JP2000272945A - Thickener for underwater concrete - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thickener having excellent underwater separation and improved setting retardation by using a water-soluble polyurethane having plural specific repeating units and a weight-average molecular weight in a specified range. SOLUTION: This thickener has >=0.5 and <=0.99 mol fraction of a repeating unit of the formula (A is a water-soluble polyalkylene polyol containing hydroxyl groups at both ends and 400-100,000 number-average molecular weight; B is a 3-18C polyisocyanate compound) and >=0.01 and <=0.5 mol fraction of a repeating unit of formula II (D is a comb hydrophobic diol of formula III (R' is a hydrocarbon group or a nitrogen-containing hydrocarbon group; R2 and R3 are each a hydrocarbon group; hydrogen in R1 to R3 is substitutable with F, Cl or Br; Y and Y' are each H, methyl or chloromethyl; Z and Z' are each O, S or methyl; n is 0-15 when Z is O) and having 100-1,000,000 weight-average molecular weight. Cement is formulated with 0.1-10 wt.% of the thickener.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thickener for underwater concrete, comprising a novel polymer mainly composed of a water-soluble polyalkylene glycol, and a thickener for underwater concrete. The present invention relates to a composition for underwater concrete.

[0002]

2. Description of the Related Art It is known to add a water-soluble thickener to concrete as a non-separating agent in water in order to avoid the separation of mortar and aggregate in water when casting concrete in water. (For example, Japanese Patent Laid-Open No. 57-12385).
0, etc.). A high aqueous solution viscosity is necessary in order to exhibit sufficient inseparability in water, but at present this polymer is methylcellulose (MC), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC) or hydroxyethylcellulose (HE).
Water-soluble cellulose ethers such as C) are widely used.

[0003] However, water-soluble cellulose ethers have a problem that the hardening time of concrete is delayed (setting delay), and as a result, the strength of concrete is apt to be reduced.

[0004] Further, water-soluble cellulose ethers are semi-synthetic polymers using specific natural pulp as a raw material, and therefore are relatively expensive, which has increased the raw material cost. In addition, the resources of pulp are limited, and a new thickener for underwater concrete that can be synthesized from cheaper industrial raw materials has been awaited.

[0005]

Existing thickeners for underwater concrete, such as water-soluble cellulose ethers, still have problems in setting retardation. Water-soluble cellulose ethers are relatively expensive because specific natural pulp is used as a raw material. In addition, the resources of natural pulp as a raw material are limited, and a thickener for underwater concrete that can be synthesized from cheaper industrial raw materials has been awaited. Accordingly, an object of the present invention is to provide a new thickener for underwater concrete, which is more economical, has excellent inseparability in water, and has an improved setting delay, replacing water-soluble cellulose ethers.

[0006]

The present inventors have made intensive studies to solve the above problems, and as a result, have found that a thickener for underwater concrete comprising a novel water-soluble polyurethane having a comb-shaped hydrophobic diol as an associating group. And completed the present invention.
The present invention provides a compound represented by the following chemical formula 1:

[0007]

Embedded image And a repeating unit (1) represented by the following formula:

[0008]

Embedded image A polymer comprising a repeating unit (2) represented by the formula:
The molar ratio of the repeating unit (1) is 0.5 or more and 0.99 or less, the molar ratio of the repeating unit (2) is 0.01 or more and 0.5 or less, and the weight average molecular weight measured by GPC is 10 or more. It is a thickener for underwater concrete comprising water-soluble polyurethane in the range of 10,000 to 1,000,000.

However, A is HO-A-OH having a hydroxyl group at least at both terminals and having a number average molecular weight of 400 to 10
A divalent group which is a 000 water-soluble polyalkylene polyol (compound A), and B is a polyisocyanate in which OCN-B-NCO is selected from the group consisting of polyisocyanates having 3 to 18 carbon atoms in total. A divalent group which is a nate compound (compound B), and D is HO-D-OH represented by the chemical formula 3

[0010]

Embedded image

(However, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group. R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms. Part or all of hydrogen in the hydrocarbon groups R ¹ , R ² and R ³ may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different. Y
And Y ′ are hydrogen, a methyl group or a CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ groups, and Z and Z ′
May be the same or different. N is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group. N ′ is 0 to 1 when Z ′ is oxygen.
An integer of 5 and 0 when Z ′ is a sulfur or CH ₂ group;
And n and n ′ may be the same or different.), Which is a comb-shaped hydrophobic diol (compound D). Also, the present invention provides a compound represented by the formula (4):

[0012]

Embedded image

(However, R ^{1 ′} is a chain alkyl group having 4 to 18 carbon atoms, and R ^{2 ′} and R ^{3 ′} are each a chain alkyl group having 4 to 18 carbon atoms.)
Wherein the total number of carbon atoms of R ^{1 ′} , R ^{2 ′} and R ^{3 ′} is 12 to 40, and R ^{2 ′} and R ^{3 ′}
Is the thickener for underwater concrete, which is a comb-shaped hydrophobic diol represented by

The present invention is also a thickener for underwater concrete, wherein the compound B is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate. The present invention is also a thickener for underwater concrete, wherein the compound B is hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate or norbornene diisocyanate. Further, the present invention is a thickener for underwater concrete comprising the water-soluble polyurethane having a 2% aqueous solution viscosity of 1,000 to 500,000 centipoise. The present invention is also a composition for underwater concrete, wherein the thickener for underwater concrete is added in an amount of 0.1 to 10% by weight based on cement.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer used in the present invention is a polymer having a comb-shaped hydrophobic group obtained by connecting a water-soluble polyalkylene polyol and a substantially monodispersed comb-shaped hydrophobic diol with a polyisocyanate. is there.

The water-soluble polyalkylene polyol (Compound A) used in the present invention is an alkylene oxide polymer having hydroxyl groups at least at both ends of a polymer chain. However, when a polyalkylene polyol having three or more hydroxyl groups is used, the solubility of the product in water tends to decrease. Therefore, it is more preferable to use a polyalkylene glycol having primary hydroxyl groups at both ends of the polymer chain.

Examples of the monomer alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin. In order to enhance water solubility, the content of ethylene oxide must be at least 60% by weight. preferable. More preferably, a polymer of ethylene oxide (polyethylene glycol; hereinafter abbreviated as PEG) is used.

The compound A has a number average molecular weight of 40.
Those having 0 to 100,000 are preferred. More preferably, 1,500 to 50,000, and still more preferably, 3,000.
~ 20,000. If the molecular weight is less than 400, a product having a sufficient aqueous solution viscosity cannot be obtained, and cannot be used as a thickener. On the other hand, if the molecular weight is larger than 100,000, the reaction rate decreases, and a product having a sufficient aqueous solution viscosity cannot be obtained. 3,000-20,000 molecular weight
Within the range, a product exhibiting a sufficient aqueous solution viscosity is most easily obtained.

The polyisocyanate compound (compound B) used in the present invention has a total number of carbon atoms selected from the group consisting of linear aliphatic polyisocyanates, cycloaliphatic polyisocyanates and aromatic polyisocyanates. Is (N
3-18 polyisocyanate compounds (including the carbon of the CO group). Polyisocyanates having a total carbon number of 18
If it is larger, the solubility of the polymer tends to decrease. However, when a polyisocyanate having three or more NCO groups in the molecule is used, the solubility of the product in water tends to decrease. Therefore, it is more preferable to use diisocyanates having two NCO groups in the molecule.

In the reaction of diisocyanates with polyalkylene glycols, the reactivity is higher in the order of aromatic diisocyanates> chain aliphatic diisocyanates> cycloaliphatic diisocyanates, but aromatic diisocyanates Isocyanates react sharply when reacted in the absence of a solvent, so that the reaction tends to be non-uniform and the control of molecular weight is somewhat difficult. Further, a polymer produced using an aromatic diisocyanate may change with time in a mortar that is strongly basic, and the effect as an auxiliary may decrease with time after kneading. It is considered that the mortar is a strong alkali having a pH of about 14, so that the bond between the aromatic diisocyanate and the polyalkylene glycol, which is susceptible to hydrolysis by the alkali, is cleaved.

Accordingly, it is more preferable to use chain and cyclic aliphatic diisocyanates having 3 to 18 carbon atoms in total. More preferably, hexamethylene diisocyanate (commonly abbreviated as HDI), isophorone diisocyanate (commonly abbreviated as IPDI), hydrogenated xylylene diisocyanate (commonly abbreviated as HXDI) or norbornene diisocyanate (commonly abbreviated as NBDI) It is to use. Particularly preferably, HDI is used.

The chain aliphatic diisocyanates are NCO
A diisocyanate compound having a structure in which groups are connected by a linear or branched alkylene group, and specific examples include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, and 1-methylethylene. Diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, 2,2′-dimethylpentane -1,5-diisocyanate, lysine diisocyanate methyl ester (LD
I), octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4
-Trimethylpentane-1,5-diisocyanate, nonamethyldiisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, decamethylenediisocyanate, undecamethylenediisocyanate, dodecamethylenedi Isocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate,
Pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, trimethylhexamethylene diisocyanate and the like can be mentioned.

Cycloaliphatic diisocyanates are NCO
A diisocyanate compound in which an alkylene group connecting the groups has a cyclic structure, and specific examples thereof include cyclohexane-1,2-diisocyanate and cyclohexane-1,3.
-Diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4-
Diisocyanate, 4,5-dimethylcyclohexane-
1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω′-diisocyanate, 1,4-dimethylcyclohexane-ω, ω′-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane -4,4'-diisocyanate, dicyclohexylmethylmethane-4,4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,2'-dimethyldicyclohexylmethane
4,4′-diisocyanate, 3,3′-dimethyldicyclohexylmethane-4,4′-diisocyanate,
4,4′-methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexyl isocyanate) (IPCI), 1,3-bis (isocyanatomethyl) cyclohexane, hydrogenated tolylene diisocyanate (HTDI), Hydrogenated 4,4'-diphenylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), norbornene diisocyanate (NBDI) and the like can be mentioned.

Aromatic diisocyanates are diisocyanate compounds in which NCO groups are linked by an aromatic group such as a phenylene group, an alkyl-substituted phenylene group and an aralkylene group or a hydrocarbon group containing an aromatic group. Specific examples thereof include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), and 1-methyl-2,6-
Phenylene isocyanate (2,6-TDI), 1-
Methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3
-Dimethyl-2,4-phenylene diisocyanate,
1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, m-xylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1- Methyl-3,5-diethylbenzene-
2,4-diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5
-Triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-
1,5-diisocyanate, 1-methylnaphthalene-
1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'- Diisocyanate, biphenyl-4,4'-diisocyanate, 1,3-bis (1
-Isocyanato-1-methylethyl) benzene, 3,
3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate And xylylene diisocyanate (XDI).

Other polyisocyanates include 1,
6,11-undecatriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane,
1,3,6-hexamethylene triisocyanate and the like. The comb-shaped hydrophobic diol (compound D) used in the present invention is represented by the following chemical formula 3

[0026]

Embedded image Are hydrophobic diols having two secondary hydroxyl groups in the molecule and three hydrophobic chains in the molecule.

Here, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group, or a nitrogen-containing hydrocarbon group such as a dialkylaminoalkyl group. R ₂ and R ₃ are a hydrocarbon group having 4 to 21 carbon atoms such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group. A part or all of hydrogen in the hydrocarbon groups R ¹ , R ² and R ³ may be substituted by a halogen atom such as fluorine, chlorine, bromine or iodine. R ² and R ³ may be the same or different, but are more preferably the same.

The hydrophobic diols can be obtained by adding various oxirane compounds (compounds having an oxirane ring) to primary amines. As the oxirane compound, various glycidyl ethers, 1,2-epoxyalkanes, 1,2-epoxyalkenes, glycidyl sulfides, and the like can be used. The addition reaction between the amino group of the amines and the oxirane compound has a high activity, and the reaction proceeds sufficiently without a catalyst. On the other hand, the activity of the addition reaction between the hydroxyl group and the oxirane compound generated as a result of the reaction is relatively low, and the reaction hardly proceeds under conditions without a catalyst such as an acid or a base. Thus, by reacting the amines and the oxirane compound under mild reaction conditions such as no catalyst, it is possible to suppress further reaction between the diol and the oxirane compound generated as a result of the addition reaction.

More specifically, the primary amines include primary linear or cyclic alkylamines, primary linear or cyclic alkenylamines, primary aralkylamines and primary dialkylamino. Alkylamines,
Primary N-benzylaminopyrrolidines, primary N-aminoalkylmorpholines, primary arylamines,
Primary aminopyridines and primary aminoalkylpyridines can be mentioned as examples.

Examples of primary chain alkylamines include:
Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, ter-butylamine, sec-butylamine, n-pentylamine,
n-hexylamine, n-heptylamine, 2-aminoheptane, n-octylamine, isooctylamine,
2-aminooctane, 2-ethylhexylamine, 2-
Amino-6-methylheptane, nonylamine, isononylamine, 1,4-dimethylheptylamine, 3-aminononane, 2-amino-6-ethylheptane, n-decylamine, n-undecylamine, 2-aminoundecane, 6 -Aminoundecane, n-dodecylamine, n-
Tridecylamine, 2-aminotridecane, n-tetradecylamine, 2-aminotetradecane, n-pentadecylamine, 8-aminopentadecane, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n Linear alkylamines such as -nonadecylamine, 2-aminononadecane and 1-aminoeicosane. Examples of primary chain alkenylamines include allylamine and oleylamine.

Examples of primary cyclic alkylamines include:
Cyclohexylamine, cycloheptylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, aminomethylcyclohexane, cyclooctylamine, 2,3-dimethylcyclohexylamine, 3,3,5-trimethylcyclohexylamine , 4-ter-butylcyclohexylamine, 1-cyclopentyl-2-aminopropane,
1-aminoindan, cyclododecylamine, o-aminobicyclohexyl, 3-aminospiro [5,5] undecane, bornylamine, 1-adamantanamine, 2
-Aminonorbornane, 1-adamantanemethylamine and the like.

Examples of primary cyclic alkenylamines include dihydroabiethylamine and 2- (1-cyclohexenyl) ethylamine. Examples of primary aralkylamines include benzylamine, phenethylamine, p-methoxyphenethylamine, α-phenylethylamine, 1-methoxy-3-phenylpropylamine, N-aminopropylaniline and the like.

Examples of primary dialkylaminoalkylamines include N, N-dimethylethylenediamine, N, N
N-diethylethylenediamine, N, N-diisopropylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, diethylaminopropylamine, dibutylaminopropylamine, 1-dimethyl Amino-2-propylamine, N2, N2-dimethyl-1,2-propanediamine, 4-dimethylaminobutylamine, 1-dimethylaminoethyl-2-aminopropane, N, N-dimethylpeopentanediamine, 1-diethylamino- 2-propylamine, 6-dimethylaminohexylamine, 2-
Di-n-propylaminoethylamine, N-ethyl-N
-Butylethylenediamine, 7-diethylaminoheptylamine, N1, N1-di-n-propyl-1,2-propanediamine, N ′, N′-di-n-propanediamine, 5-diethylaminoamylamine, 2- Amino-5
-Diethylaminopentane, N, N-di-n-butylethylenediamine, N, N-di-tert-butylethylenediamine, 2-diisobutylaminoethylamine,
-Diisopropylaminobutylamine, 7-ethylaminoheptylamine, 3- (di-n-butylamino) propylamine, N, N-diisobutyl-1,6-hexanediamine, 1- (2-aminoethylpiperidine, 3-pi Peridinopropylamine, 4-pyrrolidinobutylamine, N-aminoethyl-4-pipecholine, 3-aminotropane, 5-pyrrolidinoamylamine, N-aminopropyl-4-pipecholine, 1- (3-aminopropyl)-
2-Pipecoline, 1-aza-bicyclo [2.2.2] oct-3-ylamine, 1-benzyl-3-aminopyrrolidine, N1-ethyl-N1-phenylpropane-1,
3-diamine and the like.

Examples of primary N-benzylaminopyrrolidines include N-benzyl-3-aminopyrrolidine and N-benzylaminopyrrolidine.
-Benzyl-2-methyl-3-aminopyrrolidine and the like. Examples of primary N-aminoalkylmorpholines include N-aminoethylmorpholine, N-aminopropylmorpholine and the like.

Examples of primary arylamines include aniline, 2-chloroaniline, 2,3-dichloroaniline, 2,4-dibromoaniline, 2,4,6-tribromoaniline, o-toluidine, -Chloro-4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2-ethylaniline, 2-isopropylaniline, 4-tert-butylaniline, p-decylaniline , P-dodecylaniline, p-tetradecylaniline, 4-cyclohexylaniline, 2-aminobiphenyl, 1-naphthylamine, 5-aminoindane, 1-aminonaphthacene, 6-
Aminochrysene, 1-aminopyrene and the like can be mentioned.

Examples of primary aminopyridines include 2
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-4, 6-dimethylpyridine, 2
-Amino-3-nitropyridine and the like. Examples of primary aminoalkylpyridines include 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 3-aminomethyl-6-chloropyridine, and the like. Other primary amines include 2-aminomethylpyrazine, 2-aminopyrazine,
Pyrazines such as sulfalene;

Examples of the glycidyl ether include alkyl glycidyl ethers, alkenyl glycidyl ethers, aralkyl glycidyl ethers, and aryl glycidyl ethers. Examples of alkyl glycidyl ethers include n-
Butyl glycidyl ether, sec-butyl glycidyl ether, ter-butyl glycidyl ether, glycidyl pentyl ether, glycidyl hexyl ether,
Glycidyl octyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, glycidyl nonyl ether, decyl glycidyl ether, dodecyl glycidyl ether, glycidyl lauryl ether, glycidyl tridecyl ether, glycidyl tetradecyl ether, glycidyl pentadecyl ether, glycidyl hexa Decyl ether, glycidyl stearyl ether, 3- (2- (perfluorohexyl) ethoxy) -1,2-epoxypropane, 3- (3
-Perfluorooctyl-2-iodopropoxy)-
1,2-epoxypropane and the like.

Examples of alkenyl glycidyl ethers include allyl glycidyl ether and oleyl glycidyl ether. Examples of aralkyl glycidyl ethers include benzyl glycidyl ether and phenethyl glycidyl ether. Examples of aryl glycidyl ethers include phenyl glycidyl ether, 4-ter-butylphenyl glycidyl ether, 2-ethylphenyl glycidyl ether,
-Ethylphenyl glycidyl ether, 2-methylphenyl glycidyl ether, glycidyl-4-nonyl phenyl ether, glycidyl-3- (pentadecadienyl) phenyl ether, 2-bisphenyl glycidyl ether, benzyl glycidyl ether, α-naphthyl glycidyl ether And dibromophenyl glycidyl ether.

Examples of other glycidyl ethers include glycidyl ethers of alkylene oxide adducts of alcohols and phenols (ethylene oxide adduct, propylene oxide adduct, epichlorohydrin adduct, etc.). It is represented by a general formula in Chemical Formula 5 (Chemical Formula 10).

[0040]

Embedded image (Where R is an alkyl or aryl group, Y is hydrogen,
A methyl group or a CH ₂ Cl group, n is an integer of 1 to 15. Examples of the glycidyl ether of the ethylene oxide adduct include glycidyl ether of 2-ethylhexyl alcohol-ethylene oxide adduct, glycidyl ether of lauryl alcohol-ethylene oxide adduct,
Examples include glycidyl ethers of 4-ter-butylphenol-ethylene oxide adducts and glycidyl ethers of nonylphenol-ethylene oxide adducts.

Similarly, it is also possible to use glycidyl ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts.
The glycidyl ethers of industrial chemicals usually contain glycidyl ethers of epichlorohydrin adduct as by-products, but such low-purity raw materials can also be used. The addition number n is suitably about 1 to 15.
When the number of additions exceeds 15, the aqueous solution viscosity of the polyurethane tends to decrease.

Further, 1,2-epoxyalkanes and 1,2-epoxyalkanes
Examples of epoxy alkenes include 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, and 1,2-epoxidedodecane. , 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,
Examples thereof include 2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-7-octene, and 1,2-epoxy-9-decene. Other oxirane compounds include alkyl glycidyl thioethers (alkyl glycidyl sulfides) such as 2-ethylhexyl glycidyl sulfide and decyl glycidyl sulfide, and aryl glycidyl thioethers (aryl glycidyl sulfide) such as p-nonylphenyl glycidyl sulfide.

The above amines and oxirane compounds are
Compound D can be obtained by reacting one molecule of the amine with two molecules of the oxirane compound. Chemical formula 6
Represents a reaction formula (Chem. 11).

[0044]

Embedded image (However, R ^a , R ^b , and R ^c are appropriate substituents.) The reaction was carried out in comparison with the case where 1,2-epoxyalkanes, 1,2-epoxyalkenes, and glycidyl sulfides were used as oxirane compounds. This is easier when glycidyl ethers are used. This is probably because the reactivity of glycidyl ethers with amines is high.

Compound D has three hydrophobic chains in the molecule, and since these hydrophobic chains are close to each other,
This has the effect of facilitating hydrophobic association between water-soluble polyurethanes in an aqueous solution. The number of carbon atoms in each hydrophobic chain needs to be long enough for the polymer to form a sufficient association. The amines preferably have 1 to 20 carbon atoms. When amines having more than 20 carbon atoms are used, the solubility of the polyurethane may decrease. More preferably, chain or cyclic alkylamines having 1 to 18 carbon atoms, still more preferably 4 to 1 carbon atoms.
8 chain alkylamines.

The hydrophobic group of the glycidyl ethers preferably has 4 to 21 carbon atoms. When a glycidyl ether having less than 4 carbon atoms is used, the aqueous solution viscosity of the polyurethane may not be sufficiently high. When a glycidyl ether having more than 21 carbon atoms is used, the solubility of the polyurethane may decrease. More preferably, alkyl glycidyl ethers having a linear or branched alkyl group having 4 to 18 carbon atoms as a hydrophobic group, or 6 to 18 carbon atoms
Aryl glycidyl ethers having an aromatic group or an alkyl-substituted aromatic group as a hydrophobic group. For the same reason, the hydrophobic group of 1,2-epoxyalkane, 1,2-epoxyalkene, alkyl glycidyl thioether and aryl glycidyl thioether has 4 to 21 carbon atoms.
The following is preferred.

As the total number of carbon atoms of the three hydrophobic chains (the total number of carbon atoms of the substituents R ¹ , R ² and R ^{3 in} the above formula (3)) increases, the polymer becomes more soluble in water. Although it is easy to associate and obtain a high aqueous solution viscosity, if the total number of carbon atoms is too large, the solubility of the polymer in water tends to decrease. The total number of carbon atoms in the hydrophobic group is more preferably in the range of 12 to 40. More preferably, the total number of carbon atoms is in the range of 12 to 34. Most preferably, the total number of carbon atoms is 12 to
24. If the total number of carbon atoms is less than 12, it is difficult to obtain a polymer having a high aqueous solution viscosity.
When the total number of carbon atoms exceeds 40, the solubility of polyurethane in water tends to decrease.

The method for producing the comb-shaped hydrophobic diol will be described below, but the method for synthesizing the comb-shaped hydrophobic diol used in the present invention is not limited to this example. Raw materials amines and oxirane compounds are charged into a reaction vessel having a stirrer, a raw material introduction mechanism, and a temperature control mechanism, and reacted while stirring at a predetermined reaction temperature. The reaction can be performed without a solvent, but a general solvent such as DMF may be used. For the introduction of the raw materials, the amines and the oxirane compounds may be charged all at once, or one of them may be charged into a reaction vessel, and the other may be introduced continuously or stepwise.
The reaction temperature is from room temperature to about 160 ° C., more preferably 60 ° C.
A temperature of about -120 ° C is appropriate. The reaction time is about 0.5 to 10 hours, depending on the reaction temperature and the like. The degree of dispersion of the diol after completion of the reaction can be determined by GPC. Further, the OH value can be determined by a conventional method. The water-soluble polyurethane having a comb-shaped hydrophobic group is represented by the following chemical formula (7).
2)

[0049]

Embedded image

As shown in the above formula, it is synthesized by the reaction of two hydroxyl groups of polyalkylene glycol (compound A) and comb-like hydrophobic diol (compound D) with two NCO groups of diisocyanate compound (compound B). You. The water-soluble polyurethane in which the molar ratio of the repeating unit (1) is (1-x) and the molar ratio of the repeating unit (2) is x is such that the molar ratio of the compound A to the compound D is (1-x): x It is obtained by reacting in a ratio.

Hereinafter, a method for producing a water-soluble polyurethane will be described by way of example. However, the present invention is, of course, not limited to the following method. The inside of a reaction vessel having a stirring device, a raw material introduction mechanism, and a temperature control mechanism is replaced with an inert gas.
A polyalkylene glycol is charged into a reaction vessel. In some cases, a solvent is charged. The catalyst is added while controlling the reaction vessel at the set reaction temperature. While stirring the inside of the vessel, the diisocyanate compound and the comb-shaped hydrophobic diol are introduced into the reaction vessel. The method of introduction is not particularly limited. It may be introduced continuously or intermittently. Also, the diisocyanate compound and the comb-shaped hydrophobic diol may be introduced simultaneously, or even if the comb-shaped hydrophobic diol is introduced after the introduction of the diisocyanate compound, the diisocyanate compound may be introduced after the introduction of the comb-shaped hydrophobic diol. Is also good.

It is not necessary to add the catalyst to the polyalkylene glycol before the reaction, and the reaction can be started by adding the catalyst after adding the diisocyanate compound or the comb-shaped hydrophobic diol to the polyalkylene glycol. Alternatively, it is also possible to add a catalyst to the diisocyanate compound or the comb-shaped hydrophobic diol in advance, and to react these with the polyalkylene glycol. After a predetermined reaction time, the product is taken out of the reaction vessel and processed into pellets, flakes, powders, solutions, and the like to obtain products.

The catalyst used in the reaction is not particularly limited, but may be any known one generally used in the reaction between isocyanates and polyols, such as organometallic compounds, metal salts, tertiary amines, and other base catalysts and acid catalysts. Can be used. Examples include dibutyltin dilaurate (hereinafter abbreviated as DBTDL), dibutyltin di (dodecylthiolate), stannous octanoate, phenylmercuric acetate, zinc octoate, lead octoate, zinc naphthenate, lead naphthenate, and triethylamine (TEE).
A), tetramethylbutanediamine (TMBDA), N
-Ethylmorpholine (NEM), 1,4-diaza [2.
2.2] Bicyclooctane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DB
U), N, N'-dimethyl-1,4-diazacyclohexane (DMP) and the like. Among them, DBTDL is more preferable.

The amount of the catalyst used in the reaction varies depending on the reaction temperature and the type of the catalyst, and is not particularly limited.
0.0001 per mole of polyalkylene glycol
0.1 mol, more preferably about 0.001 to 0.1 mol is sufficient.

The reaction can be carried out without a solvent, but the reaction can be carried out using a solvent in order to reduce the melt viscosity of the product. Solvents include halogenated solvents such as carbon tetrachloride, dichloromethane, chloroform and trichlene; aromatic solvents such as xylene, toluene and benzene; and saturated hydrocarbons such as decane, octane, heptane, hexane, cyclohexane and pentane. Activity of solvents, ether solvents such as dioxane, tetrahydrofuran, diethyl ether, dimethyl ether and ethylene glycol dimethyl ether; ketone solvents such as diethyl ketone, methyl ethyl ketone and dimethyl ketone; and ester solvents such as ethyl acetate and methyl acetate. A solvent having no hydrogen is effectively used. However, not using a solvent is advantageous in terms of manufacturing cost because the step of removing the solvent is unnecessary, and is more preferable because there is less risk of environmental pollution.

The amount of the diisocyanate compound used in the reaction is such that the total number of moles of the polyalkylene glycol and the comb-shaped hydrophobic diol is 1 mole, and the number of moles (NCO / OH) of the diisocyanate compound is 0 mole. It is 0.8 to 1.3 mol, more preferably 0.9 to 1.2 mol, and further preferably 1.0 to 1.1 mol. If it is less than 0.8 or more than 1.3, the average molecular weight of the product is small, and the ability as a thickener auxiliary for underwater concrete is insufficient. The product having the highest molecular weight can be obtained under the condition that the mole number of the diisocyanate and the mole number of the polyalkylene glycol and the comb-shaped hydrophobic diol are substantially equal. However, when water is contained in the polyalkylene glycol or the comb-shaped hydrophobic diol, the amount of the above-mentioned diisocyanate compound needs to be used in excess of the amount by which the diisocyanate is decomposed by the water. Therefore, it is more preferable to use a sufficiently dried raw material. If possible, the water content of the raw material should be 5,0
00 ppm or less is preferable. More preferably 1,000
ppm or less, more preferably 200 ppm or less.

The amount of the comb-shaped hydrophobic diol used in the reaction is as follows:
Depending on the molecular weight of the polyalkylene glycol and the number of carbon atoms in the hydrophobic group of the comb-shaped hydrophobic diol, the number of moles of the comb-shaped hydrophobic diol is 0.01 to 1 mole per mole of the polyalkylene glycol (x is 0.01 to 0). .5) is appropriate. If it is less than 0.01 mol, the thickening effect may not be exhibited. In addition, it is not preferable to cause the reaction to exceed 1 mol because the solubility may be reduced. ()
The numerical values in the parentheses represent the value of x in the chemical formula 7.

When polyethylene glycol having a number average molecular weight in the range of 3,000 to 20,000 is used as the polyalkylene glycol, the most excellent polyurethane as a thickener aid for underwater concrete is easily obtained. In this case, the amount of the comb-shaped hydrophobic diol used in the reaction was 0.01 to 1 mol of polyethylene glycol.
１1 mol (x is 0.01 to 0.5) is preferred. More preferably, 0.03 to 0.67 mol (x is 0.03 to 0.
4). If it is less than 0.01 mol, the effect as a thickener aid for underwater concrete may not be sufficient.

The reaction temperature varies depending on the type and amount of the catalyst used, but is preferably from 50 to 180 ° C. More preferably 60 to 150 ° C, further preferably 80 to 12 ° C.
It is in the range of 0 ° C. If the reaction temperature is lower than 50 ° C., the reaction rate is low and it is not economical. If the temperature exceeds 180 ° C., the product may be thermally decomposed. The reaction time varies depending on the type and amount of the catalyst used, the reaction temperature and the like, and is not particularly limited, but about 1 minute to 10 hours is sufficient. The reaction pressure is not particularly limited. The reaction can be carried out under normal pressure, reduced pressure or increased pressure. More preferably, the reaction is carried out under normal pressure or weak pressure.

The characteristics of the water-soluble polyurethane obtained by the present invention are described below. In the present invention, a 2% aqueous solution viscosity (a value obtained by measuring the viscosity of an aqueous solution having a polyurethane concentration of 2% by weight at 20 ° C. at a rotation speed of 6 rpm using a B-type rotational viscometer) is about 1,000 to 500, An associative polymer of 000 centipoise (cP) is effectively used. If the 2% aqueous solution viscosity is less than 1,000 cP, the aggregate inseparability of the concrete tends to be insufficient. If the 2% aqueous solution viscosity exceeds 500,000 cP, the adhesive force is too strong and the pumpability of concrete is likely to decrease.

For use as a thickener for underwater concrete, the weight average molecular weight measured by GPC is about 1
Polymers in the range of 10,000 to 1,000,000 are suitable. GPC
Used a chloroform solution and calibrated the molecular weight with standard polystyrene. If the weight average molecular weight is less than 100,000, the viscosity of the aqueous solution is often insufficient. On the other hand, if the weight average molecular weight exceeds 1,000,000, the aqueous solution has spinnability, and thus may not be suitable as a thickener for underwater concrete.

In order to use these water-soluble polyurethanes as thickeners for underwater concrete, they can be used as flake-like solids or diluted with solvents such as aqueous solutions and alcohols. More preferably, it is used in the body. The particle size of the powder is 16 mesh (1 m
m) The following are preferably used: Powder having a particle size of more than 16 mesh may have poor solubility. The thickener for underwater concrete contains the water-soluble polyurethane as a main component, and may contain an antioxidant, a stabilizer, a plasticizer, a diluent, an anti-caking agent, and the like.

The composition for underwater concrete used in the present invention is a thickening agent for underwater concrete according to the present invention instead of a cellulose ether such as methylcellulose or hydroxypropylmethylcellulose which has been conventionally used as a thickening agent for underwater concrete. Except for containing, the same composition as the known composition for underwater concrete is effectively used. Concretely, it is mainly composed of hydraulic powder such as ordinary Portland cement, special Portland cement, blast furnace cement, fly ash cement, alumina cement, gypsum, etc., fine aggregate, coarse aggregate, thickener for water and underwater concrete. including. In addition, inorganic materials such as fly ash, silica fume, bentonite, and clay, redispersible resin powder, various water reducing agents, surfactants, defoamers, setting accelerators, setting retarders, and the like may be included.

The amount of the thickener for underwater concrete of the present invention varies depending on the composition of the concrete used.
The appropriate amount is usually about 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and still more preferably 0.5 to 5% by weight, based on hydraulic powder such as cement. If it is less than 0.1% by weight, a sufficient effect of the thickener may not be obtained. Addition of more than 10% by weight is not preferred because the adhesive strength is too strong and the workability is reduced.

One of the features of the thickener for underwater concrete of the present invention is that even if it is added to the cement in an amount of about 10% by weight, the setting delay of concrete hardly occurs. In the case of conventional thickeners such as cellulose ethers, even with an addition amount of about 0.5 to 5% by weight, the setting delay may adversely affect the strength of concrete. Regarding the method of adding the thickener to the concrete, the thickener of the powder may be added to the concrete and dissolved with stirring, or the thickener may be added to the concrete as an aqueous solution. Further, a mixture of cement and a thickener for underwater concrete in powder form in advance may be used as a raw material for concrete. Of course, the thickener for underwater concrete of the present invention can be used in combination with other existing thickeners such as cellulose ethers, polyacrylic polymers, polyethylene oxide, and polyvinyl alcohol.

The ratio of water contained in the composition varies depending on the type and amount of fine aggregate and coarse aggregate used, and cannot be unconditionally determined. However, the weight ratio of water to hydraulic powder such as cement (water / water) Cement ratio) is preferably in the range of 0.2 to 1. More preferably 0.3 to 0.7, further preferably 0.3 to 0.7
0.5 is appropriate. If the water / cement ratio exceeds 1, sufficient concrete strength may not be obtained.
On the other hand, if it is less than 0.2, the water required for hydration of the cement is insufficient, and high strength concrete may not be obtained.

The amount of the fine aggregate may be the same as that of the conventional underwater concrete. Typically, the fine aggregate such as sand is about 10 to 500% by weight based on the hydraulic powder such as cement. is there. The amount of the coarse aggregate may be the same as that of conventional underwater concrete, but is typically about 10 to 500% by weight based on hydraulic powder such as cement.

The method for producing underwater concrete is not particularly limited. For example, a predetermined amount of a thickener powder or aqueous solution is added to fresh concrete and mixed. In addition, a mixture of cement and a powder of a thickener in advance can be used as a raw material for concrete. The obtained composition for underwater concrete can be applied in the same manner as conventional underwater concrete. By way of example, it can be supplied underwater using a free-fall or transport pump, or it can be supplied underwater via buckets, chutes, hoses or Raymey tubes and cured in water.

[0069]

The present invention will be described below with reference to examples.
Of course, the present invention is not limited to this embodiment. (Synthesis example of comb-shaped hydrophobic diol) Example 1 A magnetic stirrer was placed in a 500 ml round bottom flask,
A thermometer and a dropping funnel were installed, 64.6 g of 2-ethylhexylamine (Kanto Chemical) was charged, and the atmosphere in the flask was replaced with nitrogen. The flask is heated to 60 ° C. in an oil bath, and while stirring, 2-ethylhexyl glycidyl ether (Nagase Kasei Kogyo, Denacol EX
(−121, epoxy value: 188) 188.0 g was added dropwise over 40 minutes. After dropping, raise the temperature of the oil bath to 80 ° C.
And heated the flask for 10 hours. Subsequently, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances was distilled off under reduced pressure using a vacuum pump at a degree of vacuum of 3 mmHg. Comb-shaped hydrophobic diol 1 (average molecular weight 49 based on OH value) in which 2-ethylhexylglycidyl ether is added in a ratio of 2 mol per 1 mol of 2-ethylhexylamine.
0) was obtained with a yield of 98%.

Example 2 A comb-shaped hydrophobic diol 2 was synthesized by adding 2 mol of n-butyl glycidyl ether (Tokyo Kasei) to 1 mol of n-butylamine (Tokyo Kasei). Example 3 Comb-shaped hydrophobic diol 3 was synthesized by adding 2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of n-butylamine. Example 4 Comb-shaped hydrophobic diol 4 was synthesized by adding 2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of dodecylamine (Kanto Chemical).

Example 5 To 1 mole of n-octylamine (Tokyo Kasei), 2 moles of dodecyl glycidyl ether (dodecyl / tetradecyl glycidyl ether manufactured by Aldrich Co.) was added at a ratio of 2 moles to give a comb-shaped hydrophobic material. Synthetic diol 5 was synthesized. Example 6 n to 1 mol of n-octadecylamine (Kanto Chemical)
-Octyl glycidyl ether (P & B) was added at a ratio of 2 mol to synthesize a comb-shaped hydrophobic diol 6. Example 7 Comb-shaped hydrophobic diol 7 was synthesized by adding octadecyl glycidyl ether (Nippon Oil & Fats, Epiol SK) at a ratio of 2 mol to 1 mol of n-butylamine. Table 1
The results are summarized below.

[0072]

[Table 1]

(Synthesis Example of Water-Soluble Polyurethane) A synthesis example of a water-soluble polyurethane using the hydrophobic diol of Example 1 is shown below. However, the present invention is not limited to the following example. Example 8 Commercially available PE was placed in a 500 ml SUS separable flask.
100 g of G # 6000 (Pure Chemical, number average molecular weight 8,700) was charged and melted at 150 ° C. under a nitrogen seal. This was dried under reduced pressure (3 mmHg) for 3 hours while stirring. The residual moisture was 200 ppm. 80
The temperature was lowered to 0 ° C., and while stirring the inside of the flask, 1.00 g of the comb-shaped hydrophobic diol 1 obtained in Example 1 and 2.35 g of hexamethylene diisocyanate (Tokyo Kasei) were charged. When 0.01 g of DBTDL is added as a catalyst,
The viscosity rapidly increased in about 10 minutes. The stirring was stopped and the reaction was continued for another 2 hours. After the reaction was completed, the product was taken out of the flask, cut into small pieces, and allowed to cool. This was cooled with liquid nitrogen and pulverized with an electric mill to a particle size of 1 mm (16 mesh) or less. The 2% aqueous solution viscosity was 200,000 cP, and the weight average molecular weight measured by GPC was 550,000.

Examples 9 to 12 The same as Example 8 except that the charge amount of the comb-shaped hydrophobic diol 1 and the amount of HDI were different. (NCO / OH = 1.0) so that the number of moles of HDI is 1.03 times the sum of the number of moles of each of PEG and comb-shaped hydrophobic diol.
3), the amount of HDI was chosen. The results are summarized in Table 2.

[0075]

[Table 2]

Examples 13 to 23 The same as Example 8 except that the kind and the charge amount of the comb-shaped hydrophobic diol were different. However, in Example 18,
19 has a slightly different molecular weight due to a different synthesis lot of PEG. Examples 20 and 21 Commercially available PEG # 4000 (number average molecular weight 3,000) was used as PEG. Examples 22 and 23 Commercially available PEG # 20000 (number average molecular weight 20,000) was used as PEG. Table 3 summarizes the results.

[0077]

[Table 3]

In Tables 2 and 3, "molecular weight of PEG" is the number average molecular weight of PEG obtained from OH value (OHV). The “total carbon number of the hydrophobic group” is the sum of the carbon numbers of the hydrophobic groups R ¹ , R ² and R ³ of the hydrophobic diol. Further, “hydrophobic diol / PEG” indicates the weight ratio of the hydrophobic diol to PEG in the raw material in percentage. “The coefficient x of the repeating unit” is the coefficient x of the repeating unit represented by the chemical formula 7. The “2% aqueous solution viscosity” is an aqueous solution viscosity (unit: centipoise, cP) measured at 20 ° C. using a B-type rotational viscometer at a rotation speed of 6 rpm for an aqueous solution having a concentration of 2% by weight. The “weight average molecular weight” is a value determined by GPC measurement using monodispersed polystyrene as a standard. As a solvent, chloroform was used.
x is 0.01 to 0.5, weight average molecular weight is 100,000 to 10
In the range of 100,000, a 2% aqueous solution viscosity of 1,000 to 500,
A water soluble polyurethane of 000 cP has been obtained.

(Measurement of Setting Delay Time) The setting delay time of the water-soluble polyurethane obtained in Example 8 was measured and compared with a commercially available cellulose ether. The measurement was carried out with a cement paste and a mortar, but the results of both were almost the same. Therefore, only the results of the cement paste are shown below. A measuring method was as follows: a predetermined amount of a thickener powder was added to and mixed with 100 g of ordinary portland cement, and 40 g of water was further added and mixed well to obtain a cement paste. This was filled in a cylindrical heat-insulating container, and a thermocouple was inserted into the center portion to record the time change of the temperature inside the cement paste. The results are shown in Table 4.

[0080]

[Table 4]

It can be said that the thickener of the present invention has substantially no setting delay, whereas the commercially available Metroze has a setting delay. It is widely known that cellulose ethers cause setting retardation of cement, and it is generally considered that this is due to the effect of a large number of hydroxyl groups in the polymer main chain. When a large number of strong polar groups such as hydroxyl groups are present in the polymer, the polymer is strongly bonded to calcium in cement, and the cause is that the concentration of calcium required for the hydration reaction is insufficient.

On the other hand, the reason why the thickener for underwater concrete of the present invention does not cause setting delay has not been elucidated yet, but one of the reasons is that the ether group which is a hydrophilic group in the polymer main chain has a polarity. Since it is relatively weak and does not strongly bind to calcium, it is considered that no setting delay occurs. (Placement test of underwater concrete) Cement, sand, gravel,
The test was performed using concrete consisting of a thickener and water.

100 parts by weight of ordinary Portland cement,
A predetermined amount of a thickener was added to 180 parts by weight of sand and 250 parts by weight of gravel, and mixed with a concrete mixer. 50 parts by weight of water was added to this composition and further mixed to obtain a composition for underwater concrete. The concret was filled in a cylindrical form having a diameter of 10 cm and a height of 20 cm submerged in a pool having a depth of 1 m by free fall in water. Twenty-four hours later, the test specimen was taken out, the mold was removed, the specimen was cured underwater, and the 7-day strength and the 28-day strength were measured. In addition, the presence or absence of aggregate separation inside the specimen was observed.

Table 5 shows the water / cement ratio (W / C) of the type and amount (% by weight based on cement) of the thickeners used in the examples and comparative examples, and the insolubility in water (for the aggregate in water). Ability to prevent separation) and compressive strength after curing. To determine the presence or absence of aggregate separation, observe the specimen before and after the compression strength measurement,
When no separation was observed, it was evaluated as good (◎), when the separation was slightly observed but not remarkable (可), and when the separation was clearly observed, it was evaluated as poor (×). As a comparative example, an example using Shin-Etsu Chemical's 90SH-30000, which is a typical methylcellulose as a commercially available cellulose ether-based thickener, and an example in which no thickener was added were shown.

[0085]

[Table 5]

Comparison between the examples and the comparative examples shows that the thickener for underwater concrete according to the present invention has at least the same water inseparability as that of a commercially available product (water-soluble cellulose ethers) and a strength. It is clear that it is superior to the commercial product. The inseparability in water is considered to reflect the high thixotropy of concrete. Although the reason is not necessarily clear, the high thixotropy of the concrete (composition for underwater concrete) of the present invention not only increases the viscosity of the water-soluble polyurethane aqueous solution, but also the moderate thixotropy between the comb-shaped hydrophobic group of the water-soluble polyurethane and the cement particles. It is considered to reflect the effect of a simple interaction. Regarding the strength after hardening, the strength in the initial stage is particularly superior to concrete using a commercial product. It is considered that there is no setting delay.

(Synthesis Examples of Hydrophobic Diols Other than Examples 1 to 7 and Synthesis Examples of Water-Soluble Polyurethanes Using the Same) Example 44 1 mol of 2-ethylhexylamine to phenyl glycidyl ether (Nagase Chemical Industry, Denacol) EX-1
41) was added at a ratio of 2 mol to synthesize a comb-shaped hydrophobic diol 8. Example 45 Comb-shaped hydrophobic diol 9 was synthesized by adding 2 mol of p-tert-butylphenylglycidyl ether (Nagase Kasei Kogyo, Denacol EX-146) to 1 mol of n-butylamine.

Example 46 2-Ethylhexyl glycidyl ether was used in an amount of 2 mol per mol of 2-cyclohexylethylamine (Aldrich).
By adding in a molar ratio, a comb-shaped hydrophobic diol 10 was synthesized. Example 47 A comb-shaped hydrophobic diol 11 was synthesized by adding 2 mol of lauryl alcohol (EO) 15 glycidyl ether (Nagase Kasei Kogyo, Denacol EX-171) to 1 mol of 2-ethylhexylamine. (EO) 15
Is ethylene oxide to 1 mole of lauryl alcohol
It indicates that it is a glycidyl ether of an EO adduct to which 5 mol has been added. Example 48 3- [2- (Perfluorohexyl) ethoxy] -1,2-epoxypropane (Kanto Chemical) was added at a ratio of 2 mol to 1 mol of n-butylamine to give a comb-shaped hydrophobic diol 11. Synthesized.

Example 49 Glycidyl-3- (pentadecadienyl) phenyl ether (Aldrich) per mol of n-butylamine
Was added in a ratio of 2 mol to synthesize a comb-shaped hydrophobic diol 12. Example 50 Comb-shaped hydrophobic diol 13 was synthesized by adding 2-ethylhexyl glycidyl ether to 1 mol of dibutylaminopropylamine (Kouei Chemical) at a ratio of 2 mol. Example 51 1,2-Epoxydecane (Tokyo Kasei) was added at a ratio of 2 mol to 1 mol of 2-ethylhexylamine,
Comb-shaped hydrophobic diol 14 was synthesized. Example 52 2-mol relative to 1 mol of p-dodecylaniline (Wako Pure Chemical Industries, Ltd.)
Ethylhexyl glycidyl ether was added at a ratio of 2 mol to synthesize a comb-shaped hydrophobic diol 15. Example 53 Comb-shaped hydrophobic diol 16 was synthesized by adding decyl glycidyl thioether at a ratio of 2 mol to 1 mol of 2-ethylhexylamine. Table 6 summarizes the results of the hydrophobic diol synthesis.

[0090]

[Table 6]

Table 7 summarizes the results of polyurethane synthesis.
In the last three examples, isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI) and hydrogenated xylylene diisocyanate (HXDI) are used as diisocyanates instead of HDI.

[0092]

[Table 7] Table 8 summarizes the results of the underwater casting test.

[0093]

[Table 8]

[0094]

According to the present invention, an inexpensive thickener for underwater concrete having high inseparability in water and improved strength in water can be used.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G012 PA04 PB33 PC08 PC11 4J034 BA08 CA04 CB03 CB08 CC05 CC08 CC62 CD01 CD03 DA01 DA02 DB04 DB08 DE02 DG02 DG03 DG04 DG05 DG09 DH02 HA01 HA07 HC03 HC17 HC22 HC46 HC52 HC61 HC64 HC71 KC17 KD02 KD04 KD12 KE02 QA07 RA10

Claims (6)

[Claims] [Claim 1] Chemical formula 1 And a repeating unit (1) represented by the following formula: A polymer comprising a repeating unit (2) represented by the following formula:
The molar ratio of the repeating unit (1) is 0.5 or more and 0.99 or less, the molar ratio of the repeating unit (2) is 0.01 or more and 0.5 or less, and the weight average molecular weight measured by GPC is 10 or more. Thickener for underwater concrete comprising water-soluble polyurethane in the range of 10,000 to 1,000,000. However, A
Is a divalent group in which HO-A-OH has a hydroxyl group at least at both terminals and is a water-soluble polyalkylene polyol (compound A) having a number average molecular weight of 400 to 100,000, and B is OCN-B-NCO Is a divalent group which is a polyisocyanate compound (compound B) selected from the group consisting of polyisocyanates having 3 to 18 carbon atoms, and D is HO-D-OH represented by the chemical formula 3 Embedded image (However, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group. R ² and R ³ are a hydrocarbon group having 4 to 21 carbon atoms. A part or all of hydrogen in R ¹ , R ² and R ³ may be substituted by fluorine, chlorine, bromine or iodine.
² and R ³ may be the same or different. Y and Y ′ are hydrogen, a methyl group or a CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z '
Is an oxygen, sulfur or CH ₂ group, and Z and Z ′ may be the same or different. N is 0 when Z is oxygen.
An integer of 15 and 0 when Z is a sulfur or CH ₂ group;
It is. N ′ is an integer of 0 to 15 when Z ′ is oxygen, and 0 when Z ′ is a sulfur or CH ₂ group;
n and n ′ may be the same or different), and are a comb-shaped hydrophobic diol (compound D). 2. The compound D is represented by the following chemical formula 4: (However, R ^{1 ′} is a chain alkyl group having 4 to 18 carbon atoms, R ^{2 ′} and R ^{3 ′} are an alkyl group or an aryl group having 4 to 18 carbon atoms, and R ^{1 ′} , R ^{2 The} thickener for underwater concrete according to claim 1, which is a comb-shaped hydrophobic diol represented by the following formula: wherein the total number of carbon atoms of ^' and R3 ^' is 12 to 40, and R2 ^' and R3 ^' are the same. 3. The thickener for underwater concrete according to claim 1, wherein the compound B is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate. 4. The thickening for underwater concrete according to claim 1, wherein the compound B is hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate or norbornene diisocyanate. Agent. 5. A 2% aqueous solution having a viscosity of 1,000 to 500,
The thickener for underwater concrete according to any one of claims 1, 2, 3 to 4, wherein the thickener is 000 centipoise. 6. An underwater concrete, wherein the thickener for underwater concrete according to any one of claims 1, 2, 3, 4 to 5 is added to the cement in an amount of 0.1 to 10% by weight. Composition.