〇〇〇 ppm or less, and most preferably 2 〇〇〇 Ppm or less. Further, in order to obtain good productivity and a sufficient reaction rate, it is preferably 10 ppm or more. More preferably, it is 5 〇 or more, and further preferably 1 〇 〇 p p m or more, and Yu Wei a 0 Λ Λ 兀 is preferably 200 ppm or more. In the case of using an epoxy-based addition reaction using a compound material containing a (poly)-extended diol chain, it is possible to use only a compound containing a (poly)alkylene glycol chain as a raw material. The catalyst is subjected to an addition reaction, and the catalyst may be added or removed as needed. Further, in order to increase the introduction rate of the secondary alcohol group, the reaction temperature in the addition reaction is preferably 50 to 20 (TC, more preferably 70 to 17 Torr, further preferably 9 to 150 C, and particularly preferably 100). ～130. 〇 In terms of preventing side reactions, the above conditions are preferred even when no secondary alcohol group is introduced. In the addition reaction, in order to prevent generation of impurities f, it is preferred to sufficiently feed the raw materials. In particular, the water content is preferably iOOOOppm or less, more preferably 5 〇〇〇 ppm or less, more preferably 1 〇〇 ton or less, and more preferably 500 ppm or less, more preferably 500 ppm or less. 2 〇〇 ppm or less. ～ The preferred range of the outer bamboo 于 于 于 于 于 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 及 及 及 及 及 及 及 及 及 及 及 及 及The synthesis of the compound of the (poly)-extended diol bond represented by the formula (5) is also the same. (The average addition molar number of the oxygen-extended base), the inch 敎 J car is preferably 1 to 1 〇〇 〇. By setting it to a number of 1 or more, the above-mentioned polymerization can be made, and the product can be sufficiently utilized based on the performance of the (poly)-stretched fermentation chain. When „, n exceeds 1000, it is useful to manufacture the above polymer (i); Li & human r is insufficient... The viscosity of the two substances is increased or the reactivity is insufficient to be deflated Preferably, the lower limit of the average number of repetitions, L RP s . . . 〇 住 住 住 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The average average addition mole number of the above alkylene oxides refers to the (poly)alkylene fermentation chain of the (poly)alkylene 201240937 alcohol compound of the 3 (one) atom of the present dairy base. The average value of the molar number of the alkylene oxide added to the molar is preferably the organic residue represented by the above γ, and the molecular weight is less than 1000. If it exceeds 1,000, it is difficult to introduce the base, and the economical damage is impaired. More preferably, it is 500 or less, and further preferably 300 or less. The organic residue may be a linear, branched or % alkyl group having a carbon number of 2 to 30, or a carbon number of 6 to 30. a divalent aromatic group (phenylene, alkylphenyl, and a valent group derived from pyridine, thiophene, pyrrole, furan, thiazole, etc.) For example, a group which may be substituted with a substituent such as a hydroxyl group, an amine group, an ethyl fluorenyl group, a cyano group, a carbonyl group, a carboxyl group, a halogen group, a sulfonyl group, a nitro group or a decyl group is preferred. More preferably, it is a divalent organic residue having a carbon number of 2 to 18 and a part of the carbon residue is substituted by a hydroxyl group, and more preferably a linear or branched alkyl group having a carbon number of 2 to 8 and One of the parts is substituted by a hydroxyl group. In the present invention, the 'sub-sub-salt is preferably a salt formed from a sub- cephalic acid and any one of a metal, ammonia or an organic amine. The metal is preferably An alkali metal, a soil for a soil test, etc. The organic amine may, for example, be an alkylamine having 1 to 18 carbon atoms, a mercaptoamine or a polyalkylene polyamine, etc., among which sodium or potassium is preferred. , a salt formed by ammonia or triethanolamine. The (poly)alkylene glycol compound containing a phosphorus atom of the present invention preferably has the following formula (1):

X • Γ \—/ ο (Α ΟΗΡ ΟΗΡ-ο m \1/ ^1 2 201240937 where x represents a residue of a compound having an active hydrogen or a hydrogen atom. 〇: the same or different, indicating a carbon number 2~ 18 oxyalkylene. Y1 is the same or 5 S non-organic residue. γ2 is the same or different 'is an organic residue or hydrogen, the same or different oxime' represents a metal atom, an ammonium group or an organic amine group. η is the same or different , 矣J is the structure represented by the average addition molar number of the non-oxyalkylene group, which is the number of 〇, m is an integer from 1 to 50). In the above formula (1), the specific U of the oxyalkylene group represented by AO is the same as that of the above-mentioned (poly)alkylene glycol chain (pAG) having a carbon number of 2 to ^. Further, the organic residue represented by γ1 is the same as the above-mentioned compound: 'the metal atom of the oxime', and the organic amine group is the same as the i-gen atom and the organic amine group forming the hypophosphite. The preferred value of 11 is the same as the preferred value of the average number of repetitions of the epoxy burn in the above (poly)alkylene glycol (〇). The organic residue in γ2 of the above formula (1) may, for example, be a linear bond, a branched or cyclic alkyl group having a carbon number of 1 to 3 Å, or a monovalent aromatic group having a carbon number of 6 to 30. (Phenyl, pyridylphenyl, D is more than a butyl group, a thiophene group, a phenylidene group, a furamyl group, a thiazolyl group, etc.). These may be substituted, for example, by a substituent such as a hydroxyl group, an amine group, an ethyl hydrazino group, a cyano group, a carbonyl group, a carboxyl group, a halogen group, a sulfonyl group, a nitro group or a decyl group. Among these, a monovalent organic residue having 2 to 18 carbon atoms is preferred. More preferably, it is a linear or branched alkyl group having 2 to 8 carbon atoms. Γ2 in the above formula (1) is an organic residue or a hydrogen atom. That is, in the (poly)alkylene glycol-based compound containing a phosphorus atom of the present invention, a hydrogen atom derived from a sub-acid (salt) is substituted with an organic residue.

In the case of A 13 201240937 °H, the domain-containing shield compound of the present invention functions as a chain transfer agent, and the Y2 is preferred. It is a hydrogen atom. The compound comprises a compound having a multi-branched structure, a compound which does not degenerate a non-branched (linear) structure; "::, the structure of the character of the structure ^ b has a multi-branched knot = do not, refers to the following structure' The structure is a polymer chain having at least three or more active gas site bonding-containing pits-(four) of the compound having:: the polymer chain having the residue having three or more living compounds as a base point The compound is a radiation-like structure, and a compound having a non-branched structure means a structure in which the residue having three or more compounds of the wind-like compound is branched and formed into a radial chain. The (poly)erythritol-based compound having a constituent atom of a branched structure is a structure in which a polymer having no reactive hydrogen compound having three or more active hydrogen compounds as a base point is branched and formed into a radial shape, for example, The γ 丨 in the above formula (1) has a branching structure in the overall structure of the compound as in the case of an alkylene group having a bipartite structure. The above-mentioned non-multi-branched (linear) structure contains a phosphorus atom (poly Stretch The alkanediol-based compound has a structure in which the compound in the above formula (丨) is a residue of a compound having hydrazine or two or more active hydrogens, and one or two of the residues are bonded to the residue ( a polyalkylene glycol chain, and a terminal oxygen atom at the other end of the (poly)alkylene glycol chain is bonded to a hypophosphite (salt) via an organic residue, and the organic residue is bonded to the disc atom a carbon bond. In this case, the 201240937 structure of the non-multi-branched (linear) structure of a phosphorus-containing (poly)alkylene glycol compound is one of the following: (丨) with i or 2 The residue of more than one active hydrogen compound is bonded to a (poly)alkylene glycol chain, and the phosphorus-containing (poly)alkylene glycol compound is a residue of a compound having i 2 or more active hydrogens. a structure in which the base is located at the end of the structure of the (poly)alkylene glycol compound having a phosphorus atom; (2) a residue of a compound having two or more active hydrogens bonded to two (poly)alkylene glycols a chain, the phosphorus-containing (poly)alkylene glycol compound having 1 or more active hydrogens The structure in which the residue of the compound is located between two (poly)alkylene glycol chains. The non-multibranched (linear) structure of the above-mentioned (1)-containing (poly)alkylene glycol compound Preferably, the structure having one (poly)alkylene glycol chain bonded to a residue having one active hydrogen compound is further a structure of the above (2), and the non-occasion branch (linear) structure The (poly)-extended diol-based compound containing a phosphorus atom is preferably one in which a residue having two active hydrogen compounds is bonded to two (poly)-extension diol chains. The (poly)alkylene glycol-based compound containing a phosphorus atom has a structure in which X in the above formula (丨) is a residue having three or more active hydrogen compounds' at the residue bond. There are more than three (poly)alkylene glycol chains, and the oxygen atom at the other end of the (poly)alkylene glycol chain is bonded to the hypophosphite (salt) via the organic residue, and the organic residue The group is bonded to the phosphorus atom by a phosphorus-carbon bond. Further, the above-mentioned multi-branched (poly)alkylene glycol compound having a phosphorus atom has a multi-branched structure, and as described above, the so-called multi-branched structure means having 3 乂/tongue! The residue of the hydrogen-generating compound is branched into a radiation-like structure as a base point. That is, it means a structure in which a residue having three or more active λ. 15 201240937 hydrogen compounds is used as a base point, and then a bond is condensed from a base point via a (poly) diol chain and an organic residue. Phosphorous acid (salt), and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond. The polymer produced by using such a multi-branched (poly)alkylene glycol compound containing a phosphorus atom is capable of rapidly improving the performance of dispersing cement particles due to the steric repulsion caused by the multi-branched structure and is preferably improved. Used as a cement admixture. In the above formula (1), when m is 1 or 2, the (poly)alkylene glycol compound having a phosphorus atom is a non-multi-branched structure, and when the claw is 3 or more, it becomes a multi-point. Branch structure. The preferred number of m is different depending on the use of the (poly)-extended diol-based compound containing a dish atom, etc., and the atom-filled (poly)-alkylene-based compound of the present invention is used for the production of cement. In the case of a chain transfer agent in the case of a polymer used in the use of a mixture, it is more preferably 3 or more for the above reasons. More preferably, it is 4 or more, More preferably, it is 5 or more. In addition, the 'm car is better than 5 inches. More preferably, it is preferably 10 or less. When the above compound having an active nitrogen is used for the production of a (poly)stretched di(tetra) compound having a multi-branched structure, the active hydrogen number of the compound having active hydrogen is 3 Further, it is preferably 5 or less in terms of polymerizability. r The lower limit of the above active hydrogen number is preferably 4, 吏/f goes to the rabbit <; you! The upper limit of the 'and' is preferably 20, and more preferably 10.斤: The residue of the above-mentioned compound having active hydrogen means a structure having a structure for removing active hydrogen from a gas-containing δ, and the activity C·16 201240937 虱 means addition of an alkylene oxide. hydrogen. _ ^ compound of two or more active hydrogens (iv) gI, specifically, for example, preferably having an alcohol residue from an active hydrogen structure of a hydroxyl group of a georgite* alcohol, having a self-molecular limb The amine residue of the structure in which the active oxime is removed from the amine group, and the imine residue having the structure of the imine group of the imine quinone imine, which is derived from the structure of the oxime, is present as -X. A stearic amine residue having a structure in which an active hydrogen is removed from a hydrazine group of a monohydric or polyhydrazide compound. Among them, preferred are amine residues, imine residues and alcohol residues. Thereby, a compound suitable for various uses can be produced. Further, the form of the residue of the compound having active hydrogen may be any one of a structure which is crosslinked into a chain, a branch, or a three-dimensional structure. In a preferred embodiment of the residue of the compound having active hydrogen, the polyamine (polyamine) X is preferably a compound having an average of three or more amine groups in the i molecule, and is preferably, for example, conventional. A homopolymer or a copolymer obtained by polymerizing one or more of the following monoamine compounds, wherein the monoamine compound is methylamine, ethylamine, propylamine, butylamine, 2- Ethyl butylamine, octylamine, didecylamine, dipropylamine, dimethylethanolamine, dibutylamine, tridecylamine, triethylamine, cyclobutylamine, cyclohexylamine, laurel An amine such as a mercaptoamine; a mercaptoamine such as an allylamine; an aromatic amine such as a benzene fee 'monoamine; a nitrogen compound such as ammonia, gland or thiourea. The polyamine residue of the above (poly)alkylene glycol compound containing a phosphorus atom is formed by such a compound. Further, it may also be an ethyl diamine, a diethylidene diamine, a tri-ethylidene tetraamine, a tetraethylidene pentamine, a penta-ethylhexamine, a di-propyltriamine, a tri-propyl propyl group. Tetraamine, tetra-propyl pentamine, etc., in the poly-201204937 amine, usually having a tertiary amine group or a secondary amine group (imine) containing an active gas atom in addition to a tertiary amine group in the structure. base). Among these, it is preferred to use a polyalkylamine to form an alkylamine of a polyalkylamine, preferably an alkylamine having 8 to 18 carbon atoms such as laurylamine. Further, the polyalkyleneimine may be a compound having an average of three or more imine groups in the ruthenium molecule, and for example, it is preferred to carry out ethyleneimine, propyleneimide, 1, by a conventional method. 2—Anythracene or a mixture of two or more carbons having 2 to 8 carbon atoms such as butyl imidate, 2, 3 butyl imidate and 1,1-dimethylexidine is obtained by polymerization. Homopolymer or copolymer, and the like. The polyalkyleneimine residue of the above (poly)alkylene glycol-based compound containing a phosphorus atom is formed by such a compound. Further, the polyalkylenimine is crosslinked into a three-dimensional structure by polymerization, and usually has a primary amine group or a secondary amine group (imino group) having an active hydrogen atom in addition to the tertiary amino group in the structure. Among these, from the viewpoint of the performance of the polymer produced by using the above (poly)alkylene glycol compound containing a phosphorus atom, it is more preferred to be a polyalkylenimine in which the ethyleneimine is the main component. . The term "subject" in this case means that when the polyalkylenimine is formed of two or more kinds of imidazoles, the majority of all the alkylenes are present. In the present invention, in the alkyleneimine which forms a polyalkylenimine chain, most of them are ethyleneimine, whereby the following effects can be sufficiently exerted: the above-mentioned phosphorus-containing atom (poly) The hydrophilicity of the alkylene glycol-based compound is improved, and the character produced by using the (poly)alkylene glycol-based compound containing a phosphorus atom becomes suitable for a large amount of it's The degree of use of ethiethylene as the form & a 6-imine bond (polyurethane 18 201240937 imine residue) of the appearance of imine, and the above-mentioned stomach "occupies the majority =" one. It is preferably 50 to 1% of the moles of all the moles of the ethylenimine in the total of 16% of the moles. If the molybdenum is not reached, the hydrophilicity of the polyalkyleneimine chain becomes insufficient, and it is preferably more than 70 mol%, and more preferably 8 mol% or more. Take better than 9% of the moles. The average number of polymerizations of the imidazole of each of the above-mentioned polyalkylene imino chains is preferably 300 or less. By setting it as such a range, the effect by the structure of the above-mentioned phosphorus-containing (poly)-expanding compound can be more fully exhibited. For example, the compound (tetra) compound can be suitably used. Special purpose cement cements that exhibit excellent cement dispersion properties. The lower limit is more than 3, and more preferably 5, and more preferably ι. Further, the upper limit value is more preferably 200' and further preferably 1 Å, more preferably 5 Å, most preferably 25 Å, and the average polymerization number of the ethylidene diamine is 2, and the triamethylenetetramine The average number of aggregates is 3. The number average molecular weight of the above polyamine and the polyamine is preferably from (10) to 100,000', more preferably from 300 to 50%, still more preferably from about 1 to about 1, and particularly preferably from 800 to 5,000. The above-mentioned polyol is preferably a compound composed of three elements of carbon, hydrogen and oxygen as long as it is a compound having an average of three or more groups in the i molecule. Specifically, for example, polyglycidol, glycerin, polyglycerin, trimethylethane, trimethylolpropane, ...-pentanetriol, erythritol, neopentyl alcohol, dipentaerythritol, etc. are preferred. Alcohol, sorbitol, sorbitan, sorbitol glycerol condensate, flavonol, arabitol, xylitol, 201240937 mannitol, and the like. Further, the saccharide is preferably a hexose such as glucose, fructose, mannose, idose, sorbose, gulose, talose, tagatose, galactose, alo [ lolone], aldose Sugars; sugars of pentoses such as arabinose, ribose, ribose, xylose, xylulose, and threose; sugars of butyose such as threose, erythrokose, and erythroglucose; rhamnose , other maltose, sea sugar, recommended sugar, raffinose, sugar, and other sugars; such sugar alcohols, sugar acids (saccharides: glucose; sugar alcohol: glucose alcohol; sugar acid: gluconic acid). Further, a derivative such as a partial ether compound or a partial ester compound of the above-exemplified compounds is also preferred. The polyol residue of the above-mentioned (poly)-extended 9-diol compound containing a scaly atom is formed by such a compound. Among them, dimethylolpropane or sorbitol is more preferable from the viewpoint of industrial production efficiency. The number of the (poly)-extension diol chain bonded to the compound having three or more active hydrogens is preferably equal to the number of active gases in the compound having three or more active nitrogens. Namely, it is preferred that all of the active hydrogen atoms in the compound having the above-mentioned active oxime of 3 M are bonded to a (poly)/alcohol chain. By using a stilbene alcohol-based compound having a phosphorus atom of such a structure to produce a polymer, it is possible to provide a cement admixture capable of exhibiting more excellent dispersibility. Here, 'the number of the above-mentioned (poly)alkylene glycol chains bonded to the above-mentioned cerium having three or more active hydrogens is equivalent to the active hydrogen in the compound having three or more active hydrogens. The structure of the number case can be expressed as follows. Ο 20 201240937 The formula (A) schematically indicates that a compound having three or more reactive nitrogen compounds has a residue in the structure of the structure, and the glycerol residue is a glycerol residue. All of the active hydrogens are bonded to the sub-phosphorus (salt) via the organic residue, 'σ (D), and the following formula (Β) is a model surface. There are three or more lower structures, the structural alcohol residue), and several: the residue of the dimer is a sorbitol residue (polyphosphate (salt) linkage. Further, in the following formula (A ), (b) zhongyi 乂 P represents a hypophosphite (salt) residue.

In the poor phosphorus-containing primary alcohol chain and through the organic shirt (tetra) alcohol active hydrogen bonding (poly) extension II, μ, τ ^ 兀 - 哔糸 compound is a compound with more than two active argon residues The case where the group is bonded (poly) to the alkylene glycol chain and is bonded to the hypophosphorous acid via the organic residue, and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond. Residue bonding of a compound having two or more active gases in addition to a (poly)alkylene glycol chain bonded to a sub-squaric acid (salt) via a residue (poly) 201240937 Alcohol chain. The terminal of the (poly)alkylene glycol chain (end of the side opposite to the residue of the compound having two or more active hydrogens) is preferably, for example, a 'valent metal atom' bonded to a hydrogen atom. A structure of an atom, an ammonium group, an organic amine group, a hydrocarbon group having 1 to 30 carbon atoms, an oxohydrocarbyl group, a mercaptohydrocarbyl group, a carboxyhydrocarbyl group, a carbon number of 3030, or the like (hydrocarbon) group, etc. When there are two or more (poly)alkylene glycol chains in one molecule, the terminal structures may be the same or different. Among such terminal structures, in terms of versatility, it is preferably a structure bonded to a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrocarbon group bonded to a hydrogen atom or a carbon number of 1 to 1 fluorene. The structure is preferably an alkyl group or an alkyl group or an alkenyl group in the hydrocarbon group having 1 to 碳. That is, for example, the (poly)alkylene glycol compound containing a phosphorus atom of the present invention may be of the following formula (2): Ο X- ~ < AO) n - Y - P - Y2 jm OM (2) 1 (ΑΟ>η, a γ3—Q jp (wherein 'again, 八0, 丫1, 1^[, 丫2, 111, and 11 are the same as general formula (1). Y3 is the same or different, indicating direct bonding Or an organic residue. Q is the same or different and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. η' is the same or different, and represents an average addition of an alkyl group to an alkyl group. The compound represented by the number of 1 to i. The number of ρ is 1 or more. The organic residue in Y of the above formula (2) is the same as γ! 22 201240937. The maximum number of hydrogen atoms is determined by the number of hydrogen produced by the & The effect of the (poly)alkylene glycol chain (salt) is preferably such that p is [(all active hydrogen numbers of compounds having 2 or more active hydrogens) - 2] or less, so that More than one The number of the (poly)alkylene glycol chain to which the compound of the hydrogen is bonded is 2 or more. 〇 Consider the operation of the (poly)alkylene glycol compound containing a phosphorus atom of the present invention! When the polymer produced by the compound is used for the viscosity of the cement composition in the case of cement mixing and the like, the average weight of the compound/knife (Mw) is preferably 500,000 or less, more preferably 30,000. In the following, it is more preferably 10,000 or less, and particularly preferably 50,000 or less, and most preferably 30,000 or less. In addition, when it is used in the case of a cement admixture, the dispersibility is increased to a certain extent. Mwfe is preferably (10) or more, more preferably 3 Å or more, further preferably 5 Å or more, and particularly preferably more or more, and most preferably 2,000 or more. Further, the number average molecular weight (?η) is preferably 5 〇. More preferably 10,000 or less, more preferably 30,000 or less, further preferably 1 10,000 or less, particularly preferably 50,000 or less, and most preferably 30,000 or less. Further, preferably 1 Torr or more. More preferably, it is more than Preferably, it is 500 or more, especially preferably _ or more, and the best is 诵 or more. Furthermore, the weight average molecular weight of the compound The amount and the number average molecular weight can be determined by a gel permeation chromatography (GPC) analysis method described later. The disc atom-containing (poly) exfoliating diol-based compound of the present invention has 23 201240937 derived from hypophosphorous acid ( The structure of the salt) is thus used as a chain transfer agent for radical polymerization, and can be preferably used in the production of various polymers using a radical polymerization reaction, in particular, by using the present invention. The (poly)-extended diol-based compound of a phosphorus atom is used as a chain transfer agent to radically polymerize an acetyl group-based monomer component. It is easy and efficient to produce cement dispersibility (water-reducing) or enthalpy at low cost. It is excellent in retainability and can be preferably used as a polymer of a cement admixture. Such a chain transfer agent containing a (poly)alkylene glycol-based compound containing a phosphorus atom of the present invention is also one of the inventions. Further, the polymer produced by using the chain transfer agent of the present invention is also one of the inventions. <Production method of (poly)alkylene glycol-based compound containing phosphorus atom> The (poly)-alkylene glycol compound of the phosphorus atom of the present invention is preferably a sub-sub-acid (salt) The addition is carried out by a compound having a structure in which a terminal oxygen atom of a (poly)-extended diol chain is bonded to an organic residue having a carbon 1 double bond, and such a process is also one of the inventions. The method for producing a (poly)alkylene-based compound containing a phosphorus atom is also a method for producing a three-filled (poly)-extended diol-based compound, and comprises the following Formula (3): X-KAOWv^ 1 Jm (3) (wherein, X represents a residue of a compound having an active hydrogen or a hydrogen atom. AO is the same or different, and is -. ^ is not a slave 2 to 18 oxygen Base alkyl group. γ4 is the same or 24 201240937, different, indicating the residue of a compound having a carbon-carbon double bond. n is the same or different, and the average addition mole number of the alkyl group is ι~ι〇〇 The number of 〇 。 m m m ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” Specific examples of the oxyalkylene group represented by A〇 are preferably the same as those of the above-mentioned (poly)alkylene glycol chain (pAG) having a carbon number of 2 to 18, in the above formula (3) Then, it is the same as X in the above formula (1). The compound containing the (poly)alkylene glycol chain represented by the above formula (3) (hereinafter also referred to as compound A) In the above formula (3), in the case where the melon is a compound, the compound A may be an unsaturated (poly)alkylene glycol compound represented by the following formula (5). (b) such a form of evil is one of the preferred embodiments of the present invention. In the above formula (3), when m is 2 or more, the above-mentioned chemical & A is also made unsaturated The compound of the group is synthesized by adding a polyalkylene oxide obtained by adding an alkylene oxide to a compound having two or more active hydrogens. In the form of addition, esterification, etherification, amide or the like can be used. The method of a 4. The unsaturated compound to be added may be added to a polyepoxy group. For example, in the case of acetification, 'preferably a compound having an unsaturated group and a carboxyl group' may preferably be used. The unsaturated carboxylic acid monomer (a) represented by the following formula (4) is used. The compound having an unsaturated group in the synthesis of the above compound A is etherified in the form of addition to the compound. In the case, it is preferred to use chlorine 25 201240937: dilute, (meth)allyl chloride, chlorine - 3—mercapto- 2—butene, 1-chloro 3, methyl-3-butane, 3-chloro-3-methyl-1-, fast, chloroprene I:: odorized propylene, iodine Halogen-containing unsaturated compound such as alkene, 'ethylene dioxypropyl sulphate, (γ-based) propyl propyl epoxy fluorene, (meth) acrylic acid ring: propyl, (meth) acrylic acid基 炫 醋 醋 环氧 环氧 环氧 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧The method for producing a (poly)alkylene glycol-based compound containing a phosphorus atom can be preferably used. The method for producing the above-mentioned compound A and sub-squaric acid (salt) is only 匕3. The stepper' can also include other steps. In the above formula (3), when X is an IT form of a residue of a compound having an active hydrogen, the above compound A can be obtained by adding a residue structure represented by Y4 at the terminal of the (8) alkylene glycol. The compound is synthesized by addition to a method of active hydrogen. In this case, it is preferred to use an acid catalyst or a basic catalyst. The acid catalyst is preferably a metal and a semi-metal tooth of a Lewis acid catalyst such as boron trifluoride, an inorganic acid such as an evolved hydrogen, an evolved hydrogen or a sulfuric acid, or a toluene-based acid; It is hydrogen hydroxide, sodium hydroxide and sodium nitride. The reaction time of the above addition reaction may be appropriately set depending on the kind or amount of the catalyst to be used, the solution concentration, and the like. In the above formula (3), the residue of the compound having a carbon-carbon double bond of Y4 may, for example, be a linear, branched or cyclic alkene having 2 to 30 carbon atoms.

26 201240937 Ke et al. Such groups may, for example, be argon amine groups (phenyl, alkylphenyl, phenyl, thienyl, pyrrolyl, yl, decyl, etc.) having a carbon number of 6 to 3 G. Partially substituted with a substituent such as an amine group, an aryl group, a aryl group, a aryl group, a dentate group, a fluorenyl group, a nitro group, and a mercapto group. Among these, it is more preferably a linear or branched alkenyl group having a carbon number of 2 to 18 and a part of the alkyl group substituted by a hydroxyl group, and more preferably a linear or branched carbon number of 2 to 8. Branched alkenyl groups and one of these parts are substituted by a hydroxy group. The step of subjecting the above-mentioned compound A to the hypophosphorous acid (salt) to be subjected to an addition reaction may be carried out by using a radical polymerization initiator in the form of a solution dissolved in a solvent. The solvent to be used at this time may, for example, be water; alcohol such as methanol, λ ethanol or isopropanol; benzene, toluene, ..., cyclohexane, hexamethylene or aliphatic hydrocarbon; vinegar such as ethyl acetate; A compound; a propionate, a methyl ethyl ketone compound; a tetrahydroanthracene, a diterpene, etc., a ring-shaped compound, etc., preferably using water as a solvent. In the case where the above-mentioned compound A and hypophosphorous acid (salt) are subjected to an addition reaction step using water in a solvent, the case of using a water-soluble radical polymerization initiator is not required to remove insoluble components after the reaction. J can be cited as persulfate such as ammonium persulfate, sodium persulfate or potassium persulfate: pervaporated hydrogen; organic peroxide such as t-butyl hydroperoxide; 2, 2, : azobis-2 An arsenazo compound such as methyl propyl hydrazine hydrochloride, 2, 2, ~ even = 2 ~ (2 - imidazolin-2-yl) propane hydrochloride, etc. Azo nitrile compound such as mercapto azoisobutyronitrile, 2,4, mono- and {2-methyl-N-[2-mono(hydroxybutyl)]propanamine} , 4,4'-azobis(4-cyanovaleric acid) and (alkoxy) poly(ethylene oxide) 27 201240937 Alcoholic azo-based initiators such as alcoholic auxin; One or two or more of these. Among them, a persulfate-based initiator is preferred. The amount of the radical polymerization initiator to be used may be appropriately determined according to the state or amount of the (poly)thro-glycol-based compound or the vinyl-based monomer component containing a phosphorus atom. When the polymerization initiator is too small with respect to the ethylene-based monomer component to be polymerized, the radical concentration is too low to slow the polymerization reaction, and if too large, the radical concentration is too high. The polymerization reaction from the monomer component of the ethylenic base is prioritized over the s/reaction caused by the phosphorus atom, and the yield of the atom-filled (poly)throic diol-based polymer of the present invention cannot be improved. Therefore, the amount of the radical polymerization initiator to be used is 100 moles per mole of the vinyl monomer component, preferably more than moles, more preferably 0 to 01 moles, and still more preferably 01 moles.上上佳佳为〇·2 moles or more, and more preferably 1 mole or more, preferably 5 moles or more, and preferably 5 〇 or less, more preferably 莫 乂 进而It is 1 〇 or less, and more preferably 5 mA or less, and particularly preferably 2 mA or less, and most preferably 丨 Moel or less. : in the step of adding a reaction of a long-term phosphorous acid (salt) with the above-mentioned compound A, it is preferred to add a sub-subscale to the unsaturated bond i mole contained in the compound A at a ratio of 0.1 to 100 moles. The acid (salt) is reacted. From the viewpoint of increasing the reaction rate of the above compound A, the linoreic acid (salt) is preferably 0:1 or more with respect to i: the compound A of the ear, and it is more preferably From the viewpoint of 0.5 mol or more and less anti-red salt, it is preferably 10 mol or less, more preferably 5 m or less, relative to 1 mol of the compound A. 28 201240937 and more preferably 2 moles or less.步骤 The step of the addition reaction of the hydrazine A is preferably 〇~20 (the temperature of the rc is π and then the enthalpy is introduced. More preferably, it is carried out at 20 to 150 ° C, and then preferably the rabbit l2 It is carried out at a temperature of 〇t:, more preferably at a temperature of 50 to 100 ° C. After the hypophosphite (salt) and the above step, it is preferred to make the obtained ruthenium-containing addition reaction Purification step: the purification step can be carried out by removing the solvent from the solvent and drying it in the purification solvent to remove any of the methods of suspending and suspending, and extracting, or both For the purification solvent, the chloroform, the isopropyl alcohol, and the like may be appropriately prepared. For example, it is preferred to avoid, and the extraction solvent may be appropriately selected, and it is preferred to use hydrazine or the like as a highly polar solvent. Extraction. It is preferred to use a two-extraction/coating, gas-like, two-gas-fired or the like as a low-polar solvent to carry out a <phosphorus-containing (poly)alkylene glycol-based polymer> :: Phosphorus atomic (poly) extender diol-based polymer has the following, 'constructor, the structure (poly) stretch At least the terminal oxygen atom of the diol chain (PAG) is bonded to the sub- succinic acid (salt) (SHP) via the organic residue (Y), and the organic residue and the phosphorus atom are bonded by a phosphorus-carbon bond. Further, the disc atom is bonded to a polymer containing a vinyl monomer unit. When it has at least one such structure, it may have another structure. The same may be the same as 29 201240937. It is understood that the polymer containing the vinyl soap cell unit refers to the formation of ethylene A, which must be contacted with two of the vinyl groups of the king's g-alkenyl precursor. A polymer bond formed by continuously bonding a carbon atom to a carbon atom of an adjacent vinyl monomer. Hereinafter, the phosphorus-containing propylene-based polymer of the present invention having the following structure is also referred to as "polymerization." (1)", the structure is = diol chain (PAG, ten s I 丄 ^ A condition ^ one end of the oxygen atom via the organic residue 2) and the sub-Asia (tetra) (salt) (SHp) 嶙 atom bonding And having _I, a phosphorus atom bonded by a phosphorus-carbon bond, and the phosphorus atom is bonded to a polymer containing a vinyl monomer unit The primary bond; also contains the B-containing squamous atom: the polymer of the base monomer unit is called "polymer (8)". "Eye" also polymerizes the phosphorus atom-containing (poly) propylene glycol system of the present invention. The polymer is a phosphorus-containing PAG polymer. The polymer containing a vinyl-based monomer unit (polymer-based vinyl monomer component, preferably containing an unsaturated carboxylic acid-vinyl group monomer unit) It is necessary to contain unsaturated carboxylic acid, which can improve the hydrophilicity of the polymer, and can be made into various useful people. In the case of use in cement mixing agents, etc., it is further improved. The above-mentioned ethylene (tetra)-based monomer component preferably contains an unsaturated (poly)-terminated diol-based monomer, especially when the (8)-alkylene glycol-based compound containing a filler atom has a multi-branched structure. The steric repulsion of the (poly) stretch-alcohol chain derived from the multi-knife branch, the steric repulsion of the '= structure, which is derived from the unsaturated (poly) stretching diol monomer, can be considered as the effect of complementing each other. The performance of dispersing cement particles is drastically improved. Better for

30 C 201240937 The vinyl precursor is a form containing an unsaturated carboxylic acid monomer (a) and an unsaturated (poly)alkylene glycol monomer (b). ^ The above unsaturated carboxylic acid monomer (a) (hereinafter also referred to simply as "monomer (a)") is preferably, for example, the following formula (4): R\ /R, (4) r3 coom1 (wherein R, R and r are the same or different and represent a hydrogen atom, a methyl group or (CH2)xC00M2. Further, _(CH2)xCOOM2 may form an anhydrate with "c〇〇Ml or another one (ch2)xcoom2. x is 〇 An integer of ～2.... and M2 are the same or different and represent a compound represented by a hydrogen atom, a monovalent metal, a divalent metal, a trivalent metal, a quaternary ammonium salt or an organic amine salt. In addition, the structural unit derived from the monomer (a) corresponds to a structure in which a polymerizable double bond of a monomer represented by the general formula (4) is opened by a polymerization reaction (double bond (C=C) Become a single bond (-C-c-) structure). In the above formula (4), the metal atom represented by 'M1 and M2' may, for example, be a monovalent metal atom such as an alkali metal atom such as lithium, sodium or potassium; and calcium, money·# soil-based metal atom a metal atom; a trivalent metal atom such as a neon or a ruthenium. Further, examples of the organic amine salt group include an alkanolamine group such as an ethanolamine group or a diethanolamine group 'triethanolamine group, or a triethylamine group. Specific examples of the unsaturated acid monomer represented by the above formula (4) include, for example, a mono-reactive acid monomer such as acrylic acid, methyl acetoacetate or butyric acid; maleic acid; a diacid acid monomer such as methyl succinic acid or fumaric acid; an anhydride or a salt of the carboxylic acid (for example, an alkali metal salt, an alkaline earth metal salt, a trivalent metal salt, an ammonium salt, an organic amine salt) )Wait. Among them, from the viewpoint of the polymerization λ 31 201240937, acrylic acid, f-based acrylic acid, maleic anhydride, and the like are preferable, and acrylic acid or the like is more preferable. The maleic acid, the methylpropionic acid, and the above unsaturated (poly)alkylene glycol monomer (b) (hereinafter also simply referred to as "monomer (b)") are preferably, for example, the following formula ( 5):

\(CH2)y(CO)z (5) '0—(AO)r-~R7 ? (wherein R4, R5& R6 are the same or different and represent a hydrogen atom or a methyl group. R7 represents a hydrogen atom or a carbon number. a hydrocarbon group of 20, which is the same or different, and which has one or two or more kinds of oxyalkylene groups having 2 to 18 carbon atoms. Further, when two or more kinds of oxyalkylene groups represented by A〇 are present, The group may be introduced in a blocking manner or may be introduced in a random manner. 丫 is an integer of 〇~2. z is 〇 or represents the average addition molar number of the alkyloxy group, which is represented by the number ι~3〇〇) Compound. In addition, the structural unit derived from the monomer (b) corresponds to a structure in which a polymerizable double bond of the monomer (b) represented by the formula (5) is opened by a polymerization reaction (double bond (C) = C) becomes the structure of a single key (—C _ c —). In the above formula (5), among the terminal groups represented by R7, the ketone group having a carbon number of 1 to 20 may be exemplified by an aliphatic alkyl group having a carbon number of i to 2 Å and an alicyclic ring having a carbon number of 3 to 20. a calcined base, an alkenyl group having 2 to 2 carbon atoms, an alkynyl group having 2 to 2 carbon atoms, an aryl group having 6 to 20 carbon atoms, etc.

32 201240937 The end group shown in the opening is preferably a hydrophilic group from the viewpoint of dispersibility of the cement particles, and is a hydrocarbon group having a gas atom of 1 to 8. More preferably, it is a hydrocarbon group of a hydrogen atom or a slave, and further preferably a hydrogen atom or a hydrocarbon group of carbon number 3, and particularly preferably a hydrogen atom or a mercapto group. Further, in the above formula (5), fA〇) "is not shown (poly) extended diol:: by: the number 2 of the oxygen extending ethyl (epoxy phantom), obtained 4 The hydrophilicity of the polymer becomes sufficient, and the cement mixture using the t σ substance is given the end point ^ At the thief, the water solubility of the razor and the dispersion property of the cement particles. The so-called "main" means The moles of all of the oxygen-forming groups (extension diol units) of the (poly) diol group in the 1 (10) mole % are preferably expressed as 5 〇 1 to 1 〇〇. If it is not reached, the hydrophilicity of the oxy (tetra) group becomes insufficient and the dispersion property of the cement particles is not sufficiently obtained. More preferably, it is 60 mol% or more, and = 0.00 is mol%. The above is especially good for 8 〇mol%, 90 mol% or more. The (poly)-expressed diol chain is not included in one part: it contains more hydrophobic The oxygen base of 3 or more is extended to the base. The reason is that the right hydrophobic group is introduced into the cement mixture (dispersant) and is used in the aqueous solution (poly). The extended diol chains show a slight hydrophobic interaction with each other 'by adjusting the viscosity of the cement composition and modifying the operation (4). When the oxy group is extended to a carbon number of 3 or more, the relative 100 mol% of all the oxygen-extension groups (extension 33 201240937 alkanediol unit) constituting the (poly)-extended diol chain, preferably 50 mol% or less in order to ensure sufficient water solubility. More preferably 25 More preferably, it is preferably 10 mol% or less. Further, in order to improve workability, it is preferably 丨 mol% or more, more preferably 2.5 mol% or more, still more preferably 5 mol% or more. The above alkyl group having a carbon number of 3 or more has an alkyl group, and is preferably an oxypropylene group and a butylene oxide group, and more preferably an oxypropylene group, more preferably an oxyalkylene group. When the monohydric alcohol chain is composed of an oxygen-extended ethyl group having a carbon number of 2 and an alkyloxy group having a carbon number of 3 or more, the arrangement may be random or blocked, and if it is blocked, Then, compared with the random arrangement, the hydrophilic barrier shows a stronger hydrophilicity. The hydrophobic barrier shows more The strong hydrophobicity is further improved as a result of further improving the dispersibility or handleability of the cement composition, and more preferably, such as (oxyl ethyl group having a carbon number of 2) - (oxyalkylene having a carbon number of 3 or more) The carbon number of 2 is extended to the group A-B-A. In the above formula (5), the number of r is 1 to 3, and if it exceeds 3, it is produced. In the case of a bad condition, when the cement composition is used as a cement admixture, the viscosity of the cement composition becomes high and the workability becomes insufficient. From the viewpoint of production, §, r is preferably 300 or less, preferably. It is 2 Torr or less, more preferably 150 or less, further preferably 100 or less, particularly preferably 75 or less, and most preferably 50 or less. Further, in terms of sufficiently dispersing the cement particles, ^ is preferably 4 the above. More preferably, it is 6 or more, further preferably 丨〇 or more, and particularly preferably 25 or more. The unsaturated (poly)alkylene glycol monomer represented by the above formula (5) is exemplified by 34, 2012, 937, and the specific examples, for example, an unsaturated alcohol (poly)alkylene glycol adduct, (poly)alkylene Alcohol ester monomer. The above unsaturated alcohol (poly) extendable diol adduct may be a compound having a structure in which a (poly) extender diol chain is added to an alcohol having an unsaturated group. The alcohol ester monomer may be a monomer having a structure in which an unsaturated group and a (poly)alkylene glycol chain are bonded via an ester bond, and preferably an unsaturated carboxylic acid (poly)alkylene glycol vinegar A compound in which (alkoxy) (poly)alkylene glycol mono(meth)acrylate is preferred. The above unsaturated alcohol (poly) extender diol adduct is, for example, preferably an ethyl bake alcohol epoxy compound adduct, a (methyl) fuchsyl alcohol epoxy burn adduct, or a 3-butanol-alcohol Epoxy-fired adduct, 3-methyl- 3 butyl steep., T-based 3-butene-anthracene alcohol alkylene oxide addition 3 methyl 2~ butene-alcohol alkylene oxide adduct, 2 —Methyl-3'-butene-2-alcohol Epoxyalkylene and human Ming 1 methyl-2-butene-1-one-enoxygenate adduct, 2-methylpyrazine q ^ ^ ± methyl- 3 - Butene mono-alcohol alkylene oxide adduct. "Hai 4, preferably epoxy, and the milk knife becomes the form of ethylene oxide. The above unsaturated alcohol (poly) secondary pull _ good) alkylene-known adduct, in particular, for example: for the polyethylene glycol monoethyl amide, the polyethylene alloy (2 -曱 〜 ~ 早 烯 allyl ether, poly fluorenyl (5), poly stretched B: alcohol single two =): poly-ethylene glycol mono (2-butanediol single (3-methyl 1-2 butyl) 1 Butenyl)ether, poly(ethylene bromide) ether, polyethylene glycol mono(2-butenyl) ether, polyethylidene ethylene glycol (1,1-12 Methyl-butenyl)ether, polydiethylene glycol mono(3-methyl-3-trione), poly(ethylene glycol)-butenyl)ether, methoxypolyethylene-2 Alcohol mono (3 35 201240937 - methyl 3- 3 -butenyl) ether, ethoxy- butyl W. gas-based polyglycol ethylene glycol mono (3-methyl-3 butenyl) ether '1- - C Oxypoly-extension Ethylene, Yuping-Methyl-3, Dingsongji) shouting, cyclohexyloxy-polyethylene glycol monopoly lean$β goods T^ — 3 — butenyl) ether, oxy-poly Ethylene glycol monoglycol (3-methyl- 匕-妒-咕二#丁席基), T-oxylate-extension B-% early allyl ether 'ethoxy group Alcohol mono-propyl propylene, loaded with negative-based polyglycol ethylene monoallyl ether, A Teach Oxygen T-rolled polyglycol monoglycol (2 - comparable to 2-propenyl) ether, ethoxylated Ethylene diethylene ether, phenoxy-polyethylene glycol mono(2-methylmethanyl-2-propenyl)methyl-2-propenyl ether, etc. The above (alkoxy) (poly) extension Alkanediol mono (,, ^ 砰 early (7-base) acrylate, such as 鲛 为 于 于 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇The base (poly) oxime diol, especially the epoxy (poly)alkylene glycol and (meth)acrylic acid vinegar. The above alcohols, for example, methanol, ethanol , propanol, 1-butanol, 2-butanol, 1-pentanol 2-pentanol, 3-pentanol, alcohol, 2-hexanol, 3-hexanol, octanol, 2-ethyl -1 - hexanol, lauryl alcohol, whale glycerol, stearyl alcohol, etc., carbon number Μ. of aliphatic alcohols, % of yeast and other alicyclic alcohols with a carbon number of 3 to 3 ;; Butene - alcohol methyl - 3 - butyl sterol - carbon number 30 And the above-mentioned acetate, specifically, preferably shown below (the appearance of oxyethylene (5) (carbon number 2 to 4, propylene glycol) (fluorenyl) acrylic acid Polyethylene glycol mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol} mono (indenyl) acrylate, methoxy {polyethylene (poly) stretched two Alcohol}mono (meth)acrylic acid vinegar, methoxy {polyethylene glycol (poly) 36 201240937 propylene glycol (poly) butanediol} mono (indenyl) acrylate, ethoxylated polyethylene glycol Mono(indenyl) acrylate, ethoxy {polyethylene glycol (poly) propylene glycol} mono (indenyl) acrylate, ethoxy {polyethylene glycol (poly) butyl butyl hydride ( Acrylate, ethoxylate {polyethylene glycol (poly) propylene glycol (poly) butanediol} mono (meth) acrylate, propoxy polyethylene glycol mono (meth) acrylate Ester, propoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, propoxy {polyethylene glycol (poly) butane diol} mono (meth) acrylate, Propoxy {poly Ethylene glycol (poly) propylene glycol (poly) butyl butane diol mono (meth) acrylate, butoxy polyethylene glycol mono (indenyl) acrylate, butoxy oxime poly(ethylene glycol) Poly) propylene glycol} mono(meth)acrylic acid g, butoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, butoxy fluorene polyethylene (poly) ) propylene glycol (poly) butylene glycol mono(indenyl) acrylate, pentyloxy polyethylene glycol mono(meth) acrylate, pentyloxy {polyethylene glycol (poly) propylene glycol) Mono(indenyl)acrylate, pentyloxy{polyethylene glycol (poly)-tertylene glycol mono-(meth)acrylate, pentyloxy{polyethylene glycol (poly)-propylene glycol (poly) Butylene glycol} mono(indenyl) acrylate, hexyloxypolyethylene glycol mono(indenyl) acrylate, hexyl-based {poly(ethylene) (poly) propylene glycol} mono(indenyl) acrylate vinegar , hexyloxy {polyethylene glycol (poly), butanediol, mono (indenyl) acrylate, hexyloxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol (fluorenyl) acrylate, heptyloxypolyethylene glycol mono(methyl)propanate g, heptyloxy {polyethylene glycol (poly) propylene glycol} mono(indenyl) acrylate, heptoxy Base (polyethylene glycol (poly)) butanediol} mono (meth) acrylate, heptoxy oxime, polyethylene glycol (poly), propanol (poly), butyl alcohol, mono Acrylic acid, octyloxypolyethylene glycol mono(meth)acrylate, octyloxy {polyethylene glycol (poly) propylene glycol} single. 37 201240937 (fluorenyl) acrylate, octyl Base {polyethylene glycol (poly) butylene glycol} mono (indenyl) acrylate, octyloxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol] single (methyl) Acrylic vinegar, decyloxypolyethylene glycol mono(meth) acrylate, decyloxy {polyethylene glycol (poly) propylene glycol} mono (sub) acrylate, decyloxy {polyethylene Alcohol (poly) butanediol} mono (meth) acrylate vinegar, decyloxy (polyethylene glycol (poly) propylene glycol (poly) butyl propylene) mono (indenyl) acrylate. In the vinyl monomer component, the content of the unsaturated acid-based monomer (a) is preferably 丄% by mass or more, more preferably 2% by mass or more, based on all the monomer-based monomer components (10). It is preferable that it is preferably 99% by mass or less, and more preferably: % by mass or less, from the viewpoint of sufficiently exhibiting the performance of other vinyl-based precursors. Further, it is preferably 3% by mass or less, and most preferably 5% or less. In addition, the unsaturated (poly)alkylene glycol monomer (b can be appropriately adjusted according to the performance required for the 3), as long as it is based on the performance of the 4P, it is derived from the monomer ( b) More than ir? All of the maternal base monomer (10) mass. /,, preferably! Negative amount % or more, more preferably 2 〇 mass 4 〇 mass. /. Above, preferably 6 〇, and thus preferably From the viewpoint of the performance of other ethylene-based monomers, the second is more preferably 9% by mass or less, and further preferably 80% by mass or less. Further, in the above vinyl monomer component, : and _ monomer ") and not only (poly) glycerin; other copolymerizable monomers (to the factory (1) to the early morning Body (c)"). 38 201240937 In this case, the constituent unit of the polymer (1), the so-called -3 has the original self-escape early body U: Ιέ * take the person S", the constituent unit of the above monomer (c), the phase a# hunting by the hydration reaction When the single dirty phase is broadcasted, the polymerizable double bond of the body (C) is opened to form (double bond (C=C) becomes a single bond (-c is opened to use the above monomer (), The content of the alkenyl monomer component (10): is preferably 25 or less by mass based on all of B. The content is preferably 30% by mass or less. The lower portion is further preferably 20% by mass or less. 'A specific example of the above-mentioned monomer (e) can be used as the compound of the above-mentioned monomer, and the above-mentioned monomer (e) can be used, for example, the following compounds can be used. Two or more types. -Unsaturated dicarboxylic acid monomers such as maleic acid, maleic anhydride, fumaric acid, methylene buty-S夂 methyl maleic acid, and carbon atoms 23~30 alcohol half vinegar, double g purpose class; the above unsaturated: (4) is a single (four) carbon atomic number 23~30 amine heptylamine, diamines; make Bu (10) Mo a semi-ester or diester of an alkyl (poly)alkylene glycol obtained by adding an epoxy group of 2 to 18 to the above alcohol or amine and the above unsaturated dicarboxylic acid monomer. , the above-mentioned unsaturated dicarboxylic acid monomer and a diol having 5 to 18 carbon atoms or the addition of the diol to a half ester or a diester of a (poly)alkylene glycol having a molar number of 2 to 5 Å. a phthalic acid of maleic acid and a diol having 5 to 18 carbon atoms or an addition of the diol to a semipolyamine of a (poly)alkylene glycol having a molar number of 2 to 500; Di(indenyl)acrylate, (poly)ethylene glycol bis(indenyl) acrylate, propylene glycol di(decyl) acrylate, (poly)ethylene glycol (poly) propylene glycol di(decyl) Acrylate or the like (poly)alkylene glycol di(meth)acrylic acid 39 201240937 Ester; hexanediol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, trishydroxyl Polyfunctional (meth) acrylates such as propane di(meth) acrylate; triethylene glycol dimaleate, polyglycol dimaleic acid S, etc. Stretching diol di-butyl succinic acid sulphate; ethyl sulphate, (mercapto) allyl sulphonate, 2-(methyl) propyl decyl oxyethyl acid S 曰, 3- (Methyl) propylene oxide oxypropyl acid, 3 (meth) propylene oxime 2- 2 - hydroxypropyl sulfonate '3 - (meth) propylene oxy group 2 - phenyl group Base performance phenyl ether, 3-(indenyl)propenyloxy-2-hydroxypropyloxy benzoate, 4-(meth)acryloxybutyl sulfonate, (fluorenyl) An unsaturated sulfonic acid such as acrylamide methylsulfonate, (meth) acrylamide ethyl sulfonate, 2-methyl propyl methacrylate or styrene sulfonic acid; and the like a shell metal salt, a monovalent metal salt, a salt and an organic amine salt; an unsaturated monobasic acid such as methyl (mercapto) acrylamide and an amine of an amine having 1 to 30 carbon atoms; Styrene, α-methylstyrene, vinyl, and methyl aromatics; 1,4-butanediol mono(meth)acrylate, 1,5-pentanediol ( Methyl) acrylate, 丨"- Alkylene glycol mono(meth)acrylates such as mono(meth)acrylate; butadiene, isoprene, 2-methyl-1,3-butadiene, 2-gas-ι, 3 Diene such as butadiene; (fluorenyl) acrylamide, (fluorenyl) propylene alkyl decylamine, N-hydroxymethyl (meth) acrylamide, N, N-dimethyl (methyl) Unsaturated guanamines such as acrylamide, unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate; and mono(2-hydroxyethyl) phosphate ) methacrylate, diammonium [(2-hydroxyethyl) methacrylic acid] g, diammonium [(2-hydroxyethyl) decyl acrylate], mixtures thereof, etc. having 201240937 linonic acid a monomer having a sulfonic acid group, such as a monomer having a squary group (A) in the examples described later; a sulfonic acid group such as a potassium salt of a sulfopropyl (meth)acrylate; A 2-methyl group (meth)acrylic acid vinegar or the like having a transbasic (meth) acrylate. The weight average molecular weight of the (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention in consideration of workability or retention of a cement composition in the case where the polymer is used for a cement mixture application (Mw) is preferably 1,000,000 or less. More preferably, it is less than 500,000, and is more than 30,000, and more preferably 200,000 or less, and the best is less than 150,000. Further, when it is used for a cement mixture application, Mw is preferably more than a circle from the viewpoint that the cement particles are adsorbed to the cement particles at a m-degree, and the adsorption force is increased as the Mw is increased. More preferably, it is 5,000 or more, and further preferably 10,000 or more, more preferably 20,000 or more, and most preferably 30,000 or more. Further, the number average molecular weight (Mn) is preferably less than 50,000. More preferably, it is 250,000 or less, and further preferably 150,000 or less, particularly preferably 1,000,000 or less, and most preferably 75,000 or less. Further, it is preferably more than coffee. More preferably, it is more than 2,500, and more preferably 5,000 or more, and it is more preferably i or more, and most preferably 15 or more. The weight average molecular weight of the compound is determined by a gel permeation chromatography (Gpc) analysis method described later. The (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention preferably has the following formula (6): 41 201240937 0 x- (6) '(ΑΟ)η-γ1—ρ_1 1

OM (wherein X represents a residue of a compound having an active hydrogen or a hydrogen atom. A 〇 is the same or different 'is an oxy group having a carbon number of 2 to 18 and a 6-group. γ 丨 is the same or different 'is an organic residue. The same or different, meaning that the metal atom, the ammonium group or the organic amine group are the same or different, and the poly(n) containing the ethylenic monomer unit is the same or different, indicating that the average addition molar number of the oxyalkylene group is The structure represented by the number of 1 to 1000. The integer represented by 4 (9). In the above formula (6), the specific examples of the alkylene group represented by hydrazine and the more expensive ones are the same as the % of the carbon number U of the above-mentioned constituent (poly)-extension: alcohol chain (pAG). Further, the organic residue represented by γ1 is the same as the above γ, and the metal atom and the organic amine group of ruthenium are the same as the metal atom and the organic amine group forming the hypophosphorous acid (over). Niobium is the same as the above polymer (u). The preferred value of η is the same as the preferred value of the average number of repeats of the epoxy compound in the above (poly) condensed diol chain (pAG). (Poly)alkylene glycol-containing polycondensation of a phosphorus atom represented by the above formula (6) = a polymer having a multi-branched structure, and a structure having a multi-branched structure of a gentleman's knife & (straight chain) polymer. The term "multi-branched polymer" as used herein refers to a structure in which at least 3 extracts of a compound having 3 or more active hydrogens are added to V 3 or more sites having an active hydrogen bond. a polymerized bond of a diol bond which has a residue of the above-mentioned active compound as a base point and is branched into a radial form, and the polymer of the non-multi-branched structure means that it does not have such a A structure in which the residue of the compound having 3 42 201240937 or more active gases is branched as a base point to form a radiation-like polymer chain. Further, the (poly)alkylene glycol-based polymer having a phosphorus-containing atom of a non-multi-branched structure is required to have three or more active hydrogens without the above-mentioned polymer chain. When the residue of the substance is branched into a radiation-like structure as a base point, for example, in the case where the y1 in the above formula (6) is an alkylene group having a branched structure, it has a branch in the entire structure of the polymer. Branch structure. The (poly)alkylene glycol-based polymer having a non-multi-branched (linear) structure and having a phosphorus atom has a structure in which X in the above formula (6) has 1 or more. a residue of a compound of active hydrogen bonded to the residue, "1 or 2 (poly) extended diol chain, and the terminal oxygen atom of the (poly) extended diol chain is organically The residue is resistant to the atomic bond with the hypophosphite (salt), and the far organic residue is bonded to the constituent atom by a phosphorus-carbon bond, and the phosphorus atom is bonded to the polymerization containing the vinyl monomer unit. When the main chain of the substance is in the case of 3 hai, the structure of the (poly)alkylene glycol polymer having a non-multi-branched (linear) structure is one of the following: (1) having i or 2 The residue of the above active hydrogen compound is bonded to a (poly)alkylene glycol chain, and the (poly)alkylene glycol polymer containing the phosphorus atom is a compound having hydrazine or more than two active hydrogens. The residue is located at the end of the structure of the (poly)alkylene glycol-based polymer containing a phosphorus atom; (2) has 2 The residue of the above active hydrogen compound is bonded to two (poly)alkylene glycol chains, and the 64 atomic (small) swellable alcohol polymer is a compound having one or more active hydrogens. The structure is located between two (poly)alkylene glycol chains. The scaly atom of the non-multi-branched (straight bond) structure of the above-mentioned (1) is a polycondensed diol of 201240937 The polymer is preferably a structure in which a residue of a compound having one active hydrogen is bonded to one (poly)alkylene glycol chain. Further, the form of the above (2) is non-multi-branched (straight chain). The (poly)alkylene glycol-based polymer having a phosphorus atom is preferably one in which a residue of a compound having two active hydrogens is bonded to two (poly) extender diol chains. The (poly)alkylene glycol-based polymer having a phosphorus atom of a branched structure has a structure in which X in the above formula (6) is a residue of a compound having three or more active hydrogens. The residue is bonded to more than 3 (poly)alkylene glycol chains, and the oxygen at the other end of the (poly)alkylene glycol chain a child is bonded to a phosphorus atom of a hypophosphite (salt) via an organic residue, and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond, and the phosphorus atom is bonded to the vinyl-containing monomer unit In the main chain of the polymer, the above-mentioned multi-branched (poly)alkylene glycol-based polymer having a multi-knife structure is as described above, and the so-called multi-branched structure means having three or more active hydrogens. The residue of the compound is branched into a radial structure as a base point. That is, 'is a structure in which a residue having a compound having three or more tongue hydrogen generations is used as a base point, and a (poly)alkylene glycol chain and an organic residue bonded to a phosphorus atom of a hypophosphite (salt), and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond, and the phosphorus atom is bonded to The main chain of the polymer containing a vinyl monomer unit. The multi-branched (poly)alkylene glycol polymer containing a phosphorus atom becomes a cement particle by steric repulsion due to the multi-branched structure. The performance of dispersion is dramatically improved and better As cement admixtures. In the above formula (6), when the claw is 丨 or 2, when the phosphorus-containing diol-based polymer of the phosphorus-containing genus 44 201240937 is not more than branched, it becomes a multi-branched structure. The ratio of 1 to m is 3, and the number of (poly)alkylene glycol-based polymers containing phosphorus atoms is preferably based on the use of the (10)-containing (5)-extended diol-based polymer of the present invention. In the case of the above, it is used for cement mixing 4 α Η, and good y is from & horse 3 or more. More preferably, it is 4 or more and further preferably 5 or more. Further, m is preferably preferably 20 or less, more preferably 10 or less. When the above compound having an active nitrogen is used in the production of a hole-filled (poly) stretched diol-based polymer having a multi-branched structure, the active hydrogen number of the compound having an active oxime must be more than 3 or more. Further, from the viewpoint of polymerizability, it is preferably 5 (or less). The lower limit of the active hydrogen number is preferably 4, more preferably 5, and the upper limit is more preferably 2, and more preferably 1 or more. It is to be noted that the residue of the above-mentioned compound having active hydrogen means a group having a structure in which active hydrogen is removed from a compound having active hydrogen, and the term "active hydrogen" means hydrogen which can be added to epoxy burning. a residue of a compound having 1 or more active hydrogens, specifically, for example, an alcohol residue having a structure in which an active hydrogen is removed from a radical of a monohydric or polyhydric alcohol, having a mono- or poly-amine An amine residue in a structure in which an active gas is removed from an amine group, an imine residue having a structure in which an active hydrogen is removed from an imine group of a monovalent or polyimine, and a guanamine group having a mono- or poly-p-amine compound is removed. A guanamine residue or the like of the structure of active hydrogen. Among them, preferred are amine residues, imine residues and alcohol residues. Thereby, a compound suitable for various uses can be produced. 45 201240937 The form of the compound residue of the tongue/growth can be either a chain, a branch, or a three-dimensional structure. In a preferred embodiment of the residue of the compound having an active hydrogen, the polyamine (polyamine) may be a compound having an average of three or more amine groups in the molecule, and is preferably, for example, a conventional method. A homopolymer or a copolymer obtained by polymerizing one or more of the following monoamine compounds: methylamine, ethylamine, propylamine, butylamine, 2- Ethylbutylamine, octylamine, dimethylamine, dipropylamine, dimethylethanolamine 'dibutylamine' trif-amine, triethylamine, cyclobutylamine, cyclohexylamine, laurel Alkylamines and the like; amines such as propylamine; aromatic amines such as aniline and diphenylamine; and nitrogen compounds such as urea and thiourea. The polyamine residue of the above (poly)alkylene glycol compound containing a phosphorus atom is formed by such a compound. Further, it may also be an ethyl diamine, a diethylidene triamine, a tri-ethyltetramine, a tetraethylidene pentaamine, a penta-ethylhexamine, a di-propyltriamine, a tri-propylidene. Tetraamine, tetra-propyl pentamine, etc., in the polyamines, which usually have a tertiary amine group or a secondary amine group (imino group) in addition to a tertiary amine group in the structure. . Among these, it is preferred to use a polyalkylene amine, and the alkylamine constituting the polyalkylamine is preferably a tertiary amine having a carbon number of 8 to 18 such as laurylamine. Also, poly-bending imine, as long as it is! A compound having an average of 3 or more imine groups in the molecule can be used, for example, preferably by the method of & oxime, ethimine, propylenimine, quinone, butylimine, 2,3 A homopolymer or a copolymer obtained by polymerizing one or two or more kinds of alkyleneamines having 2 to 8 carbon atoms such as an imine or a dimethyl thiamine. By such a compound

46 201240937 A polyalkyleneimine residue of the above (poly)alkylene glycol-based polymer containing a phosphorus atom is formed. Further, the polyalkylenimine is crosslinked into a three-dimensional structure by polymerization, and usually has a tertiary amine group or a secondary amine group (imino group) containing an active hydrogen atom in addition to the tertiary amino group in the structure. . The t is more preferably a polyalkyleneimine in which the ethyleneimine is the main component from the viewpoint of the performance of the (poly)alkylene glycol polymer having a phosphorus atom. The term "subject" in this case refers to the formation of polycondensation in the present invention when the polyalkylenimine is formed from two kinds of excipients. The alkyleneamine of the alkylenimine chain is an ethylenediamine, whereby the hydrophilicity of the (poly) glycerol-based polymer containing the phosphorus atom is sufficiently enhanced and becomes suitable for comparison. In many cases, the effect of the use of the product is such that, in order to sufficiently exert the above-mentioned effects, ethidium is used as a salt for forming an exhaled imine of a poly-extension imine bond (polyimide-imine residue). It became the "majority" mentioned above. It is preferably 50 4 (10) mol% if it is expressed by the % of the molar amount of exoethylenimine in 100% by mole of the alkyleneimine. If it is less than 5 Gmol%, the hydrophilicity of the polyimidazole chain becomes insufficient. More preferably, it is preferably 6 〇 mol, and more preferably 7 〇 mol% or more, and particularly preferably 80 mol% or more, and most preferably 90 mol% or more. Preferably, the average number of polymerizations of the imines of the polyazide chain is more than eight, preferably less than 3 〇 1 is set to be such a range, and J is more fully utilized by the above The effect of the structure of the solid structure: a wide (poly)-extended diol-based polymer ^ such a polymer can be used as a cement admixture suitable for 201240937 to exhibit excellent cement dispersibility. The lower limit value is more preferably 3, further preferably 5, and particularly preferably 1 Torr. Further, the upper limit is more preferably 200, further preferably 1 Torr, and particularly preferably 5 Torr, and most preferably. Further, the average number of polymerizations of the diterpenoid was 2, and the average number of polymerization of the diethylidene tetraamine was 3. The number average molecular weight of the above polyamine and polyalkyleneimine is preferably from 1 〜 to 100,000, more preferably from 300 to 50,000, still more preferably from 600 to 1 Torr, still more preferably from 800 to 5,000. The number average molecular weight of the polyamine and the polyamines can be determined by gel permeation chromatography (GPC) analysis. The polyhydric alcohol is preferably a compound composed of three elements of carbon, hydrogen and oxygen, as long as it is a compound having an average of three or more merid groups in the i molecule. Specifically, for example, glycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, hydrazine, 3,5-pentanetriol, erythritol, neopentyl alcohol, and second are preferable. Neopentyl alcohol, sorbitol, sorbitan sorbitol glycerol condensate, flavonol, arabitol, xylitol, sorbitol, and the like. Also as 'sugars, preferably glucose, fructose, mannose, idose, sorbose, gulose, talose, tagatose, galactose, allose' naloxone, altrose, etc. Sugars of hexoses; sugars of pentoses such as arabinose ribulose, ribose, xylose, xylulose, and threose; sugars of butyose such as threose, erythrokose, and sucrose; rhamnose , fiber disaccharide, maltose, isomaltose, sea sugar, strict sugar, raffinose, gentian trisaccharide, pine trisaccharide and other sugars; such sugar alcohols, sugar acids (saccharides: glucose 'sugar alcohol: glucose Alcohol; sugar acid: gluconic acid) and the like. Further, such derivatives as the partially etherified or partially esterified compounds of the compounds of the invention are also preferred. The polyol residue of the above (poly)alkylene glycol-based polymer containing a phosphorus atom is formed by such a compound. Among the 5th and the like, it is more preferable to be trimethylolpropane or sorbitol from the viewpoint of industrial production efficiency. The number of the (poly)-extended diol bonds to which the compound having three or more active hydrogens is bonded is preferably equal to the number of active hydrogens in the cerium having three or more active hydrogens. Namely, it is preferred that all of the active hydrogen atoms in the compound having three active hydrogens are bonded to a (poly) extendable alcohol bond. By forming a (poly)-sintering-alcohol-based polymer having a phosphorus atom having such a structure, it is possible to provide a cement admixture capable of exhibiting more excellent dispersibility. Here, 'the number of the above-mentioned (poly)-extended diol chain to which the above-mentioned active hydrogen having 3 (5) or more is bonded is equal to the number of active hydrogens in the compound having 3: active hydrogen on the hydrazine. The structure of the situation can be expressed as follows. There are three ^" (c) which are structurally represented as follows: the residue of the compound having a residue of more than the active hydrogen is a glycerol residue (all active hydrogens of the polyol glycerol) The bond (8) extends to the diol chain and is bonded to the phosphorous acid (salt), and the organic residue is bonded to the monomer by a single bond, and the atom of the material is bonded to the polymer containing the vinyl tile. Further, it is a structure in which the formula (9) schematically represents a structure in which the residue of the active hydrogen compound on the structure is a sorbitol residue (poly-a-49 201240937 alcohol residue) An active hydrogen bonding (poly)alkylene glycol chain with sorbitol and bonded to a subphosphorus (salt) via an organic residue, and the organic residue and the phosphorus atom are phosphorus-carbon The bond is bonded, and a plurality of the phosphorus atoms are bonded to the main chain of the polymer containing the vinyl monomer unit.

(6) (D) The (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention is a residue-bonded (poly)alkylene glycol chain having a compound having two or more active hydrogens and is organic The residue is bonded to a phosphorus atom of a hypophosphite (salt), and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond, and the phosphorus atom is bonded to the phosphorus atom. In the case of the structure of the main chain of the polymer containing the monomer unit of the fused monomer unit, 'the residue of the compound having two or more active hydrogens may be bonded to the hypophosphite via the organic residue. a (poly) extender diol chain other than the (poly)alkylene glycol chain. The terminal of the (poly)alkylene glycol chain (end of the side opposite to the residue of the compound having two or more active hydrogens) is preferably, for example, bonded to a hydrogen atom, a monovalent metal atom, or a divalent metal. Atom, Suki's organic amine group, carbon number 1~3 0, oxyhydrocarbyl group, amine amine group, mercapto group, carbon number 〇

50 201240937 The structure of any one of sulfonate (hydrocarbon) groups and the like of 30 to 30, and when there are two or more (poly)alkylene glycol chains in the industrial molecule, the terminal structure may be the same. Can be different. Among such terminal structures, in terms of versatility, it is preferably a structure bonded to a hydrogen atom or a hydrocarbon group of a carbon number, and more preferably bonded to a hydrogen atom or a hydrocarbon group having a carbon number of 丨~(7). The structure, in the group of carbon number i to 10, is preferably an alkyl group or an alkylene group. In other words, the (poly)alkylene glycol-based compound containing a phosphorus atom of the present invention may be, for example, a compound represented by the above formula (2). <Method for Producing (Poly)alkylene Glycol-Based Polymer Containing Phosphorus Atom> The (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention is preferably contained in the following formula (1) X—(AO)—Υ1 Μο ^Ίριιο ε \—/ i:-/(\ (where x represents a residue of a compound having an active hydrogen or a hydrogen atom. AO is the same or different, and represents a carbon number of 2 to 18) The oxy group is an alkyl group, which is the same or different, and represents an organic residue. Y2 is the same or different and represents an organic residue or a hydrogen atom. The same or different Μ represents a metal atom, a magnetic group or an organic amine group. n is the same or different The average addition molar number of the alkyloxyalkyl group is 1 to 1000. The m is an integer of i to 50) and the phosphorus atom is represented by a (poly) alkylene glycol compound in the presence of a vinyl group. It is produced by a method in which the monomer component is subjected to polymerization, and it is more preferable to use a poly(alkylene glycol) compound containing a phosphorus atom in which the oxime 2 in the above formula (1) is a hydrogen atom. Said that the compound represented by the formula (1) has a function as a chain transfer agent by using the compound By subjecting the ethylenic monomer component to radical polymerization by a chain transfer agent, the phosphorus atom-containing (poly)alkylene glycol-based polymer of the present invention can be produced simply and efficiently at low cost. The method for producing a (poly)alkylene glycol-based polymer containing a phosphorus atom is also one of the inventions. The (poly)alkylene glycol compound containing a phosphorus atom represented by the above formula (1) is used as In the case of producing a polymer by a chain transfer agent, the vinyl monomer component is sequentially added via a phosphorus atom (p) of a (poly)alkylene glycol compound containing a phosphorus atom to form a polymer moiety. The polymer formed by the method is formed as a main component, and may have a form in which the structure of the polymer portion formed by the vinyl monomer component is repeated two or more times or has a monomer derived from the monomer (a a polymer of a monomer or a monomer of one or more monomers of the monomer (c). The phosphorus-containing (poly)alkylene of the present invention represented by the above formula (1) is used. Alcohol-based compound as a chain transfer agent When the polymer component (i) is produced by radical polymerization of the body component, the amount of the (poly)alkylene glycol compound containing the phosphorus atom and the vinyl monomer are added to the polymerization reaction. The relationship between the monomer (a), the monomer (1), and the monomer (C) used in the component (% by mass) is represented by the above-mentioned (poly)alkylene glycol compound containing a phosphorus atom / (monomer (a) + The ratio of the monomer (1) + monomer (〇) is preferably 5/% to 1/4, more preferably 10/90 to 97/3, and still more preferably 20, in the case where the monomer (a) is a main component. /80~95/5, especially good for 30/70~92.5 eight 5. Also, in the monomer (1) as the main component 52 201240937 ▲ shape when 'better 2/98~95/5' is better 4 /96~90/1〇, further preferably 8/92~80/20, more preferably 10/90~75/25, especially preferably 15/85~70/30, especially preferably 17.5/82.5 ~65/35, the best is 20/80~60/40. In particular, monomer (a) is a ratio of monomer (a) / (phosphorus-containing (poly)alkylene glycol compound + monomer (b) + monomer (c)) (unit is 1% by mass) The amount is preferably from 1 to 50/99 to 5 Torr, more preferably from 2.5 to 40/97.5 to 60, and still more preferably from 5 to 35/95 to 65. In the case where the monomer (c) is a main component, the monomer (a) in the preferred range of use of the above monomer (&amp;) may be replaced with the monomer (c). . Shangtong early body I a ) ...... heart dry, d; about jade · points, the above monomer (〇 &amp; main component of the use of the situation; the scope can also be applied Only (4) monomer (a) material B is a single component, only monomer (b) ethylene substrate, monomer component, shape, only hang monomer (e) as a vinyl series In the case of the body composition, the above-mentioned bismuth compound of the (poly)-excited bis(10) compound containing a phosphorus atom is used to completely dilate the monomer component of the berry-based base by NaQH (using NaOH + ψ 4, , A ^ ^ 疋 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中Agents, for example, 二 ] 举 锍 锍 锍 乙醇 乙醇 乙醇 乙醇 乙醇 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 锍 ; ; ; ; ; ; ; ; ; ; _ r , brother-level knowledge; phosphorous acid, hypophosphorous acid and its (- sodium human phosphite, potassium hypophosphite potassium), sulfurous acid, hydrogen sulfite, 253, 201240937 sulfur acid, Heavy sulfite and its salts (sodium sulfite, sodium bisulfite, sodium disulfite, sodium metabisulfite, etc.), lower-grade oxides and their salts, and other hydrophilic bond transfer agents. Also - the above chain transfer agent, can also use hydrophobic A chain transfer agent. For example, a butane thiol, a octyl thiol, a decyl thiol, a decyl thiol, a hexadecane thiol, an octadecyl thiol, or a ring can be preferably used. a thiol-based chain transfer agent having a hydrocarbon group having a carbon number of 3 or more, such as hexyl mercaptan, sulphur, octyl thioglycolate or octyl propionate, in addition to the phosphorus atom-containing (poly) of the present invention. When the above-mentioned chain transfer agent is used in addition to the alkylene glycol-based compound, the amount of the chain transfer agent may be appropriately set, and the total amount of the vinyl monomer component is 4 mm, which is preferably (M or more). More preferably, it is 0.25 mol or more, further preferably 〇5 mol or more, and is preferably 2 G mole or less, more preferably 15 mol or less, further preferably 10 mol or less. Depending on the need, the solution may be polymerized or aggregated, or the like, or refined or continuous. Incorporation/two liquids... The use of the back points can be exemplified by: water; methanol, acetonitrile, a solvent such as an alcohol such as alcohol, isopropanol, or the like; an aromatic or aliphatic group such as benzene, toluene, dioxon, dihexyl hexyl alcohol Smoke; acetic acid, ethyl acetate, etc. r compound; acetone, methyl ethyl A _ wild defeat c from the day 4 酉曰 appearance and other cyclic compounds, etc.:: ketone compounds; four gas gnaw, two obstacles as an aqueous solution In the case where the use as a cement admixture is carried out by polymerization by aqueous solution polymerization, it is preferred to use a water-soluble free 201240937-based polymerization initiator in the above solution polymerization. In this case, since it is not necessary to remove insoluble components after the polymerization, it is preferably, for example, persulfate such as ammonium persulfate, sodium persulfate or potassium persulfate; hydrogen peroxide; 2, 2, azobis-2 Azo sulfonium compound such as propyl hydrazine hydrochloride, cyclic azo lung compound such as 2,2, azobis 2_(2-imidazoline-2-yl)propane hydrochloride, 2 _ amine sulfhydryl group Azonitrile compound such as azoisobutyronitrile, 2,4,-azobis{2 _mercapto-N-[2 one (i a azoamine compound such as hydroxybutyl)]propanolamine}, a azo compound such as an ester of 4,4 ι-azobis(4-cyanovaleric acid) and (alkoxy)-glycolic acid glycol A water-soluble azo initiator; one or two or more of these may be used. Among them, a persulfate-based initiator is preferred. At this time, it is also possible to use together an alkali metal sulfite such as sodium hydrogen sulfite, a metabisulfite, a sodium hypophosphite, a molar salt or the like Fe (π) salt, a hydroxymethyl sodium hydride dihydrate, a hydroxylamine. Promoters (reducing agents) such as hydrochloride, thiourea, L-ascorbic acid (salt), erythorbic acid (salt). For example, it may be a combination of peroxygen: nitrogen and an organic reducing agent. As the (four) reducing hydrazine, L-ascorbic acid (salt), L-ascorbic acid vinegar, isoascorbic acid (extension), erythorbic acid _, etc. may be preferably used. These radical polymerization initiators or agents may be used alone or in combination of two or more. In addition, the amount of the above-mentioned accelerator (reducing agent) is not particularly limited, and if the total amount of the polymerization initiator to be used in combination is more than or equal to Momo, it is more preferably Preferably, it is 5 〇 Mo Er:: 2 is better... Mohr below is better than 5 〇〇 Mo ear, and then #父佳 is below 400 Mo. Further, in the case of a solution polymerization or a bulk polymerization using a lower alcohol, a bitter alcohol, a fragrant or aliphatic hydrocarbon, an ester or a ketone 55 201240937 as a solvent, for example, a peroxylation initiator can be used. a peroxide such as benzamidine, oxidized laurel, sodium peroxide or the like; hydrogen peroxide such as t-butyl hydroperoxide or isopropyl bromide;

Azonitrile compound such as azobisisobutyronitrile, 2,4·-azobis{2-methyl-N

[2~(1-Hydroxybutyl)]propanamide} and other azoguanamine compounds, 4,4,-azobis(4-cyanovaleric acid) and (alkoxy)polyethylene glycol One or two or more kinds of azo-based initiators such as a macro azo compound such as an ester. Among them, the car described below is also an azo initiator. Further, at this time, an accelerator such as an amine compound may be used in combination.

Further, in the case where a solvent mixture of water and a lower alcohol is used, a combination of various radical polymerization initiators or the above-mentioned radical polymerization initiators is appropriately selected and used. The amount of the radical polymerization initiator to be used may be appropriately set according to the aspect or amount of the (poly)alkylene glycol compound or the vinyl monomer component containing a phosphorus atom. When the amount of the agent is too small with respect to the vinyl monomer component to be polymerized, the radical concentration is too low to slow the polya reaction, and if the amount is too large, the radical concentration is excessive; The polymerization reaction of the vinyl monomer component takes precedence over the polymerization reaction initiated by the dish atomic bow and does not improve the yield of the (8) exodiol polymer having a dish atom of the present invention. The above-mentioned radical polymerization initiator: used in an amount relative to the total amount of the vinyl monomer component. It is said that Moer is better than 丨. 〇 1 mole or more, and further preferably. 2 ears or more 'especially more than 0.2 m or more, and more preferably more than U ears, preferably 5 m or more, and 'better than 5 〇 mo ear, more preferably Mo 56 201240937 and then preferably 10 moles or less, and then better, especially better than 5 moles, 兀仫 2 moles or less, the best is below the moles. In the above polymerization reaction, polymerization conditions such as polymerization temperature are appropriately set according to the polymerization method, solvent, polymerization initiator, and chain transfer agent used. The polymerization temperature is preferably οι or more, and preferably 15 Generation below. More preferably 30. (The above is further preferably a thief or more. Further, it is more preferably hereinafter or less, and further preferably 1 〇〇. 〇 below. Further, the method of introducing the vinyl monomer component into the reaction container is not The special limit ^ ' can be the initial total amount - and the method of injecting into the reaction vessel, the method of dividing the total amount into the reaction vessel continuously, and initially filling a part of the reaction and the remaining amount Any one of the methods of dividing into or continuously feeding into the reaction vessel. Further, the radical polymerization initiator or the chain transfer agent may be initially placed in the reaction vessel or may be dropped into the reaction vessel, or According to the purpose, the phosphorus-containing (poly)-extended diol-based polymer (the above polymer (1)) of the present invention is preferably obtained by initially preliminarily using the phosphorus atom-containing (poly)alkylene of the present invention. The total amount of the diol-based compound is introduced into the reaction container and continuously introduced into the vinyl monomer component. When the method is used for production, the obtained polymer is used as a cement. Mixing agent Further, the fluidity of the cement is further improved. In the above polymerization reaction, it is preferred to stably carry out the polymerization reaction in order to obtain a polymer having a specific molecular weight with good reproducibility. Therefore, in solution polymerization, it is preferred to use it. The dissolved oxygen concentration of the solvent at 25t &gt; c is set to be less than 5 Ppm (preferably 〇. 〇 1 to 4 ppm 'more preferably 二. 22: 201240937 PP and further preferably 〇·〇 1 to lppm). In the case where a nitrogen substitution or the like is carried out after the V-ethylene monomer component in a solvent, it is preferred to set the dissolved oxygen concentration of the system having a vinyl monomer component to the above range. The above-mentioned adjustment of the dissolved oxygen concentration of the granules may be carried out in the polymerization reaction tank or may be adjusted in advance using the dissolved oxygen amount. For the method of removing oxygen in the solvent, for example, the following (1) to (5) may be mentioned. Method (1) Reducing the pressure in the sealing volume H by pressurizing and filling an inert gas such as nitrogen in a sealed container filled with a solvent, thereby reducing the partial pressure of oxygen in the solvent towel, which can also be lowered under a nitrogen gas flow. The pressure inside the closed container. 2) In the state in which the gas phase portion in the solvent-containing container is replaced with an inert gas such as nitrogen, the liquid phase portion is vigorously searched for a long time. (3) An inert gas such as nitrogen is allowed to be filled in the solvent in the container for a long time. () After temporarily boiling the solvent, it is cooled in an inert gas atmosphere such as nitrogen. () A static mixer (static mixer) is placed in the middle of the piping to transfer the agent to the piping in the polymerization tank. The polymer (i) obtained by the above polymerization reaction may be adjusted to a pH which is weakly acidic or more (more preferably pH 4 or more, further preferably _ or more, and particularly preferably PH 6 or more) by an aqueous solution or the like. The range is made easy to operate. On the other hand, if the polymerization is carried out above PH7, the polymerization rate is

58 201240937 The cohesiveness at the same time has also become eight. The shape of the product is used. For example, it is used in cement blending agents, and it is not possible to fully exert the dispersing performance. Therefore, it should preferably be in the PH region from acidic to neutral (preferably not up to pH 6, - 1 /5 = PH5 5 ' and preferably not up to PH5). As a preferred polymerization initiator for the polymerization from acidic to neutral, for example, it is better to use persulfate such as ammonium persulfate, sodium persulfate or persulfate, or arsenazo. - water-soluble azo such as tiangan nitrogen and 2-anthranyl hydrazine hydrochloride, such as hydrazine, Α _ &amp;&amp; D agent 匕 emulsified hydrazine, hydrogen peroxide and organic reducing agent Combinations, etc. Further, it is more preferred to use at least (iv) (iv) initiator. Therefore, it is preferred to adjust the polymerization to a higher yang by adding a test substance or the like after the polymerization reaction at a lower pH. Specifically, a method of adjusting the pH to 6 or more after adding the test substance after the polymerization reaction is not carried out at pH 6, and adding the test substance to the pH 5 or higher after the polymerization reaction is not carried out at pH 5; After the polymerization reaction, a test substance is added to adjust the pH to 6 or higher. The pH can be adjusted, for example, by using a hydroxide of a monovalent metal or a divalent metal, or an inorganic salt such as a carbonate, or an alkaline substance such as ammonia or an organic amine. In the case of lowering the pH, especially when it is necessary to adjust the pH during polymerization, phosphoric acid, sulfuric acid, nitric acid, alkylphosphoric acid, alkylsulfuric acid, alkylsulfonic acid, (alkyl)benzene can be used. The acidic substance such as a sulfonic acid is adjusted in pH, and among these acidic substances, in terms of 1) 11 buffering action, etc., phosphoric acid or sulfuric acid which can be added in a small amount to lower the pH is preferable. Further, after the completion of the reaction, the concentration can be adjusted as needed. In the reaction product obtained by the above polymerization reaction, in addition to the polymerization 59 201240937 (i), the ancient spit + &amp; anti-Taohai: various polymers or unreacted raw materials of the by-products, raw materials The inclusion of impurities, so that the growth of the individual polymers can be used in various applications without increasing the efficiency of the operation or the manufacturing cost. The polymer (1) of the present invention can be suitably used, for example, in various applications such as an adhesive, a softening component of various polymers, and a lotion adjuvant. In addition, inorganic fine particles such as cement or gypsum are contained. The composition 'is also preferably used as an additive for dispersing inorganic fine particles. Further, such an additive for inorganic particles containing a (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention is also one of the inventions. Among them, the (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention is preferably used for a cement admixture because it exhibits extremely high cement dispersibility as described above. Thus, the cement admixture containing the (poly)alkylene glycol-based polymer containing a phosphorus atom of the present invention is also one of the inventions. The above cement admixture may be added to a cement composition such as cement slurry, mortar or concrete, and such a cement composition containing the above cement admixture is also one of the inventions. The above cement composition preferably contains cement, water, fine aggregates, coarse aggregates, etc. 'Cement can be enumerated: Portland cement (common, early strength, super early strength, medium heat, sulfate resistance, and respective Low-initial form); various mixed cements (ancient furnace cement, cerium oxide cement, fly ash cement); white Portland cement; alumina cement; ultra-speed hard cement (1 clinker quick-hardening cement, 2 clinker fast-hardening Cement, magnesium phosphate cement); cement for grouting; oil well cement; low-heating cement (low-heating blast furnace cement, fly ash mixed low-heating blast furnace cement, oblique stone eve 201240937 calcium cement containing cement); ultra-high strength cement; cement The solidified material; the environmentally-friendly cement (one or more of the municipal waste incineration ash, the sewage sludge incineration ash, etc.), and the like, in addition to the above-mentioned additions, etc. Ash, coal ash, clinker ash, shell ash 'smoked sulphur dioxide, sulphur oxide powder, limestone powder and other fine powder or gypsum. In addition to gravel, crushed stone, water-crushed slag, recycled aggregates, etc., the above-mentioned aggregates can also be smashed. Stone stone, clay, recorded stone, highly oxidized, high quality, carbonized enamel, black wrong, Refractory aggregates such as chrome, chrome, oxidized and temperate. The unit water amount per lm3 of the above cement composition, the amount of cement used, and the water/cement ratio (mass ratio) are, for example, preferably set to a unit water amount (10) to ^5 kg//, and a cement amount of 2 〇〇 to 8 〇〇 kg. /Claw 3, water/cement ratio (mass 匕) 0·1~〇.7, more preferably set to unit water volume 12〇~175kg/m3 Use cement volume 250~water/cement ratio (mass...〇; Thus, the cement admixture containing the polymer (1) of the present invention can be subjected to a self-conversion to a rich blending rate (1 domain is... using 'even high water=domain' ie water/cement ratio (f ratio) ) = G15 ~ G5 (preferably 015 ~ k water / cement can be used in the lower areas, and further, for the amount of mud and water &quot; mud is relatively small high-strength concrete, 2 cement is set to seam g /m, the lower lean concrete is effective. In the early position = cement mixed concrete, even in the high water reduction rate area and high performance to achieve fluidity, retention and operability, I condensate: excellent = (four) sex, therefore also Can be effectively used for pre-sale; concrete (pre-bonded concrete) for concrete, centrifugal forming: vibrating pressure practical concrete, steam health mixing Condensate, spray concrete, etc. V: 61 201240937 Furthermore, for medium-flow concrete (a concrete with a C-degree of 22 to 25 cm), concrete flowing concrete (, the value of the town is 25 cm or more and the flow value of the flow rate) It is also effective for mortars or concretes with a high fluidity such as a range of 50 to 7 〇cm, 3 condensate +, &amp; 士固固土), self-filling concrete, and self-leveling materials. In the case where the cement admixture is used in the cement composition, the ratio of / as the ratio of the mixture is preferably such that the polymer (1) which is an essential component of the present invention is converted by the solid content relative to the total mass of the cement 1 The mass % is set to be 0.01 to 10% by mass. If it is less than 1% by mass, the performance may be insufficient. On the contrary, if it exceeds 丨〇% by mass, the effect is on the quality. It is economically disadvantageous to reach the limit. More preferably, it is 0.02 to 8 mass%, and further preferably 〇〇5 to 6 mass 0/〇. Further, the above cement mixture can also be used in combination with other cement additives. Other cement additives, for example, can be used as follows One or more of the cement additives (materials) shown, etc. Among them, an oxyalkylene-based defoaming agent or an AE agent is preferably used in combination. Further, the 'addition ratio of the cement additive' is preferably relative to the above polymer. (0 parts by mass of the solid content component is 0.0001 to 10 parts by mass. (1) Water-soluble polymer substance: polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium) An unsaturated tetacid polymer such as a sodium salt of an acrylic acid-maleic acid copolymer; a polymer of polyoxyethylene or polyoxypropylene such as polyethylene glycol or polypropylene glycol or a copolymer thereof; Cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose, etc., non-detached from 201240937 Glucan or Sanxian gum, stone-丨, 3 glucan (linear or branched chain, may be mentioned: Cardland polysaccharide, paramylon, gluten, scleroglucan, kelp Polysaccharides produced by microbial fermentation such as sugar; polypropylene decylamine; Polyvinyl alcohol; starch; starch phosphate; sodium alginate; gelatin; copolymer of acrylic acid having an amine group in the molecule and a quaternary compound thereof. (2) Polymer latex. (3) retarding agent: gluconic acid, malic acid or citric acid, and hydroxycarboxylic acids and salts thereof such as inorganic salts or organic salts of sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc.; glucose, fructose, Galactose, sucrose; sugar alcohol such as sorbitol; barium fluoride; phosphoric acid and its salts or borate esters; aminocarboxylic acid and its salts; test soluble protein; humic acid; tannic acid; phenol; Polyol; amine tris (methylene phosphonic acid), 1-hydroxyethylidene_1, hydrazine-diphosphonic acid, ethylidene diamine tetra(methylenephosphonic acid), di-ethyltriamine (methylene phosphonic acid) and such alkali metal salts - phosphonic acids such as soil-measuring metal salts and derivatives thereof. (4) Early strength agent and accelerator: soluble calcium salt such as calcium carbonate, calcium nitrite, nitric acid, calcium desertification and calcium iodide; alkanolamine; alumina cement; Ming calcium citrate. (5) Mineral oil defoamer: lamp oil, liquid paraffin, etc. (6) Antifoaming agents for oils and fats: animal and vegetable oils, sesame oil, castor oil, and such alkylene oxide adducts. (7) A fatty acid-based antifoaming agent: oleic acid, stearic acid, an alkylene oxide adduct or the like. (8) Fatty acid ester-based antifoaming agent: glycerin monoricinoleate, alkenyl sulphate 63 201240937 sorbitol trioleate, natural j white acid derivative, sorbitol monolaurate vinegar, and the like. (々) Oxidized olefin-based defoaming agent: (poly) gas method (surgery), ethylene (poly) oxypropylene adduct, and other polyoxygenated dilute; diethylene glycol age, prepared ^ ^ and heptyl ether, Polyethylene ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2_ Qiu 1 hexyl hexyl ether, oxyethylene propylene propylene adduct of higher alcohols with a carbon number of 12 to 14 (poly) oxygen (4) Class; polyoxypropylene phenyl ether, polyoxyethylene decyl benzene, etc. (poly) oxidized dilute (hospital base) fragrant; add alkylene oxide to 2,4,7,9-tetradecyl —5—decyne—4,7-diol, 2,5-dimethyl-3-hexyne~2,5-diol, 3-methyl-(-butyl _3_ alcohol, etc. Acetylene lysine; succinyldiethyl hexahydrate, ethylene glycol distearate (poly) oxyalkylene fatty acid vinegar; polyoxyethylene sorbitan monolauric, poly Oxyethylene sorbitan sorbitol trioleate vinegar, etc. (poly) oxidized dilute sorbitan fatty acid vinegar; polyoxypropylene sulfonate sodium sulfate, polyoxyethylene lauryl phenol ether sulfate, etc. (poly) alkylene oxide Alkyl (aryl) ether sulfates; (poly)oxyethylene (poly) oxyalkylene alkyl phosphates such as aliphatic phosphates; (poly) oxidized dilute alkylamines such as polyoxyethylene laurylamine; polyoxyalkylene decylamines, etc. (10) alcohol-based defoamers: xin Alcohol, hexadecanol, ethyl hexanol, glycol, etc. (11) Amidoxime defoamer: acrylate polyamine, etc. (12) Phosphate defoamer: Tributyl phosphate 'octyl phosphate Sodium, etc. (1 3 ) Metal soap defoaming agent: aluminum stearate, calcium oleate, etc. (14) Desulfurization agent: dimethyl ketone oil, lithene ketone beam, stone Ethyl ketone latex, organically modified polyoxyalkylene (polyorganohydrazine such as dimethyl polyoxane, C: 64 201240937 oxyalkylene), fluoropterin oil, etc. (1 5 ) Tanning agent. Resin, saturated or not Saturated fatty acid, sodium sulphate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenyl sulfosuccinate, α-olefin sulfonate Etc. (1 6 Other surfactants: octadecanol or stearyl alcohol is equivalent to an aliphatic monohydric alcohol having ό30 carbon atoms in the molecule; rosin alcohol is equal to an alicyclic monohydric alcohol having 6 to 30 carbon atoms in the molecule; A dialkyl thiol is equivalent to a thiol having 6 to 30 carbon atoms in the molecule; the nonyl phenol is equal to a fluorenyl group having 6 to 30 carbon atoms in the molecule; the 12-yard amine is equal to 6 to 30 in the molecule. An amine of a carbon atom; an alkylene oxide such as ethylene oxide or propylene oxide of 1 〇 mol or more is added to a carboxylic acid having a lauric acid or stearic acid equal to 6 to 30 carbon atoms in the molecule. Polyalkylene oxide derivatives; alkyl diphenyl ether sulfonates which can be ether-bonded with two phenyl groups having an alkyl group or an alkoxy group as a substituent and having a mercapto group; various anionic interfaces Active agent; various cationic surfactants such as alkylamine acetate, alkyltrimethylammonium chloride; various nonionic surfactants; various amphoteric surfactants. (I7) Water repellent: fatty acid (salt), fatty acid ester, oil, sand, sarcophagus, asphalt, soil, and the like. (1 8) rust inhibitor: nitrite, phosphate, zinc oxide, etc. (19) Crack reducing agents: polyoxyalkyl ethers; 2 - mercapto - 2,4 - pentylene 4 «·.

Jt. 65 201240937 Alkanediols such as alcohols. (20) Swelling materials. Ginger bow wears stone, coal and so on. Other cement additives (materials), for example, can be clipped · ^ Y, called, J external. Cement wetting agent, tackifier, separation reducer, aggregating agent 'dry shrinkage reducing agent, strong heart agent, self-leveling agent , anti-recording agent, coloring agent, anti-fungal agent, blast furnace, second, cinder ash, clinker ash, shell ash, smoked cerium oxide, cerium oxide, gypsum, etc. For the production of a polyalkylene glycol chain-containing compound of the above-mentioned PAG compound, the polymer, and the raw material of the above-mentioned materials, the preferred reaction conditions are shown below. The reaction is carried out uniformly, and the stirring power per unit volume (ρ" 杈 is preferably 0.1 Kw/m 3 or more, more preferably 〇 2 Kw/m 3 or more and more preferably 0.4 Kw/m 3 or more, and particularly preferably 〇 6 Kw/m 3 . The reaction tank, the device used for stirring, the stirring blade, the baffle plate, the static mixer, etc. may be appropriately selected as needed. These materials are appropriately selected according to the reaction, such as non-mineral steel, glass, and Hester. In the case of stainless steel, SUS304, SUS316 (L), etc. are preferable. The phosphorus atom-containing (poly)alkylene glycol-based compound of the present invention contains the above-mentioned a novel compound which has a structure in which a terminal oxygen atom of at least one terminal of a (poly)alkylene alcohol chain is bonded to a phosphorus atom of a hypophosphite (salt) via an organic residue, and the organic Residue and phosphorus atom of the phosphorus atom An anaerobic bond, and the compound can be used as a chain transfer agent for a radical polymerization reaction. Further, the phosphorus-containing (poly)alkylene glycol-based polymer of the present invention contains cc'. 66 201240937 And having a structure in which at least the terminal oxygen atom of the (poly)-extended diol chain is bonded to the sub-subdisk acid (the salt atom is bonded via an organic residue, and the organic residue is The 4 atom is bonded by a scale-carbon bond and the phosphorus atom is bonded to a main chain of a polymer containing a vinyl monomer unit, and the polymer can be used for cement dispersibility (water reduction) or mobility retention. The use of a cement admixture having excellent performance, etc. Further, by using: a (poly) stretched diol-based compound of each θ atom, the polymer can be produced at a low cost in a simple and efficient manner. The present invention will be described in more detail, but the present invention is not limited to the examples. Further, unless otherwise indicated, "parts" means "parts by mass" and "%" means "mass%". The various determinations in the system are as follows For &lt; H-NMR '31p-nmr &gt;means:.!; & Gt LC- MS Varian manufactured by VARIAN of 400- Mr &lt;

Device: ThermoQuest, LC-Q DECA XP (company) Shiseido, NAN OS PACE — 2 Mode: Ion trapping assay Conditioned ionization method: ESI method 'positive and negative ion detection, μ/ z= 50~2000 Dissolve ·· 0.1% formic acid, aq/AcCN= 5 / 5 Temperature: 40°C. Flow rate··1〇〇μ1/minute 67 201240937 Column: CapcelPAKMG 试样 Sample preparation: Dilute the sample to 1〇 with ultrapure water 〇〇ppm, using an autosampler to inject 5μ1. &lt;GPC&gt; The number average molecular weight and the weight average molecular weight of the (poly)alkylene glycol-based polymer containing a phosphorus atom are measured according to the following measurement conditions. (Condition 1)

Device: L - 7〇〇〇 series manufactured by Hitachi, Ltd. Using pipe column. SHODEX manufactured by Showa Denko Co., Ltd.

Asahipak GF- 3 10-HQ, GF-710 - HQ, GF-1G 7B Detector: Differential Refractometer (RI) Detector Dissolved Solution: 0.1 N Sodium Acetate / Acetonitrile = 3/1 (mass ratio) Calibration Curve : POLYETHYLENEGLYCOL STANDARD Manufactured by Chuanghe Science Co., Ltd. Temperature: 40°C Flow rate: 0.5mL/min (Condition 2) Device: Waters Alliance (e2695) Analytical software: Pipe column for Empower Professional + GPC option manufactured by Waters : TSKguardcolumna+TSKgel a5000+a4000 + a3000 Detector manufactured by Tosoh Co., Ltd.: Differential Refractometer (RI) Detector (Waters 24 14 ), UV/Vis (UV/ Vis) Detector (Waters 2489) 68 201240937 Dissolved solution: A mixed solution prepared by dissolving 89.0 g of boric acid and 28.8 g of sodium hydroxide in a solution of 14215 g of water, and further adding 3600 g of acetonitrile. Standard material for calibration curve preparation: Polyethylene glycol (peak mass (Mp) is 300,000, 200000, 101000, 50000, 27700, U84 0, 6450, 4020, 1470, 1〇1〇, 400) Calibration curve: It is produced by using the three-stage formula based on the Mp value and the elution time of the above-mentioned polyethylene glycol. Flow rate: 1 mL/min. column temperature: 40 ° C Measurement time: 60 minutes Sample solution injection amount: 1 OOpL (sample concentration: 5: 5% by mass of the solution of the solution) (Condition 3) The following synthesis examples and comparison The weight average molecular weight of the polymer obtained in the synthesis example and the comparative polymer was measured using the measurement conditions shown below. Device: Waters Alliance ( 2695 ) Analytical software: Empower Professional + GPC option by Waters Corporation Pipe column: manufactured by Tosoh Co., Ltd.

TSKguardcolumnSWXL+TSKgelG4000SWXL+G3 000SW

XL+G2000SWXL detector: differential refractive index system (RI) detector (Waters 24 14 ), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996 ) 69 201240937 Dissolution: mixed solvent of water 10 99 g, acetonitrile 6001 g In the middle, 115.6 g of sodium acetate trihydrate was dissolved, and the acetic acid was adjusted to pH 6.0. Standard material for calibration curve preparation: Polyethylene glycol [peak mass (Mp) is 2725 00, 2193 00, 1〇7〇〇〇, 50000, 24000, 12600, 7100, 4250, 1470] Calibration curve: Based on the Mp value of the above-mentioned polyethylene glycol and the elution time, it was produced by the third-order formula. Flow rate: 0.8 m 1 Sub-column temperature: 40 ° C Measurement time: _ 4 5 minutes Sample solution injection amount: lOOpL (sample concentration: 0.5 wt% of the solution solution) (GPC analysis conditions) The obtained RI layer In the analysis, the smoothing of the polymer on the baseline immediately after the dissolution of the polymer by the straight line is used, and the polymer is detected and analyzed. Wherein, in the case where the peak of the monomer or the impurity derived from the monomer is measured at the peak of the polymer, the polymer portion and the single are separated by the vertical division of the most concave portion of the polymer. The body part, 'the molecular weight and molecular weight distribution of the polymer portion just set. In the case where the polymer portion is φ ^ /, and the other portions are completely overlapped and cannot be separated, the calculation is performed by combining. As a standard of the yield of the polymer, "the purity of the polymer (hereinafter, the case where "the amount is "p%" in the following 2012 2012937) is calculated based on the ratio of the area of τ by the RI detector. Polymer purity = (polymer peak area) / (polymer peak area + peak area of monomer or impurity) &lt;Measurement conditions of solid content component&gt; A sample of about 0.5 g was taken in an aluminum suit, and about lg was used. The water is diluted to spread it evenly. In a nitrogen atmosphere and at 130. The crucible was dried for J hours, and after cooling in a desiccator ten, the weight after drying was measured. The solid content (nonvolatile content) concentration was calculated from the difference in reset before and after drying. The aqueous solution concentration of the synthesized phosphorus PAG compound or phosphorus PAG polymer, / unless otherwise specified, the solid content measured in the above order is used. &lt;Synthesis of a (poly)alkylene glycol-based compound (phosphorus PAG compound) containing a phosphorus atom&gt; Example 1 (RR-1 9 ) (1) Synthesis step as a monomer solution in sodium hypophosphite-hydration (SHP · 1Η2〇, 35.2g manufactured by Wako Pure Chemical Co., Ltd.), 3-methyl-3-ene butene-alcohol as 3-methyl-3-butene_i = alcohol alkylene oxide adduct A total of 232. g of a solution was prepared by adding ion-exchanged water to an ethylene oxide adduct (average ethylene oxide addition number: 10 mol, 87.5 g). As a starter solution, ion-exchanged water was added to sodium persulfate (aPS manufactured by Wako Pure Chemical Industries, Ltd., 〇. 6 g) to prepare a total of 51 Torr. 4 In a glass reaction with a Dairy cooling tube, Teflon (R), a stirrer with a stirring blade and a Fengzi, a nitrogen introduction tube, and a temperature sensor, the container solution is added to the container. The mixture was heated to 7 Torr while introducing nitrogen gas at 20 〇mL/min in a state of 3 pm into (4). Hey. Then, it took 3.5 hours to drip the above-mentioned initiator solution into the reaction vessel. After the completion of the dropwise addition, 97 (TC was kept for 1 hour, and the reaction was cooled to the 'dish' to obtain an aqueous solution of the target compound. (2) The purification step was rotated. The obtained aqueous solution of the target compound was distilled off under reduced pressure of an evaporator, and then dried by heating in a vacuum oven to obtain a white turbid residue. The slurry was suspended in 300 ml of THF to reduce it. Pressurization and filtration. The filtrate was decompressed by a reduced pressure evaporator, and then dried in a vacuum oven for one night to obtain a colorless oil. The obtained oil was dissolved in 150 g of ion-exchanged water, and a total of 90 ml of the ring was used. The extraction was carried out for 6 times, and only the aqueous phase was separated and distilled off under reduced pressure by a rotary evaporator, and then dried and solidified overnight by a vacuum oven heated to 5 ° C to obtain the target compound. The structure was identified by NMR and LC-MS. 1H-NMR (400MHz, D20): δ = 1.07 (d, 3H), 1.4 8 (m, 1H), 1.57 (m, 2H), 1.72 (m) , 1H), 1.97 (m, 1H), 3.64 (1;, 2H) ' 3.66 to 3.75 (m, 40H), 6.43 (s, 0.5H), 7.69 (s, 0.5H) 31P-NMR (160MHz 'D20) (phosphoric acid is set to δ = 0) : δ = 28.97 ° LC-MS (ionization method: ESI Method) (Μ+Η) + 5 93.3 5. 72 Ο 201240937 Examples 2 to 8 (1) Synthesis procedure In the first embodiment, the starting material compound or the reaction conditions were changed as described in Table 1, except for the examples and the examples. The target compound (disc PAG compounds (2) to (8)) was obtained in the same manner. The contents of the raw materials PAG compounds A to G used are shown in Table 2. (2) The purification step is shown in Table 1 in Example 1. The target compounds (phosphorus PAG compounds (2), (3), (5) to (7)) were obtained in the same manner as in Example 1 except that the purification solvent was changed as described above. Example 9 As a monomer solution, Sodium hypophosphite monohydrate (SHP.1H20, 5.6g manufactured by Wako Pure Chemical Industries, Ltd.), 3-mercapto-3 as a 3-methyl-3-butene-1-alcohol alkylene oxide adduct — A total of 205.4 g of a solution was prepared by adding ion-exchanged water to an ethylene oxide adduct of an butene-alcohol (average ethylene oxide addition number: 50 mol, 130 g). To the initiator solution, a total of 44 6 g of a solution was prepared by adding ion-exchanged water to sodium persulfate (NaPS' 〇. 4 g manufactured by Wako Pure Chemical Industries, Ltd.). It was manufactured with a Dairy cooling tube and Teflon (R). The monomer solution was added to a glass reaction vessel equipped with a stirrer and a stirrer, a nitrogen gas introduction tube, and a temperature sensor, and the nitrogen was introduced at 200 mL/min under a stirring at 300 rpm. Heat to 9 一面 on one side. Hey. -fe and 'chemical cost 2.7 5 hours, the above initiator solution was dropped into the reaction vessel and kept at 90 ° C for 1 hour after the end of the dropwise addition, the reaction was terminated, and cooled to 73 201240937 at room temperature to obtain the target compound (phosphorus PAG compound). (9)) An aqueous solution. The final pH was 5.48. (Examples 10 to 12) The target compounds (phosphorus PAG compounds (10) to (12)) were obtained in the same manner as in Example 9 except that the starting compound or the reaction conditions were changed in the same manner as in the above. The contents of the raw material PAG compound used are shown in Table 2. 74 Purification step Separation solvent cyclohexane/ml 90.0 90.0 90.0 Unpurified 90.0 90.0 90.0 Unpurified 150.0 I 150.0 I 1 150.0 1 | 150.0 1 I 150.0 II 150.0 I Purification solvent 300.0 | 300.0 I 300.0 300.0 | 300.0 I | 300.0 I Species | THF | | THF I 1 THF 1 ί THF 1 | THF I MeCN unpurified unpurified unpurified unpurified synthetic step i initiator solution 50.4 τ-^ m 1 37.8 1 | 85.3 I 1 33.2 1 | 59.8 | 105.6 | | 84.2 IL 44.2" 38.0 丨 __ 38.4 一 | 27.3 NaPS Ό 〇ο ο 〇〇〇 〇 Η Η 〇〇 H H H H H H H H H H H H H H H H H H H H H H H H H 1 260.0 | | 153.0 I 1 ^7·1 1 1 loo.o 1 100.0 69.9 | | 90.0 1 [56.0 I 90.0 SHP · 1H20 35.2 27.7 12.0 45.6 43.7 inch · 19.0 40.1 11.2 in r Η 21.2 Raw material PAG Φ1 | 87.5 1 I 68.8 1 130.0 | 25.0 I | 87.5 I 1 68.8 | 1 25.0 1 | 25.0 | | 130.0 I 60.0 1 104.0 1 60.0 Type &lt;&lt; CQ 〇Q ΕΧ( 〇PQ &lt; ω ίΧ obtained phosphorus PAG compound phosphorus PAG compound (1) phosphorus PAG compound (2) phosphorus PAG compound (3) phosphorus PAG Compound (4) Phosphorus PAG compound (5) Phosphorus PAG compound (6) Phosphorus PAG compound (7) 1 Phosphorus PAG compound (8) Phosphorus PAG compound (9) Phosphorus PAG compound (10) Phosphorus PAG compound (11) Phosphorus PAG Compound (12) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 201240937 [Table 2] PAG Compound Structure A CH2=C(CH3)CH2CH2(OC2H4)10 - OH B CH2=C(CH3)CH2CH2(OC2H4)50 — OH C CH2=C(CH3)CH2(OC2H4)i - OH D CH2=C(CH3)CH2( OC2H4)8 — OH E CH2=C(CH3)CH2(OC2H4)15() — OH F CH2=CH2 — CH2 - (OC2H4)5 - OH G CH2=CH2 — (OC2H4)2 — OH Η CH2=CH - CO - (OC2H4)9 - och3 1 ch2=ch(ch3)-CO - (oc2h4)9-och3 J CH2=CH(CH3) - CO - (OC2H4)45 - 〇ch3 κ CH2=CH(CH3) - CO - (OC2H4)9〇- och3 &lt;Production of (poly)alkylene glycol-based polymer (phosphorus PAG polymer) containing phosphorus atom&gt; Example 13 As a monomer solution, in acrylic acid (AA, 15.lg A total of 37.7 g of a solution was prepared by adding ion-exchanged water. As a starter solution, ion-exchanged water was added to sodium persulfate (NaPS, manufactured by Wako Pure Chemical Industries, Ltd., 5.2 g) to prepare a total of 40.0 g of a solution. The phosphorus PAG obtained in Example 1 was added to a glass reaction vessel equipped with a Dairy cooling tube, a stirrer with a stirring blade and a stirrer manufactured by Teflon (R), a nitrogen introduction tube, and a temperature sensor. The compound (1) (4.9 g) and ion-exchanged water (11 7.4 g) were heated to 80 ° C while introducing nitrogen gas at 200 mL/min in a state of being scrambled at 3 rpm. Then, it took 2 hours to drip the above monomer solution into the reaction vessel, and it took 3 hours to drip the initiator solution into the reaction vessel. After the completion of the dropwise addition, the polymerization was terminated by maintaining at 80 ° C for 1 hour. After cooling to room temperature, an aqueous solution of the target 76 201240937 • a liquid (rabbit PAG polymer (1)) was obtained. The final is u. G P C analysis of gentleman · ^ w , -. The result was Mn = 4723 and Mw = 7360 for the polymer. ♦. The purity of the material was 94. 〇 2 ° / °. Further, in the following, the method in which the phosphorus PAG compound is added to the dad and the monomer solution is added dropwise to carry out the polymerization is shown as the polymer method 1. Example 14 The composition of the target polymer (5) PAG polymer (2)) was obtained in the same manner as in Example 13 except that the composition was changed as described in Table 3 in the Example 13, and the results of GPC analysis were shown. In Table 3. Example 1 5 /乍 was a monomer solution, and a total of 1 3 3 ·3 g was prepared by adding ion-exchanged water to acrylic acid (AA, 15.1 g), and the hindered PAG compound (1) (49 g) obtained in Example i. Solution. A solution of 2 〇 合g was prepared by adding ion-exchanged water to sodium sulfite (NaPS 5.2 g manufactured by Wako Pure Chemical Industries, Ltd.). Adding ion-parent water (46.7g) to a glass reaction with a Dairy's cooling tube and Teflon (R) with a blender and a blender, a nitrogen inlet tube, and a temperature sensor. In the state of being mixed with 3 〇〇r{)m, it was heated to 8 Torr while introducing nitrogen gas at 200 mL//min. Then, it took 2 hours to drip the above monomer solution into the reaction vessel. The initiator solution was dropped into the reaction vessel for 3 hours, and the polymerization was terminated by holding at C for 1 hour after the completion of the dropwise addition. After cooling to room temperature, an aqueous solution of the target polymer (scaled PAG polymer (3)) was obtained. The final result is 丨29. 77 201240937 The results of GPC analysis are shown in Table 3. The monomer solution and the phosphorus method are added as the polymer method 2, and the following is the case where water is added to the dad PAG compound solution for polymerization. The case of this side. Example 16 An aqueous solution of the object (4)) was obtained in the same manner as in Example 13 as shown in Table 3 in Example 13. The composition was changed as usual, and the standard polymer (phosphorus PAG) was used. The polymer shows the GPC analysis results in the table composition (SAA/phosphorus PAG combination) The conversion ratio of the substance (completely 3° with NaOH and (1) of the polymer in Table 3) is based on the case of completely neutralizing the acidity with NaOH. Table 201240937 [ε&lt;] GPC result (condition) 1) 2 1 94.0% 1 88.1% I 91.8% I 77.0% Mw 1 7360 1 3473 I 8443 | 4455 a [4723 1 12554 1 5148 I 3310 Starter solution 34.83 36.69 14.83 16.69 NaPS /g (iv) (iv) [3.31 | Body Solution 1 22.62 I | 13.01 I |113.33| |113.33| Phosphorus PAG Compound (1) / g 0.00 0.00 4.92 11.32 8.68 15.08 8.68 Dad Add 丨117.38 126.99 ί 46.67 | | 46.67 I Phosphorus PAG Compound (1) /g 4.92 11.32 0.00 0.00 Addition of SAA/Phosphorus PAG Compound (1) (wt%) 80/20 50/50 80/20 50/50 Polymer Process 1 Polymer Process 1 Polymer Process 2 Polymer Process 2 Phosphorus PAG Polymer Obtained Phosphorus PAG polymer (1) phosphorus PAG polymer (2) phosphorus PAG polymer (3) phosphorus PAG polymer (4) | Example 13 | Example 14 | Example 15 | Example 16

6L 201240937 Example I 7 As a monomer; a solution of 41. lg was prepared by adding ion exchange water to a solution of bupropion (Aa, 32.9 g). As a starter solution, a total of 36 〇g of a solution was prepared by adding ion-exchanged water to sodium persulfate (NaPS' ll. 4g manufactured by Wako Pure Chemical Industries, Ltd.). The phosphorus PAG obtained in Example 9 was added to a glass reaction vessel equipped with a Dairy cooling tube, a stirrer with a stirring blade and a stirrer manufactured by Teflon (R), a nitrogen introduction tube, and a temperature sensor. Compound (9) (57. lg) and ion-exchanged water (65.8 g) were heated to 8 (TC) while introducing nitrogen gas at 2 〇〇 mL in a state of rpm. The above monomer solution was dropped into the reaction vessel over 2 hours, and the initiator solution was dropped into the reaction vessel over 3 hours. After the completion of the dropwise addition, the polymerization was terminated at 8 (TC for 1 hour). After cooling to room temperature, finally Yang is 1. The aqueous solution of the compound (.PAG polymer (5)) is adjusted with a 30% aqueous solution of NaHH. The result of GPC analysis is that the polymer is η== 19〇7〇' 27921. The purity was 8 1.08%. Example 1 8 to 3 3 The composition was changed in the same manner as in Example 17 except that the composition was changed as described in Table 7, except that the target polymer (disc polymer (1): ~ (2 1 )) aqueous solution. 'The mass ratio of the polymer in Table 4 to the end of NaOH” The GPC analysis results are shown in Table 4. Further, the composition (S ( Μ ) AA / phosphorus PAG compound) was fully neutralized (represented by NaOH completely neutralizing the ox acid. 80 201240937 [inch &lt;] GPC results (conditions) 2) CU 81.1% I 7S.4% I |78.3%| 77.5% 丨75.7%| 63.2% II 66.4% II 72.5% I 丨76_7%| 丨44.1%| |31.5%| I 26.3% 1 71.1%| I 68.2% I 65.9% 64.7% 1 62.3% S I27921I 19214 | ! 15430 I 13330 11780 16005 15524 15124 | 15594 丨37247 27743 23262 35875| 29961 27141I 24983 23303 C 2 1907〇| 114258 I | 12041I 10849| I 9904 I | 1121981 | 11912 II 12255 I | 22282 I 17846 | 15533 | 1 218571 j 22077 丨21652| 丨20500 | 19730 Starter solution ^4.56 128.92 30.87 |31.98| 32.69 38.86 137.72| 36.58 丨35.441 25.80 128.521 130.09| 30.97 ^3.24 34.10 丨134.55 1 34.83 NaPS /% | 11.44| g CO iri S rn 00 (N 〇j rn v〇— 10.201 to On »n S vi v〇(N 卜 monomer solution CN &lt;S οό ΟΟ CO (N 11.73 23.46 35.19 m On γ4 c^&gt; ΓΛ 00 cn »〇00 r4 &lt;N ν〇ro ΟΟ ΟΟ &lt;N CS ΟΟ ΟΟ ο {〇ο ^ 00 32.90 1 19.29 :13.20 m CO ON 〇i Ό 00 U-) 1 1 11.73 1 1 22.13 1 1 15.33 1 1 11.39 1 1 14.47 1 Os 00 rn VO ν〇&lt;Ν ! Dad added 65.78 , 69.18 70.70 i 71.57 1 72.12 128.27 1 96.54 1 1 64.81 1 [77.07 1 1 68.47 1 1 70.17 1 71-15 1 1 74.38 1 1 76.12 1 I 76.78 | 77.12 77.33 〇^ For $ 57.10 70.71 76.80 80.27 82.50 17.07 34.14 51.20 68.27 67.87 74.67 78.61 71.53 78.48 81.11 (Ν 00 83.34 (3 ·4π ^ =$彡^ 〇〇95/5 90/10 85/15 , 80/20 1 75/25 85/15 85/15 85/15 85/15 90/10 85/15 80/20 95/5 90/10 85/15 80/20 75/25 Phosphorus PAG compound used Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9 Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (11) Phosphorus PAG compound (11) Phosphorus PAG compound (11) Phosphorus ΡΑ 化合物 compound (ιι) Phosphorus PAG compound (11) Monomer used (a) (*) i 1 1 Polymer method polymerization Production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer production method 1 Polymer Process 1 | Polymer Process i| Polymer Process 1 Polymer Process 1 Phosphorus PAG Polymer Phosphorus PAG Polymer (5) Phosphorus PAG Polymer (6) Phosphorus PAG Polymer (7) Phosphorus PAG Polymerization (8) | Phosphorus PAG Polymer (9) Phosphorus PAG Polymer (10) Phosphorus PAG Polymer (11) Phosphorus PAG Polymer (12) Phosphorus PAG Polymer (13) Phosphorus PAG Polymer (14) Phosphorus PAG Polymerization (15) Phosphorus PAG Polymer (16) Phosphorus PAG Polymer (17) Phosphorus PAG Polymer (18) 1 Phosphorus PAG Polymer U9) Phosphorus PAG Polymer (20) Phosphorus PAG Polymer (21) | Example 17 Example 18|Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 | Example 26 j Example 27 | 1 Example 28| | Example 29| | 30| Example 31 1 Example 32| | Example 33 1 key t: yfB-: WW Spectrum «:«: W ^^i-&to1«o-ga (*) 201240937 &lt;About the used list Body&gt; In the following Example 34, 'Lightester P-1M&lt;&lt;&gt;&gt; manufactured by Kyoeisha Chemical Co., Ltd. &lt;1,2-hydroxyethyl methacrylate phosphate, di-[[2-hydroxyethyl]methyl phosphate A mixture of an acrylic acid ester and a tris-[(2-hydroxyethyl)methylpropionic acid] ester&gt; as a monomer having a scaly acid group (A). According to the analysis results, since the molar composition ratios of single vinegar (Mw: 210.12), double vinegar (Mw: 322.25), and diacetate (Mw: 434.37) are 6〇, 3〇, 10 (mol%), respectively, The calculation was carried out by setting the average molecular weight to 266 丨8. Further, the ellipses of the monomers in Table 5 indicate SpMp (sulfopropyl methacrylate, potassium salt manufactured by Aldrich Co., Ltd.), AAM (acrylic phthalamide manufactured by Wako Pure Chemical Industries, Ltd.), MA (manufactured by Wako Pure Chemical Industries, Ltd.). Maleic acid) 'HEA (2-hydroxyethyl acrylate). Example 3 4 ^ as a monomer solution in mono(2-hydroxyethyl) methacrylate, di-[(2-hydroxyethyl) decyl acrylate] and tris[3-(I) Ethyl)methacrylic acid] vinegar mixture (manufactured by Kyoeisha Chemical Co., Ltd.

LightesterP - 1MX 15.5g), and phosphorus pAG obtained in Example 9. (9) (24.5 g) + Adding ion-exchanged water to prepare a total of 74 g of the initiator solution, and adding ion-exchanged water to sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a total of 2&quot; It is dissolved in Luo; the ion-exchanged water is added to the anti-W of the glass made by Tie's Lengyuguan and Teflon (R) with a stirring wing, a feeder, a nitrogen gas guide, and a temperature sensor. (10) g), in the state of sandalwood 82 201240937 with 3 times Pm, one side was heated to 80 while introducing nitrogen gas at 200 mL/min. (: Then, it took 2 hours to drip the above monomer solution into the reaction vessel, and it took 3 hours to drip the initiator solution into the reaction vessel. After the completion of the dropwise addition, the polymerization reaction was terminated at 80 C for 1 hour, and the polymerization was terminated. After room temperature, an aqueous solution of the target polymer (phosphorus PAG polymer (2 2 )) was obtained by adjusting the pH of 6 with 3 〇0/〇 of Na〇H aqueous solution. The result of GPC analysis was that the polymer had Mn=48740, Mw = 7 3 1 9 6. Further, the polymer purity was 42.75%. Example 3 5 As a monomer solution, ions were added to sulfopropyl methacrylate and potassium salt (SPMP, 3 3.3 g manufactured by Aldrich). A total of 5 5.5 g of a solution was prepared by exchanging water. As a creping agent solution, ion-exchanged water was added to sodium persulfate (NaPS 3.79 g manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a total solution. The phosphorus PAG compound (9) obtained in Example 9 (56 7 g) was added to a glass reaction vessel made of a stirrer and a stirrer stirrer, a nitrogen gas introduction tube, and a temperature sensor manufactured by Teflon (R). ) Change water with ion parent (57.8g) and stir at 300rpm In the state, one side was heated to 8 Torr while introducing nitrogen gas at 200 mL/min. Then, it took 2 hours to drip the above monomer solution into the reaction vessel, and the initiator solution was dropped into the reaction vessel for 3 hours. After the completion of the addition, the polymerization reaction was terminated at 8 Torr &lt;t for 1 hour, and after cooling to room temperature, the mixture was adjusted to pH 6 with a 30% OH water bath to obtain an aqueous solution of the target polymer (small mg polymer (23)). The result of GPC analysis of 201240937 was Mn=23113 and Mw=r29364 of the polymer. Further, the purity of the polymer was 61.59%. Example 3 6 to 3 8 The composition was changed as described in Table 5 in Example 35, and An aqueous solution of the target polymer (phosphorus PaG polymer (24) to (26)) was obtained in the same manner as in Example 35. The results of GPC analysis are shown in Table 5. Further, regarding Table A, AA, HE The composition of the polymer of ruthenium (monomer/phosphorus pAG compound) is based on the complete neutralization conversion using NaOH (the case where the carboxylic acid is completely neutralized by CAM ATT λ λ &lt; μ said + α-like) The mass ratio is expressed. Ο 84 201240937 GPC results (Condition 2) CL, 42.S% 1- 61.6% 41 .0% 78.0% 73.6% 73196 29364 12189 13291 13837 1 48740 23113 10060 11142 10858 Initiator solution 24.37 26.21 25.29 1 25.61 35.08 NaPS /zm ν〇〇\ CO Inch ' 〇 \ cn inch ' (N 〇\ monomer solution Name \ 34.00 22.20 13.01 30.35 00 〇 inch monomer (C) /g 1___ 15.53 33.30 19.51 〇〇S 〇\ 〇^ &lt; ^ ^ ω) &amp;Η &lt;〇ON \ wear ¥ 24.47 〇〇〇〇〇〇 〇〇Monomer (a) /g 1_ ο ο 〇〇〇〇18.21 〇\ό Dad Add Order \ 100.00 57.80 66.99 55.65 65.92 Phosphorus PAG Compound (9) /g ο ο 56.70 70.49 65.79 73.70 Adding Component Monomer / Phosphorus PAG Compound (9) (mol%) 85/15 85/15 85/15 85/15 45/40/15 Phosphorus PAG compound used Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Monomer used (C) (*) 1 1 Oh SPMP AAM Monomer used in HEA dish (a) i 1 1 ί Polymer process polymer method 2 Polymer Process 1 Polymer Process 1 15 Phosphorus PAG Polymer Phosphorus PAG Polymer (22) Phosphorus PAG Polymer (23) Phosphorus PAG polymer (24) Phosphorus PAG polymer 1 (25) Phosphorus PAG polymer (26) Example 34 Example 35 Example 36 Example 1 37 Example 38 ί 叛, 遛韶紫肊硇 &- ^肊蝥:dHdS · ^♦^wig[铛爱"f&amp;-(ftof^-slw^#^ls¥^t€:&lt;M®-(^to4li-s_-r.sfc&lt;s^, Ii^^«^&amp;-(^N3f^—(s)1^sif:WI-d . 'K-^J-Dirol (*)

遛窝爱肊砩»0硪硪2:: V3H Helmet U love hif: vw ^1§««:WVY 201240937 Example 39 as a dropping solution in acrylic acid (AA, 15 lg), methoxy stretching Ethylene glycol acrylate (NKesterAM-90G, 12.6 g, manufactured by Shin-Nakamura Chemical Co., Ltd. with an average ethylene oxide addition number of 9 m) was added to the solution to prepare a total of 46.2 g of the solution. As a starter solution, a solution of a total of 3 〇g was prepared by adding ion-exchanged water to sodium persulfate (NPS 6.2 g manufactured by Wako Pure Chemical Industries, Ltd.). The phosphorus PAG obtained in Example 9 was added to a glass reaction vessel equipped with a Dairy cooling tube, a stirrer with a stirring blade and a stirrer manufactured by Teflon (R), a nitrogen introduction tube, and a temperature sensor. Compound (9) (62.3 g) and ion-exchanged water (61.5 g) were heated to 8 (rc) while introducing nitrogen gas at 2 〇〇 mL/min while stirring at 300 rpm. Then, it took 2 hours to The monomer solution was dropped into the reaction vessel, and the initiator solution was dropped into the reaction vessel over 3 hours. After the completion of the dropwise addition, the polymerization was terminated at 8 ° C for 1 hour, and after cooling to room temperature, 3% by weight was used. The aqueous solution of NaOH was adjusted to pH 6 ' to obtain an aqueous solution of the target polymer (referred to as pAG polymer (27)). As a result of GPC analysis, the polymer had η = 143 12 and Mw = 19667. Further, the polymer purity was 79.13%. An aqueous solution of the target polymer (phosphorus paG polymer (28) to (3 8 )) was obtained in the same manner as in Example 39 except that the composition was changed as described in Table 6 in Example 39. The contents of the raw material pag compound used are shown in Table 2. 86 Ο 201240937 The GPC analysis results are shown in Table 6. Furthermore, the composition (S AA/phosphorus PAG compound) is fully neutralized by the conversion of NaOH (the NaOH of Table 6 in the case of completely neutralizing the carboxylic acid with NaOH). The mass ratio is expressed. 87 201240937 〔9^1 GPC scar (condition 2) |79.1%| 1 76.3% 1 74.3% 79.5% I 78.4% II 78.7% 1 73.8% 78.3% I |81.2%| 1 72.8% I 181.5% 180.1% Mw 1196671 1 13127| 1 10317 I 20374 ! 19866 188391 I 53576I I 21490I 1 28910I 32340I 121357I 29448 G s 14312 | 10668| 1 8908 1 I 14300 I 14183 I 14023 | | 28044 | 151451 I 1781〇 | 18654| | 15833] 19771 Starting agent solution 123.76| 126.271 127.34 24.43 24.97 丨23.841 127.78| 23.79 32.18 140.421 129.201 27.261 NaPS /% 1 6.24 | 1 3-73 | 2.66 UsiJ [5.03 I 6.16 | 2.22 | kin 1 5-32 12.80 2.74 Addition solution 18.49 10.32 6.82 ^2.93⁄4 26.50^ hl9.02j 8.08 18.66 48.60 73.05 10.05 8.12 PAG Compound 00 | 12.64 | 丨7.57 1 1 5-40 1 | 22.58 | I 30.61 | | 13.62 | 0.00 | I 12.96 I 46.52 | I 78.19 | I 25.95 | 5.55 Monomer (a) CiO \ | 15.10 | 1 7. 91 4.84 I 11.80 1 丨9.14 | I 14.91 | 1 5.39 1 | 15.04 | I 12.88 | I 11.09| I 31.00 1 I 6.63 | Dad added |61.51 | 169.68| 73.18 157.08 | | 53.501 60.98 171.92| 61.34 51.40 46.95 57.95 71.88 PAG Compound/% 1 o.oo I 1 0.00 1 1 o.oo 1 1 o.oo | 1 o.oo | 0.00 | 62.41 | 1 o.oo | I 〇.〇〇| 0.00 0.00 0.00 Phosphorus PAG Compound/z 62.26 1 74.53 1 1 79.76 1 | 55.61 | I 50.25 | | 61.47 | | 22.20 | | 62.01 1 | 53.10 | | 45.72 | I 33.05 | 77.82 Add composition (Λ 80/10/10 70/20/10 60/30/10 70/10/20 60/10/30 80/10/10 80/10/10 80/10/10 80/10/10 80/10/10 80/10/10 80/10/10 PAG compound used XXXXX &lt; X &gt; 4 PAG compound phosphorus PAG compound (9) phosphorus PAG compound (9) phosphorus PAG compound (9) phosphorus PAG compound (9) phosphorus PAG compound (9) phosphorus PAG compound (9) phosphorus PAG Compound (9) | Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (9) Phosphorus PAG compound (10) Phosphorus PAG compound (11) Monomer used (a) AA ΑΛ AA AA AA Phosphorus PAG polymer phosphorus PAG Compound (27) Phosphorus PAG polymer (28) Phosphorus PAG polymer (29) Phosphorus PAG polymer (30) Phosphorus PAG polymer (31) Phosphorus PAG polymer (32) Phosphorus PAG polymer (33) Phosphorus PAG polymerization (34) Phosphorus PAG Polymer (35) Phosphorus PAG Polymer (36) Phosphorus PAG Polymer (37) Phosphorus PAG Polymer (38) | Example 39 | Example 40 | Example 41 | Example 42 I | Example 43 1 |Example 44 Example 45 | Example 46|1 Example 47| |Example 48 I Example 49 Example 501 201240937 . &lt;Epoxyalkylene addition reaction of multi-branched alcohol&gt; Synthesis example A1 : TMP—TMP — 30 Adding two Zhao Zhao Methyl Institute (manufactured by Wako Pure Chemical Co., Ltd., 2〇〇g 'hereinafter referred to as "TMP"), 30% aqueous sodium hydroxide solution (3 62g) to a blender Pressure resistant reactor. The temperature in the reaction system was heated to 100 C' using an oil bath, and the nitrogen gas was slowly bubbled in the system while using a vacuum to reduce the pressure to 1 〇〇mmT〇rr for 1 hour, and the water to the chamber was 2 53 g. Further, after the vacuum pumping was used for 1 hour to reduce the pressure to l〇〇mmT〇rr, the μ degree in the reactor was heated to i3 〇 °c, and nitrogen gas was introduced to adjust the internal pressure to 〇5 Mpa. Ethylene oxide (1969.9 g, 3 〇 mol times relative to TMP) was added while maintaining the internal temperature of the reactor at l3 〇 = t2 〇 c. Among them, the internal pressure of the reactor was not made to exceed 0.8 MPa. After completion of the addition of ethylene oxide, the reaction was terminated by maintaining the reactor at 130 T: for 1 hour. The yield was 99.7 °/ depending on the mass before and after the reaction. The trihydroxy decylpropane is an ethylene oxide 29 9 molar addition (hereinafter also referred to as r TMP - 30). Synthesis Example A2: TMP-30- TMP — 225 The starting material was set to TMP-30 (300 g), 30% aqueous sodium hydroxide solution (2.97 g), and ethylene oxide (1784 7 g, relative to TMP-3 196). The reaction was carried out in the same manner as in the synthesis example except for the molar ratio. An ethylene oxide 225 mole addition product (hereinafter also referred to as "TMP - 225") of trihydroxymercaptopropane having a yield of 99.6% was obtained. Synthesis Example A3: SB-&gt;SB-30 "A sorbitol (250 g, hereinafter also referred to as B" manufactured by Wako Pure Chemical Industries, Ltd.) 30/° aqueous sodium hydroxide solution (3, 44 g) was added thereto with stirring 89 201240937 The pressure reactor of the device. The temperature in the reaction system was heated to 130 ° C by using an oil bath. While nitrogen gas was slowly bubbled in the system, the pressure was reduced to 100 mm Torr by a vacuum pump for 1 hour, and water was distilled off. Further, after a vacuum pump was used for 1 hour to reduce the pressure to 100 mm TOrr, nitrogen gas was introduced to adjust the internal pressure to 〇5 MPa. While maintaining the internal temperature of the reactor at 13 ft. 2t, one side of the epoxy was added (1813.6 g, 30 mils relative to SB). Among them, the internal pressure of the reactor was not made to exceed 0.8 MPa. After the end of the addition of ethylene oxide, the reactor was placed at 130. (: The reaction was terminated by holding for 1 hour. An ethylene oxide 29 9 molar addition product of sorbitol (hereinafter also referred to as "SB-30") having a yield of 99.7% based on the mass before and after the reaction was obtained. Example A4: SB — 30 — SB — 120 The raw materials were set to SB-30 (600g), 30% aqueous solution of sodium hydroxide (2.66g), and ethylene oxide (1595 4g, relative to SB-3〇). In the same manner as in the synthesis example A3, the reaction was carried out. The yield of 99.7% of sorbitol ethylene oxide 12 〇 molar addition (hereinafter also referred to as " SB - 120"). Synthesis Example A5: SB~12〇-&gt; SB-450 The raw material was set to SB - 120 (550g) '30% aqueous sodium hydroxide solution (2.44g), ethylene oxide (1462, The reaction was carried out in the same manner as in Synthesis Example A3 except that SB_3 was 330 mol.) A sorbitol 45 〇 molar addition product of sorbitol having a yield of 99.6 Å was obtained ( Hereinafter also referred to as "SB-450"). &lt;Addition reaction of multi-branched alcohol with allylepoxypropyl ether&gt; Synthesis Example B1

90 201240937 A synthetic reaction example A5 is added to a glass reaction vessel equipped with a Dairy cooling tube, a stirrer with a stirring blade and a stirrer manufactured by Teflon (R), a nitrogen gas introduction tube, and a temperature sensor. SB-450 (236.3 g) and 48% NaOHaq (0.79 g) were stirred at 300 rpm while stirring with nitrogen at 1000 mL/min for 3 hours at 120 °C. While stopping the bubbling of nitrogen gas and continuing to stir, a propyl propyl propyl hydrazine (AGE, 8.1 g manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. While stirring at 300 rpm, nitrogen gas was introduced at 20 mL/min while stirring at 350 ° C for 3.5 hours. Thereafter, the mixture was stirred at 300 rpm for 2 hours, and nitrogen gas was bubbled at 1000 mL/min to remove unreacted AGE to obtain a target compound (multi-branched monomer (1)). According to the LC analysis result after the completion of the reaction, the consumption rate of SB-450 was confirmed to be 97%, and the average AGE introduction number of the SB-450-molecule was 2.97. Synthesis Example B 2 to B 5 The target compound (multi-branched monomer (2) to (5) was obtained in the same manner as in Synthesis Example B1 except that the starting compound or the reaction conditions were changed as described in Table 7 in Synthesis Example B1. )). [Table 7] Multi-branched monomer raw material obtained by multi-branched alcohol addition composition AGE/alcohol (mol) Alcohol/% 48% NaOH aq / g AGE /g Synthesis Example B1 Multi-branched monomer (1) SB450 6/1 236.31 0.79 8.09 Synthesis Example B2 Multi-branched monomer (2) SB450 3/1 235.17 0.78 4.03 Synthesis Example B3 Multi-branched monomer (3) SB30 6/1 164.35 7.29 74.85 Synthesis Example B4 Multi-branched monomer (4) SB30 3/1 194.83 8.64 44.37 Synthesis Example B5 Multi-branched monomer (5) TMP225 3/1 219.07 1.45 7.47 &lt;Synthesis Example of a multi-branched (poly)alkylene glycol compound (multi-branched phosphorus 91 201240937 PAG compound) containing a phosphorus atom 51 ( RR~86) is a monomer solution, sodium hypophosphite monohydrate 16 (SHP · 1 Η, Ο 7 / ς, ' 2 〇 '3, 6g manufactured by Wako Pure Chemical Co., Ltd.) and synthesis example Β1 Multi-branched monomer (1) § Add ion-exchanged water to prepare a total of 320. g of solution. As a starter solution, it is made in sodium persulfate (Wako Pure Chemical Co., Ltd.)

A total of 76.4 g of a solution was prepared by adding ion-exchanged water to NaPS, G.3g). &quot;Addition of the above-mentioned early body solution to the glass reaction made by the Dynacool cooling tube and Teflon (R) with the (four) wing and:: the stirring thief, the nitrogen introduction tube, and the temperature sensor 'In the state of mixing with 3 () (), one side is heated to 9 (rc., .M and * 2.7 for 5 hours to introduce the above initiator solution while introducing nitrogen gas at 2 〇〇 mL/min. Into the reaction vessel $. After the completion of the dropwise addition, the reaction was terminated at 90 ° C for 1 hour, and cooled to room fox to obtain an aqueous solution of the target compound (multi-branched phosphorus pAG compound (丨)). Examples 52 to 55 were used in Example 51. The target compound (multi-branched phosphorus PAG compound (2) to (5)) was obtained in the same manner as in Example 51 except that the starting compound or the reaction conditions were changed as described in Table 8. 92 201240937 [Table 8] Phosphorus PAG compound synthesis step obtained monomer solution initiator solution raw material PAG SHP · 1H20 /% water /% NaPS /% water /% kind /g Example 51 Multi-branched phosphorus PAG compound (1) Multi-branched monomer (1) 208. (8) 5.92 112.00 0.57 73.51 Example 52 Multi-branched phosphorus PAG compound (2) Multi-branched monomer (2) 208.00 3.01 112.00 0.29 76.70 Example 53 Multi-branched phosphorus PAG compound (3) Multi-branched monomer (3) 208.00 66.33 80.89 6.44 38.34 Example 54 Multi-branched phosphorus PAG compound (4) Multi-branched monomer (4) 208.00 27.98 112.00 2.72 49.31 Example 55 Multi-branched phosphorus PAG compound (5) Multi-branched monomer (5) 208.00 5.71 112.00 0.55 73.74 &lt;Multi-branched (poly)alkylene glycol-based polymer containing phosphorus atom ( The preparation of the multi-branched phosphorus PAG polymer) was carried out as a monomer solution, and ion-exchanged water was added to the acrylic acid (AA, 5.0 g) to prepare a total of 20. lg of the solution. A total of 30.0 g of a solution was prepared by adding ion-exchanged water to sodium (NaPS, manufactured by Wako Pure Chemical Industries, Ltd.). The stirring was carried out with a stirring blade and a stirrer manufactured by a Dynacool tube and Teflon (R). The multi-branched phosphorus PAG compound (1) (RR-86) (75.0 g) obtained in Example 51 and the ion-exchanged water (74_9 g) were added to a glass reaction vessel of a nitrogen inlet tube and a temperature sensor. Stirring at 300 rpm Under side to 200mL / min nitrogen was introduced to a heated face 8 (TC. Then, the monomer solution was added dropwise spending 2 hours the reaction vessel, takes 3 hours initiator solution was added dropwise to the reaction vessel. After the completion of the dropwise addition, the polymerization was terminated by maintaining at 80 ° C for 1 hour. After cooling to room temperature, it was adjusted to pH 6 with a 30% 93 201240937 NaOH aqueous solution to obtain an aqueous solution of the target polymer (multi-branched phosphorus PAG polymer (1)). The final pH was 3.54. The results of the GPC analysis were Μη = 61832 and Mw = 127735 for the polymer. Further, the polymer had a purity of 59.17%. The results are shown in Table 9.

94 201240937 GPC results (Condition 3) 〇H (N 〇\ U-ϊ CN *—η 1 CS m oo 3 Starting agent Ώ 8.25 NaPS /g 绂 15.08 System S wi Dad add order 74.92 〇^ 74.97 Addition of AA/Phosphorus PAG compound (mol%) 85/15 Phosphorus PAG compound used to multi-branched phosphorus PAG compound (1) Monomer polymer used in the preparation of polymer method 1 Phosphorus PAG polymer multi-branched phosphorus PAG polymerization obtained (1) Example 56 201240937 &lt; mortar test&gt; Using the aqueous solution of the polymer produced in Examples 13 to 2 1, 26 to 5, 56, a mortar was prepared in the following manner, and the initial air amount and initial amount were measured. And 15 strokes after 15 knives. In addition, the initial air volume and the initial flow rate of 15 amps were measured for the comparison of the original water-soluble night (water only). The results are shown in Tables 10 to 14, respectively. In addition, in the mortar test, the raw water sulphate is removed, and the amount of 〇4% (manufactured by BASF Pozzolith Co., Ltd.) as the defoaming agent is in the original state and is 丨〇 mass% relative to the polymer solid content. Add to the aqueous polymer solution. &lt; mortar &gt; Mortar test is carried out at a temperature of 2 (rc ± rc, relative humidity of 6〇% ± 〇 〇 % &lt; environment. The sand blending system is set to C / zS / w = 55 〇 / / 135 〇 / 22〇(1). C: '曰通 Portland cement (made by Pacific Cement Co., Ltd.) S: Standard sand for cement strength test (manufactured by Cement Association) W: ^(4)(4) or ratio (tetra) compound and ion exchange of defoamer The liquid, as w, is added to the polymerization of the addition of Tables 10 to 14. The original state is added with respect to the polymer solid amount of V + β 4 Jay. ΜΑ - 404, and then add:: 詈 詈 并使 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈#八α Τ 'The composition of the solids of the polymer mouth is expressed relative to the water. 八 / The factory is the mass% of the CC^· 96 201240937 The Yuba Bart mortar mixer (Model 50, manufactured by Hobart, Inc.) Stainless steel mixing 芎 (褽坆) 讦 讦 益 C stirring wing), put C, W and practice with the lamp 30. Then the surface is mixed at 1 speed - the surface costs 30 to invest S After 4 strokes of S, 'I practice 3G seconds at 2nd speed, '2nd mixing' takes 15 seconds to shake off the mortar, then rests for 75 seconds. After standing for 75:, then 6 seconds at 2 speeds Mixing, preparing mortar. And measuring the stone/slurry property value, when mixing the mortar, the time of mixing /, W is again 〇. "Initial" means the condition measured after the mortar is prepared. Ordering &lt;Measurement of Mortar Air Volume (Initial Air Amount)&gt; Approximately 200 mL of sand is poly-filled in a 5 〇〇mL glass measuring cylinder, and a circular rod of 8 Å is used to sway, and the hand is slightly vibrated by hand. And release & big bubbles. Further, by adding sand of about fan mL, after releasing the bubbles in the same manner, the volume and mass of the y ring are measured, and the amount of air is calculated according to the density of each material. &lt;15 Flow rate measurement&gt; The mortar was transferred from a kneading container to a 1 L container made of polyethylene, and stirred by a spatula for 2 times, and then immediately filled in a liquid amount (described in JISR5201 - 1997). The flow cone (described in JISR52〇i_i997) was applied for 15 times with a pry bar, and then the sand E was filled until the flow cone was filled, and the crowbar was used for 15 times, and finally the insufficient portion was added to form the surface of the flow cone. Immediately thereafter, the flow taper is vertically vertically, and the diameter of the diffused mortar (the diameter of the longest portion (long diameter) and the diameter of the portion which is 9 degrees with respect to the long diameter) is measured at two places, and the average value thereof is set to Beat the flow value. After measuring the value of the beater flow, s 97 201240937 immediately performed 下落5 drop movements in 15 seconds. 'Determination of the spread of the straight stalks at the 2 points (the longest part of the diameter (long diameter) and relative to the above long diameter The diameter of the portion is 90 degrees, and the average value is set to 15 flow rate. Also, the amount of mortar air is measured as needed. Further, the larger the value of the 0 flow rate value and the 15 flow rate value, the more excellent the dispersion performance. Sanding, Examples 1 to 4, and Sanding Comparative Examples 1 to 2 In the mortar Comparative Example 1, a test of the original aqueous solution (water only) was carried out, and as a result, the flow rate of 15 was 150 mm. In Mortar Comparative Example 2, the Pag compound (A) 0.5% by weight/c' as a raw material of the polymer of Examples 13 to 16 was added, and the increase in the flow rate of i 5 was hardly observed as compared with the original aqueous solution. In any of the comparative examples, no fluidity was obtained after 15 minutes, and therefore the flow rate value was not measured. On the other hand, in the examples 1 to 4 of the mortar to which the phosphorus PAG polymer was added, the 'having clearly' 15 flow rate values were remarkably improved, and the phosphorus Pag polymer had a remarkable cement dispersion effect. Example 1 The composition of the acrylic acid (AA) of the polymers of 3, 15 and 14 and 16 and the PAG-filled compound were 8〇/2〇 (wt%) and 5〇/5〇 (wt /◦, respectively). The result of the mortar test is that the mortar fluidity in any of the polymers is higher than that of the original aqueous solution. These results are shown in Table 1. Ο 98 201240937 [Table 〇] Addition amount/wt% in addition to the added phosphorus PAG polymer to C Initial air amount (vol%) 15 stroke flow rate / mm 15 stroke flow ratio (15 minutes / boring start) Initial 15 minutes mortar Example 1 Phosphorus PAG polymer (1) 0.50 2.6% 191 127 66% Mortar Example 2 Phosphorus PAG polymer (2) 0.30 2.8% 192 142 74% Mortar Example 3 Phosphorus PAG polymer (3) 0.50 2.7% 174 120 69% Mortar Example 4 Phosphorus PAG Polymer (4) 0.30 3.0% 168 138 82% Mortar Comparative Example 1 None (Original Aqueous Solution) 0.00 2.5% 140 No Flow No Flowing Mortar Comparative Example 2 PAG — A 0.50 2.7 % 147 No flow and no flow mortar Examples 5 to 17 7. Mortar Comparative Example 3 In the mortar Comparative Example 3, a test of the original aqueous solution (water only) was carried out, and as a result, the flow rate of 15 was 141 mm. On the other hand, in Examples 5 to 17 of the mortar to which the phosphorus PAG polymer was added, it was confirmed that the flow rate of the 15 hits was remarkably improved, and the phosphorus PAG polymer had a remarkable cement dispersion effect. These results are shown in Table 11. [Table 11] Added phosphorus PAG polymer addition amount / wt% to C phase initial air amount (vol%) 15 initial flow value / mm Mortar Example 5 Phosphorus PAG polymer (5) 0.30 2.0% 147 Mortar example 6 Phosphorus PAG polymer (6) 0.30 2.5% 171 Mortar Example 7 Phosphorus PAG polymer (7) 0.30 2.3% 176 Mortar Example 8 Phosphorus PAG polymer (8) 0.30 2.6% 169 Mortar Example 9 Phosphorus PAG polymer (9) 0.30 2.3% 162 Mortar Example 10 Phosphorus PAG polymer (14) 0.30 2.4% 169 Mortar Example 11 Phosphorus PAG polymer (15) 0.30 2.1% 171 Mortar Example 12 Phosphorus PAG polymer (16) 0.30 2.9 % 167 Mortar Example 13 Phosphorus PAG Polymer (17) 0.20 2.6% 163 Mortar Example 14 Phosphorus PAG Polymer (18) 0.20 2.1% 184 Mortar Example 15 Phosphorus PAG Polymer (19) 0.20 2.8% 172 Mortar Example 16 Phosphorus PAG polymer (20) 0.30 2.1% 179 Mortar Example 17 Phosphorus PAG polymer (21) 0.30 2.4% 163 Mortar Comparative Example 3 None (original aqueous solution) 0.00 2.9% 141 99 201240937 Mortar Example 1 8~23, Mortar Comparative Example 4 In the mortar Comparative Example 4, the original aqueous solution (water only) was tested, and the result was 15 flow. Value 147mm. On the other hand, in Examples 18 to 23 of the mortar to which the PAG-filled polymer was added, it was confirmed that the flow rate of the pump was significantly increased, and the phosphorus PAG polymer had a remarkable cement dispersion effect. Further, in Mortar Example 22 (phosphorus PAG polymer (26)) and mortar example (phosphorus PAG polymer (7)), the mortar also exhibited good fluidity after 15 minutes from the start of water injection. On the other hand, in Comparative Example 4, fluidity was not obtained at all after 15 minutes, and therefore the flow rate value was not measured. As apparent from the above, the phosphorus PAG polymer of the present invention not only exerts a cement dispersing effect, but also maintains the cement dispersing effect over time. The results are shown in Table 12. [Table 12] Added phosphorus PAG polymer addition amount / wt% to C initial air amount (vol%) 15 flow j: value / mm initial 15 minutes mortar Example 18 phosphorus PAG polymer (22) 0.30 2.8% 152 Unmeasured Mortar Example 19 Phosphorus PAG Polymer (23) 0.30 2.8% 152 Unmeasured Mortar Example 20 Phosphorus PAG Polymer (24) 0.30 2.6% 149 Unmeasured Mortar Example 21 Phosphorus PAG Polymer (25) 0.25 2.3% 188 Unmeasured Mortar Example 22 Phosphorus PAG Polymer (26) 0.35 2.5% 174 173 Mortar Example 23 Phosphorus PAG Polymer (7) 0.25 2.6% 183 167 Mortar Comparative Example 4 None (Original Aqueous Solution) 0.00 2.8% 147 No Flow Mortar Examples 24 to 35, Mortar Comparative Example 5 In the sand polymerization Comparative Example 5, a test of the original aqueous solution (water only) was carried out, and as a result, the flow rate of 15 strokes was 144 mm. On the other hand, in Examples 24 to 35 of the mortar to which the phosphorus PAG polymer was added, it was confirmed that the flow rate of the 15 hits was remarkably improved, and the phosphorus PAG polymer had a remarkable cement dispersion effect. These results are shown in Table 13. 100 201240937 [Table 13] Addition of phosphorus PAG polymer added amount / wt% to C Initial air amount (vol%) 15 initial flow value / mm Mortar Example 24 Phosphorus PAG polymer (27) 0.20 2.4% 190 Mortar implementation Example 25 Phosphorus PAG Polymer (28) 0.20 3.1% 164 Mortar Example 26 Phosphorus PAG Polymer (29) 0.20 3.4% 153 Mortar Example 27 Phosphorus PAG Polymer (30) 0.20 2.6% 196 Mortar Example 28 Phosphorus PAG Polymerization (31) 0.20 2.5% 194 Mortar Example 29 Phosphorus PAG polymer (32) 0.20 2.0% 185 Mortar Example 30 Phosphorus PAG polymer (33) 0.15 2.5% 201 Mortar Example 31 Phosphorus PAG polymer (34) 0.15 2.7% 170 mortar example 32 phosphorus PAG polymer (35) 0.15 2.2% 187 mortar example 33 phosphorus PAG polymer (36) 0.15 2.7% 178 mortar example 34 phosphorus PAG polymer (37) 0.25 2.7% 167 mortar implementation Example 35 Phosphorus PAG polymer (38) 0.25 2.3% 188 Mortar Comparative Example 5 None (original aqueous solution) 0.00 2.3% 144 Mortar Example 3 6. Mortar Comparative Example 6 In the mortar Comparative Example 6, the original aqueous solution (water only) was used. The test results in a flow rate of 143 mm. On the other hand, in Example 36 of the mortar to which the multi-branched phosphorus PAG polymer (1) was added, it was confirmed that the flow rate of 15 hits was increased, and the multi-branched phosphorus PAG polymer (1) had a cement dispersion effect. The results are shown in Table 14. [Table 14] Added phosphorus PAG polymer addition amount / wt% to C initial air amount (vol%) 15 initial flow value / mm Mortar Example 36 Multi-branched phosphorus PAG polymer (1) 0.70 2.7% 183 Mortar comparison Example 6 None (original aqueous solution) 0.00 3.5% 143 or more, according to the results of Tables 10 to 14, it was confirmed that the phosphorus-containing (poly)alkylene glycol-based polymer of the present invention can be preferably used in a small amount. It is a cement mixture which is excellent in initial dispersibility and dispersion retention. 101 201240937 &lt;Concrete test&gt; Concrete test examples 1 to 6 Next, the results of the performance evaluation by the concrete test of the polymer of the present invention obtained in the examples and the comparative polymer obtained in the comparative example will be described. &lt;Concrete test method&gt; Concrete blending: Using the polymer of the present invention obtained in the examples as a cement admixture, the concrete was blended and kneaded by blending as shown in Table 15. Further, the polymer of the present invention obtained in the examples or the comparative polymer obtained in the comparative example was used as a cement admixture. The blending amount of the blending agent was calculated from the amount of the solid content of the blending agent, and is shown in Table 16 as a percentage (% by mass) based on the mass of the cement. The antifoaming agent was blended with MA404 (manufactured by BASF P0ZZ0lith Co., Ltd.) with water = mass of 0.0〇8%, and the amount of air in the concrete was adjusted to 2% or less. Concrete mixing method: Add cement (8) and sand (s) to the capacity hunger and strong dragon mixing plate mixer with the blending shown in Table 15, and after 1 () seconds of dry stirring, add water and cement mixture. (W), knead until the mortar becomes uniform. After the stone slurry was homogenized, stone (G) was added and kneaded for 9 sec seconds to prepare a condensate. Here, the number of seconds spent on sand mixing is taken as "mixing time. ^, the maximum mortar mixing time is set to 12 sec." Eight evaluation methods: According to the Japanese X industry specifications (mAUG1 - recommended year m na 201240937 « year , A6204 - 2 006), the determination of the brightness flow value of the concrete obtained by blending each concrete. Furthermore, the greater the value of the mobility, the higher the fluidity of the concrete. If the flow rate values are the same, the smaller the added amount, the better the cement dispersion performance and the higher the water reduction performance. [Table 15] Content of concrete blending w/cs/a Air W c GS s Dajingchuanchuan sand Junjinshan sand 30 47 30 172 573 866 749 9 1 • Cement (c)...Ordinary Portland cement manufactured by Pacific Cement Company • Coarse aggregate (G)... Green plum hard sandstone. Fine aggregate (S)... Dajingchuan Sichuan sand (specific gravity 2.59), Junjin mountain sand (specific gravity 2.53) • Cement mixture, defoamer and water mixture (W) [ Table 16] Concrete Mixture Test Results Addition of Phosphorus PAG Polymer Addition/wt% vs. C MA-404 /wt% vs. C Temperature Flow Value/mm Air Volume / vol% Mixing Time (sec) Concrete Test Example 1 Phosphorus PAG Polymer (6) 0.38 0.008 20.0 615 0.6 40 Concrete Test Example 2 Phosphorus PAG Polymer (7) 0.50 0.008 21.5 573 0.9 40 Concrete Test Example 3 Phosphorus PAG Polymer (8) 0.75 0.008 21.0 575 0.7 35 Concrete Test Example 4 Phosphorus PAG polymer (18) 0.38 0.008 21.0 638 0.6 30 Concrete test example 5 Phosphorus PAG polymer (19) 0.52 0.008 21.0 595 0.8 40 Concrete test example 6 Phosphorus PAG polymer (20) 0.83 0.008 21.0 608 0.7 35 Concrete Comparative Example 1 None (original aqueous solution) 0.00 0.000 No 6 movable in Table 1 represents 1, concrete results of Test Example Comparative Example 1~6 of concrete. In Concrete Comparative Example 1 in which only water was used for kneading, concrete was not able to obtain fluidity, and measurement of flow rate or the like was not performed. · 103 201240937 In another aspect, a concrete test example in which the polymer of the present invention is added! ~6 t, concrete can obtain sufficient fluidity. From the above, it is clear that the polymer of the present invention has properties as a concrete mixture imparting fluidity to concrete. &lt;Hydrolysis performance test&gt; With respect to the polymer obtained in Example 19, the hydrolysis performance (storage stability) was evaluated in the following manner. &lt;Hydraulic property (60 ° C) test method&gt; Preparation 30 mass% ❹/. The aqueous solution of the polymer (phosphorus PAG polymer (7)) obtained in Example 19 was diluted to a level of 4, 7, or 9 using a 3 % aqueous sodium hydroxide solution. The respective polymer aqueous solutions were measured over time in a weight average knife (Mw) and polymer purity in the case where the liquid temperature was kept for 〇~9 丨. Further, the ratio of the weight average molecular weight () based on the short-term adjustment (preserved day) was calculated. Regarding the viscosity, the viscosity and viscosity ratio based on the viscosity adjustment (storage day) as a reference were calculated using the B-type viscometer in the same manner. Further, regarding each pH, the samples of the week, 2 weeks, and 4 weeks were evaluated for the performance by the mortar test. The liquid temperature of the aqueous polymer solution was maintained at 60 ° C during storage. The results are shown in Tables 17 to 19. Further, in Fig. i, a graph comparing the Mw ratios shown in Table 17 with the respective pH values is shown, and in Fig. 2, a graph comparing the viscosity ratio with each pH value is shown, and in Fig. 3, a mortar test is shown. A chart of performance evaluations. Further, in order to compare the hydrolysis performance, the polymer ρρτ127 obtained by using the PAG thiol compound § 己 〇 24 24 24 24 24 24 24 24 24 24 24 ( ( ( 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 128 (Example P - 39) The ratio of the weight average molecular weight (Mw) based on the short-term (storage 0 days) adjusted to pH 7 was shown in Table 20 as Comparative Example 1 and Comparative Example 2, respectively. [Table 17] Phosphorus PAG polymer pH storage time (days) Mw P% Mw ratio vs. Oday Phosphorus PAG polymer (7) pH4 0 15816 77.1% 100.0% 5 15991 76.4% 101.1% 7 16093 76.3% 101.8% 14 15644 76.4% 98.9% 21 15612 76.6% 98.7% 28 15405 76.5% 97.4% 56 15649 76.6% 98.9% 91 16272 74.6% 102.9% pH7 0 15832 76.6% 100.0% 5 16221 77.8% 102.5% 7 16524 78.4% 104.4% 14 15994 78.1 % 101.0% 21 16010 78.3% 101.1% 28 15752 78.1% 99.5% 56 16018 79.1% 101.2% 91 16314 76.6% 103.0% pH9 0 15851 76.3% 100.0% 5 16365 78.6% 103.2% 7 16518 77.3% 104.2% 14 16124 78.7% 101.7% 21 16145 79.2% 101.9% 28 15875 78.4% 100.2% 56 16023 78.2% 101.1% 91 16410 78.4% 103.5% 105 2· 201240937 [Table 18] Phosphorus PAG polymer pH storage time (days) Viscosity (cP) Viscosity ratio vs.Oday Phosphorus PAG Polymer (7) pH4 0 21.9 100.0% 7 22.2 101.2% 14 21.7 98.9% 21 22.0 100.6% 28 22.1 100.8% 56 21.8 99.5% 91 22.3 102.0% pH7 0 29.1 100.0% 7 30.6 104.9% 14 29.5 101.3% 21 29,7 102.1% 28 30.0 103.0% 56 29.5 101.4% 91 29.7 101.9% pH9 0 30.2 100. 0% 7 31.4 104.3% 14 31.3 103.7% 21 31.2 103.5% 28 30.6 101.5% 56 30.9 102.4% 91 30.8 102.3% [Table 19] Phosphorus PAG polymer PH Storage time (days) 15 strokes (mm) Phosphorus PAG polymer (7) pH4 0 215 14 220 28 216 pH7 0 215 14 215 28 211 pH9 0 206 14 208 28 208 106 201240937 [Table 20] Polymer PH storage time (days) Mw P% Mw ratio vs. Oday Comparative Example 1 ( * ) (Example p - 38) pH7 0 67503 96.4% 100.0% 7 65116 96.3% 96.5% 14 63674 96.4% 94.3% 28 61665 95.5% 91.4% 56 58599 94.9% 86.8% 84 54833 95.1% 81.2% Comparative Example 2 ( *) (Example P - 39) pH7 0 70215 96.8% 100.0% 7 66988 96.5% 95.4% 14 66590 96.5% 94.8% 28 64956 95.9% 92.5% 56 63325 94.9% 90.2% 84 60362 95.0% 86.0% (*)Comparative The information of the examples is the information of Example P-38 (Comparative Example 1) and Example P-39 (Comparative Example 2) described in WO2010/029924A1. Comparative Example 1 and Comparative Example 2 are polymers having an ester bond in the molecule, and the weight average molecular weight (Mw) thereof decreases with the passage of time. On the other hand, in any of the pH regions, the weight average molecular weight (Mw) and the viscosity ratio of the polymer obtained in Example 19, and the mortar fluidity were not largely changed. Therefore, it is clear that the phosphorus PAG polymer is relatively stable to hydrolysis. &lt;Gypsum dispersibility evaluation&gt; The evaluation method is as follows. &lt;Flowability&gt; A hydraulic material composition (gypsum slurry) was filled in a flow cone having a diameter of 5 Ommx and a height of 50 mm, and the breadth (mm) after the extraction was measured. &lt;Preparation of hydraulic material composition (gypsum slurry)&gt; According to JIS R9112 - 1978, 266 g of hemihydrate gypsum (Gravel Grade Gypsum for sculpture art manufactured by Yoshino Gypsum Sales Co., Ltd.) and defoaming The agent, the polymer obtained in Examples 19, 30, 39, and 45, and 426 g of an aqueous solution of ion exchange 107 201240937 water exchange were mixed to prepare a gypsum slurry. The fluidity (flow rate value) was measured using the obtained gypsum slurry. The results are shown in Table 21. [Table 21] Added phosphorus PAG polymer addition amount / wt% to C Defoamer / ppm to gypsum flow value / mm Gypsum Example 1 Phosphorus PAG polymer (7) 0.01 50 200 Gypsum Example 2 Phosphorus PAG polymer (18) 0.01 50 201 Gypsum Example 3 Phosphorus PAG polymer (27) 0.01 50 205 Gypsum Example 4 Phosphorus PAG polymer (33) 0.01 50 202 Gypsum Comparative Example 1 None (original aqueous solution) 0.00 0 190 Gypsum Example 1 ~4. Gypsum Comparative Example 1 In the gypsum Comparative Example 1, a test of the original aqueous solution (water only) was carried out, and as a result, the flow rate value was 1,85 mm. On the other hand, it has been clarified that in the gypsum examples 1 to 4 to which the phosphorus PAG polymer is added, the flow rate values are all increased, and the phosphorus PAG polymer of the present invention has a gypsum dispersing effect. Further, in the above examples, the effects of the (poly)alkylene glycol-based compound containing a phosphorus atom and the polymer produced by using the compound were actually confirmed. That is, a structure in which a terminal oxygen atom having at least one terminal of a (poly)alkylene glycol chain is bonded to a phosphorus atom via an organic residue and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond The (poly)alkylene glycol-based compound containing a phosphorus atom can be easily and efficiently produced at a low cost for a polymer useful in various applications, particularly cement cement applications, and the polymer is especially cement. The mechanism of action which exhibits various useful effects in the use of a mixed agent or the like is completely the same as that in the case of using the compound of the present invention. Therefore, according to the results of the above-described embodiments, the various inventions disclosed in the "Invention" section of the present invention can be applied to inorganic fine particles represented by cement or gypsum in particular; dispersion can be advantageous Fig. 1 is a graph comparing the weight average molecular weight (Mw) ratio in the hydrolysis performance (6 ° ° C) test with each pH value. Fig. 2 shows the hydrolysis performance (60. The graph of the viscosity ratio in the test compared with the respective pH values. Figure 3 is a graph showing the performance evaluation by the mortar test. [Main component symbol description] No 109

Claims (1)

201240937 VII. Patent application scope: 1. A (poly)alkylene glycol compound containing a phosphorus atom, which must have a phosphorus atom and a (poly)alkylene glycol chain, characterized in that the compound has the following structure: The terminal oxygen atom of at least one terminal of the polyalkylene glycol chain is bonded to the phosphorus atom via an organic residue, and the organic residue is bonded to the phosphorus atom by a phosphorus-carbon bond. 2. The (poly)alkylene glycol-based compound having a phosphorus atom as claimed in claim 1 wherein the phosphorus-containing (poly)alkylene glycol compound has the following formula (1) OM (wherein, X represents a residue of a compound having an active hydrogen or a hydrogen atom; AO is the same or different and represents a decylalkyl group having a carbon number of 2 to 18; γ1 is the same or different 'is an organic residue; Υ2 is the same or different , represents an organic residue or a hydrogen atom; Μ is the same or different and represents a metal atom, an ammonium group or an organic amine group; η is the same or different 'is the average addition mole number of the alkylene group, which is 1000; m is The structure represented by an integer from 1 to 50). 3 _ - a method for producing a (poly)-extended diol-based compound containing a constituting atom, for producing a phosphorus-containing (poly) stilbene diol compound containing a phosphorus atom according to claim 1 or 2 Contains the following steps. The following general formula (3) 110 201240937 (3) Χ--(ΑΟ)^—γ4 » (wherein X represents a residue of a compound having an active hydrogen or a hydrogen atom; ΑΟ is the same or different, and represents an alkylene group having a carbon number of 2 to 18; Or different 'representing residues of a compound having a carbon-carbon double bond; η being the same or different' means an average addition mole number of the alkyloxy group, which is 1 to 1 ;; m is 1 to 50 The step of performing an addition reaction of a compound containing a (poly)alkylene glycol chain represented by an integer with a hypophosphorous acid or a salt thereof. A chain transfer agent comprising a (poly)alkylene glycol compound containing a phosphorus atom according to claim 1 or 2. 5. A (poly)-extended diol-based polymer containing a wall atom, which must have a phosphorus atom and a (poly)alkylene glycol chain, characterized in that the polymer has a structure such as: An alkylene glycol chain and a structural unit derived from a vinyl (vinyi) system, wherein "the terminal oxygen atom of at least one terminal of the (poly)alkylene glycol chain is bonded to the phosphorus atom via an organic residue, and The organic residue is bonded to the can atom by a scaly-carbon bond, and the chain is bonded to the main unit derived from the structural unit derived from the acetyl group monomer. 201240937 ο (6) ν t II X - _ (AO rrY —ρ·~~ζ ΟΜ (wherein X represents a residue of a compound having an active hydrogen or an argon atom; Α〇 is the same or different and represents a fluorenyl group having a carbon number of 2 to 18; the oxime 1 is the same or different, Represents an organic residue; Μ is the same or different and represents a metal atom, an ammonium group or an organic amine group; Ζ the same or different 'is a polymer containing a vinyl monomer unit; η is the same or different, and represents an average of an alkylene group Adding a molar number of 1 to 1000; m is 丨~" Number) represented by the structure. 7. The (poly)alkylene glycol polymer having a phosphorus atom as claimed in claim 5 or 6, wherein the vinyl monomer unit necessarily contains an unsaturated decanoic acid unit. 8. A method for producing a (poly)alkylene glycol-based polymer containing a phosphorus atom for producing a phosphorus-containing (poly)alkylene monool system according to any one of claims 5 to 7. The polymer comprises the following steps: (1) (Α〇) γΓ^ΥΊ~~Ρ-Ύ2 (1) lj J m (1) OM (Wuzhong 'XA shows the residue of the compound having active hydrogen Base or hydrogen atom; AO is the same or different, represents an alkyl group having a carbon number of 2 to 18; γ ΐ is the same or different 'is an organic residue; Υ 2 is the same or different 'is an organic residue or gas 112 201240937 atom, V [the same The formula s is different, and represents a metal atom, an ammonium group or an organic amine group; an average addition molar number of n 1000 non-oxyalkylene groups, which is #^, m is an integer of 1 to 50) In the presence of (poly) ^ ^ ', δ, the vinyl monomer component is polymerized 9 ^ | j · supernatant patent range 8th phosphorus-containing (poly) alkylene glycol polymer The 劁2, sheng2, and Α2 are in the formula, γ2 is a hydrogen atom. An additive for inorganic particles, which comprises a (poly)alkylene glycol-based polymer containing a phosphorus atom according to any one of claims 5 to. An additive for cement containing a (poly)alkylene glycol-based polymer containing a phosphorus atom according to any one of claims 5 to 7. 113