JPH0379690A - Water-retaining agent for well cementing and cement slurry containing the same - Google Patents

Abstract

PURPOSE:To provide the subject novel water-retaining agent composed of a cationic water-soluble resin produced by reacting a polyalkylene glycol polyhalohydrin ether with an aziridine compound, etc., having stable properties to temperature changes and applicable without causing increase in the viscosity of cement slurry. CONSTITUTION:The objective water retaining agent is composed of a cationic water-soluble resin produced by reacting (A) 100 pts. wt. of a polyalkylene glycol polyhalohydrin ether obtained by the reaction of (i) 1 mol of a polyalkylene glycol with (ii) 1-10mol (preferably 2-5 mol) of an epihalohydrin with (B) 10-10,000 pts.wt. (preferably 80-1,000 pts.wt.) of an aziridine compound or a polyamine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a cementing water retention agent for wells and a cement slurry containing the same.

[Conventional technology and problems 1 Bentonite, hydroxyethyl cellulose (HEC), etc. have been used as water retention agents for cementing wells.However, these water retention agents generally have poor heat resistance, and in recent years When used for defenses that are excavated deep underground and exposed to high temperatures, satisfactory cementing cannot be achieved because the water retention effect decreases and the fluidity of the cement slurry is impaired.Additionally, these water retention agents reduce the viscosity of the cement slurry. However, there is a need for the development of a water-retaining agent that does not significantly change the properties of cement slurry due to temperature changes and does not increase the viscosity of cement slurry.

[Means for solving the problem] As a result of intensive studies, the present inventors discovered a new water retention agent that does not significantly change the properties of cement slurry due to temperature changes and does not increase the viscosity of cement slurry. Completed the invention.

That is, the present invention provides a polyalkylene glycol polyhalohydrin ether (a) obtained by reacting 100 parts by weight of polyalkylene glycol polyhalohydrin ether (a) with 10 to 10,000 parts by weight of an aziridine compound (b) or a polyamine (c). The present invention relates to a cementing water retention agent for wellbore consisting of a cationic water-soluble resin and a cement slurry containing the same.

The polyalkylene glycol used in the water retention agent of the present invention preferably has a molecular weight in the range of 200 to 10,00, more preferably 600 to 50,00.
00. Most preferably, those having a molecular weight of 1°000 to 20,000 are used. That is, if the molecular weight is less than 200, it will easily gel when producing a cationic water-soluble resin, while if it exceeds 100,000, the reactivity with epihalohydrin will be low, and the cationic water-soluble resin will not be suitable for the purpose of the present invention. This is because it becomes impossible to obtain a water-soluble resin.

Specific examples of epihalohydrin used in the present invention include epichlorohydrin and Ebipro.

Boria' used in the synthesis of polyalkylene glycol polyhalohydrin ether (a) in the production method of the present invention
Lukylene glycol includes polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol copolymer, and polyethylene glycol is particularly preferred.

The aziridine compound (b) used in the present invention is not particularly limited as long as it has one aziridine group in one molecule.For example, it may have a substituent on the aziridine ring, or Two or more of these aziridine compounds (b) may be used.

Specific examples of such aziridine compounds (b) include:
Ethyleneimine, propyleneimine, butyleneimine,
N-hydroxyethylethyleneimine, N-cyanoethylethyleneimine, N-methylethyleneimine, N-ethylethyleneimine, N-phenylethyleneimine, N
Examples include -acetylethyleneimine, N-methacryloylaziridine, β-aziridinylmethylpropionate, β-aziridinylethyl methacrylate, and the like.

The aziridine compound (b) used in the present invention is
As included above, economic advantages include polyalkylene glycol polyhalohydrin ethers (a
), preferred is alkyleneimine, more preferred is ethyleneimine.

Polyalkylene glycol polyhalohydrin ether (a) from polyalkylene glycol and epihalohydrin
In order to obtain polyalkylene glycol, a Brønsted acid or a Lewis acid may be added as a catalyst, and the mixture may be reacted with epihalohydrin at 30 to 150°C, preferably 50 to 100°C. Among Lewis acids and Bronsted acids, boron fluoride ether complexes are particularly preferred among sulfuric acid, para-toluenesulfonic acid, perchloric acid, and aluminum chloride.

The amount used is 0.0% relative to polyalkylene glycol.
01-1% by weight, preferably 0.02-0.5% by weight. The proportion of polyalkylene glycol and epihalohydrin is such that the amount of epihalohydrin is 1 to 10 mol, preferably 2 to 5 mol, per mol of polyalkylene glycol. That is, if the amount of epihalohydrin is less than 1 mole, unreacted polyalkylene glycol will remain, making it impossible to obtain a cationic water-soluble resin that meets the objectives of the present invention and resulting in insufficient performance as a water retention agent. On the other hand, if it exceeds 10 moles, gelation tends to occur during the production of the cationic water-soluble resin, which is not suitable.

The cationic water-soluble resin in the present invention can be produced by adding the aziridine compound (b) to the polyalkylene glycol polyhalohydrin ether (a) obtained in the above procedure or an aqueous solution thereof and carrying out a ring-opening addition polymerization reaction. can. At that time, the weight ratio of polyalkylene glycol polyhalohydrin ether (a) and aziridine compound (b) is 100 parts by weight of polyalkylene glycol polyhalohydrin ether (a).
) 10 to 10,000 parts by weight, preferably 30 to 1000 parts by weight
Parts by weight. That is, the aziridine compound (b) is 1
If it is less than 0 parts by weight, the performance will be insufficient when used as a water retention agent, while if it exceeds 10,000 parts by weight, it will be economically disadvantageous. Further, the reaction is carried out in an aqueous solution in which the final concentration of the cationic water-soluble resin is 5 to 100% by weight, preferably 10 to 70% by weight, and the temperature at which the aziridine compound (b) is normally subjected to the ring-opening polymerization reaction, for example, 0. ~200℃
The reaction is slow in an aqueous solution having a final concentration of less than 5% by weight, and the performance is insufficient when used as a water retention agent. In addition, if the reaction temperature is less than 0°C, the reaction rate is slow;
If the temperature exceeds 0°C, it is difficult to control the reaction. The cationic water-soluble resin obtained by this method can be adjusted to have a wide molecular weight, for example, 1,000 to 20
00,000, preferably s, ooo to 1,000,000.

The cationic water-soluble resin in the present invention can also be produced by adding polyamine (c) to polyalkylene glycol polyhalohydrin ether (a) or its aqueous solution and causing an addition reaction. The polyamine (c
) can be used without particular limitation as long as it has two or more amine groups in the molecule. Examples thereof include polyalkylene polyamines and polyamide polyamines, among which polyalkylene imine is preferred, and polyethylene imine is more preferred, and the preferred amount of the polyamine (c) to be used is the same as in the case of the aziridine compound (b). The same is true. However, in the present invention, the cationic water-soluble resin obtained by the former method is preferred.In the present invention, the cementing water retention agent for wellbore of the above-mentioned invention contains 0.001 to 10% by weight, preferably 0.001 to 10% by weight, based on the cement.
It is used in an amount of 1 to 5% by weight. That is, the amount added is o, o
If it is less than i% by weight, the water retention effect will not be sufficiently obtained;
If it exceeds the weight percentage, the compressive strength of the solidified cement will decrease and it will also be economically disadvantageous.

The water retaining agents used in the present invention include AE agents, AE water reducing agents, hardening accelerators, hardening retarders, antifoaming agents, thickeners, dispersants, and rust preventive agents that have been conventionally used in cement slurry compositions. Additives can be optionally used in combination.

The cement used in the present invention is applicable to all cements used in defense, such as Portland cement and blast furnace cement.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited in any way by these examples.

Synthesis Example 1 A flask equipped with a dropping funnel, a stirrer, a thermometer, and a reflux condenser was charged with 1,000 g of polyethylene glycol having a molecular weight of 1,800, and heated to 65°C. After adding 2.1 g of boron trifluoride (Nieteller) as a catalyst, 113.1 g of epichlorohydrin was added dropwise over 20 minutes, and the reaction was further carried out for 4.5 hours to obtain polyethylene glycol polychlorohydrin ether.

160 g of the obtained polyethylene glycol polychlorohydrin ether was diluted with 1,600 g of ion-exchanged water,
Heat to 80℃, then add 240g of ethyleneimine to 45℃.
The reaction was continued for 6 hours, and the reaction was completed when it was confirmed by gas chromatography that the residual ethyleneimine was 1 ppm or less and the viscosity of the resin was constant. I got it.

The concentration of the obtained water-soluble resin (1) was 20% by weight, and 25% by weight.
The viscosity at °C (Type B) was 360 cps.

Synthesis Examples 2 to 4 Except for the types of raw materials used in Synthesis Example 1, the amounts used, and the conditions for the reaction as shown in Table 1,
The same operation as in Synthesis Example 1 was repeated to obtain cationic water-soluble resins (2) to (4). The properties of the aqueous solutions of these resins were as shown in Table 1.

Synthesis Example 5 65g of polyethyleneimine with a molecular weight of 10,000 was placed in the same flask as in Synthesis Example 1, and 335g of ion-exchanged water was added.
and heated to 50°C. Next, 50 g of a 50% aqueous solution of polyethylene glycol polychlorohydrin ether obtained in Synthesis Example 2 was added, and further 0.5 g of a 50% aqueous sodium hydroxide solution was added and reacted for 2 hours to form a cationic water-soluble resin (5). Obtained.

The concentration of the obtained water-soluble resin was 20% by weight, and the viscosity (B type) at 25°C was 29 cps"C'.

Synthesis Example 6 Into the same flask as in Synthesis Example 1, 76g of polyamide polyamine obtained from the condensation reaction of diethylenetriamine and adipic acid was charged, diluted with 346g of ion-exchanged water, and 50%
heated to ℃. Next, 28 g of a 50% aqueous solution of polyethylene glycol polychlorohydrin ether obtained in Synthesis Example 1 was added, and 1.2 g of a 50% aqueous sodium hydroxide solution was added and reacted for 2 hours to form a cationic water-soluble resin (6). Obtained. The concentration of the obtained water-soluble resin was 20% by weight.
The viscosity (Type B) at 25°C was 175 cps. Examples and Comparative Examples Portland cement class G100O parts by weight, artificial seawater 583.5 parts by weight, lignin sulfonic acid 19.5 parts by weight.
9 parts of sodium silicate, 3.2 parts of stearate
Mixing in a mixer at 3°C and adding 11.7 parts of cationic water-soluble resins (1) to (6) in terms of solid content as water retention agents, the miscibility, free water content and amount of dehydration were calculated. It was measured. The results are shown in Table 2. As a comparative example, molecular weight 7
The same procedure was carried out for 0000 polyethyleneimine and hydroxyethylcellulose.

Claims (1)

[Claims] 1. To 100 parts by weight of polyalkylene glycol polyhalohydrin ether (a) obtained by reacting 1 to 10 moles of epihalohydrin per mole of polyalkylene glycol, add an aziridine compound (b) or a polyamine (c )1
A cementing water retention agent for wellbore consisting of a cationic water-soluble resin obtained by reacting 0 to 10,000 parts by weight. 2. The cementing water retaining agent for wells according to claim 1, which is obtained by reacting epihalohydrin in a range of 2 to 5 moles per mole of polyalkylene glycol. 3. Add aziridine compound (b) or polyamine (c) to polyalkylene glycol polyhalohydrin ether (a
2. The cementing water retention agent for wells according to claim 1, wherein the water retention agent is reacted in a range of 30 to 1000 parts by weight per 100 parts by weight. 4. Polyalkylene glycol polyhalohydrin ether (a) and aziridine compound (b) or polyamine (c
2. The cementing water retaining agent for wellbore according to claim 1, which is obtained by reacting the cationic water-soluble resin obtained from the above in an aqueous solution at a temperature of 0 to 200 DEG C. to give a final concentration in the range of 5 to 100% by weight. 5. Polyalkylene glycol has a molecular weight of 200 to 100
. 6. The cementing water retaining agent for wellbore according to claim 1, wherein the polyalkylene glycol is polyethylene glycol. 7. The cementing water retaining agent for wells according to claim 1, wherein the epihalohydrin is epichlorohydrin. 8. The cementing water retention agent for wellbore according to claim 1, wherein the aziridine compound (b) is ethyleneimine. 9. The cementing water retaining agent for wells according to claim 1, wherein the polyamine (c) is a polyalkylene imine. 10. Add aziridine compound (b) or polyamine (c) to 100 parts by weight of polyalkylene glycol polyhalohydrin ether (a) obtained by reacting 1 to 10 moles of epihalohydrin per mole of polyalkylene glycol.
A cement slurry comprising a cementing water retention agent for wellbore consisting of a cationic water-soluble resin obtained by reacting 10 to 10,000 parts by weight. 11. Epihalohydrin with polyalkylene glycol 1
Claim 10 wherein the reaction is carried out in a range of 2 to 5 moles per mole.
Cement slurry as described. 12. Add aziridine compound (b) or polyamine (c) to polyalkylene glycol polyhalohydrin ether (
The cement slurry according to claim 10, wherein the cement slurry is reacted in a range of 30 to 1000 parts by weight per 100 parts by weight of a). 13. Polyalkylene glycol polyhalohydrin ether (a) and aziridine compound (b) or polyamine (
Cement slurry according to claim 10, wherein the cationic water-soluble resin obtained from step c) is reacted in an aqueous solution at a temperature of 0 to 200C to a final concentration in the range of 5 to 100% by weight. 14. Polyalkylene glycol has a molecular weight of 200 to 10
11. The cement slurry of claim 10 in the range of 0,000. 15. The cement slurry according to claim 10, wherein the polyalkylene glycol is polyethylene glycol. 16. The cement slurry according to claim 10, wherein the epihalohydrin is epichlorohydrin. 17. The cement slurry according to claim 10, wherein the aziridine compound (b) is ethyleneimine. 18. The cement slurry according to claim 10, wherein the polyamine (c) is a polyalkylene imine.