JPH01146736A - Reservoir equipment - Google Patents

Abstract

PURPOSE:To reduce the organic matter dissolving into the water in a reservoir equipment by using the composition of a specified liquid diene polymer as an interior agent. CONSTITUTION:Alcohol or the mixture of alcohol and paraffin as the treating agent for mol.wt. fractionation is added to the liquid diene polymer containing hydroxyl group having 1wt.% or less of unreacted monomer content, and two- phase separation is formed. Next, the liquid diene polymer obtained by separating its lower phase, polyisocyanate compound and an curing accelerate are compounded and are mixed by agitation, whereby liquid polymer composition is prepared. This liquid polymer composition is sprayed on the inner surface of a pipe or tank, and is cure-treated, thereby forming cured film on its inner surface.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to water equipment, and more particularly to water equipment whose inner surface is provided with a hardened coating in which the elution of total organic carbon (TOC) is suppressed as much as possible. [Prior Art] In water facilities, leaching of rust from the steel materials constituting the facility has become a problem, and as a means to prevent this, the interior has been lined with organic compounds. Conventionally, such an interior material has been produced by forming a cured film of a liquid polymer composition comprising a hydroxyl group-containing liquid diene polymer and a polyisocyanate compound on the inner surface of the pipe.
It is known that anti-corrosion etc.
Publication No.). However, the hydroxyl group-containing liquid diene polymer used in conventional liquid polymer compositions (i.e., is a mixture of low molecular weight and high molecular weight polymers, and is a polymer with a wide molecular weight distribution). Therefore, when a hardened film of this liquid polymer composition is formed on the inner surface of water pipes or water storage tanks, low molecular weight organic matter will be eluted into the water, and the total organic carbon (TOC) in the water will be reduced. [Problems to be Solved by the Invention] The present invention uses a composition made of a specific liquid diene polymer as an interior material to dissolve into the water of water facilities. The purpose of this invention is to reduce organic substances. Means for Solving Problem E] The present inventor (a) has discovered that the organic substances eluted into the water of water facilities in which a liquid diene polymer composition is used for the interior. Estimating that most of the substances are low molecular weight substances of liquid diene polymers, we obtained good results by using materials with low low molecular weight content as raw material liquid diene polymers. The present invention has been completed.The hydroxyl group-containing liquid diene polymer used as the starting material of the present invention has a hydroxyl group inside the molecular chain or at the end of the molecular chain and has a number average molecular weight of 300 to 25,000, preferably 5.
Examples include liquid diene polymers of 00 to 111,000. Here, the content of hydroxyl groups is usually 0.1 to tomeq/9,
Preferably it is 0.3 to 71 eq/g. Examples of these liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specific examples include butadiene homopolymer, inbrene homopolymer, butadiene-styrene copolymer, phtadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. can. These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in a liquid reaction medium in the presence of hydrogen peroxide. Examples of the alcohol used as a treatment agent for molecular weight fractionation of the present invention include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, and n-butyl alcohol.
-Hexyl alcohol, 2-ethylhexyl alcohol, etc. can be used. - The amount used is 10 to 100 parts by weight, preferably 50 to 5 parts by weight, per 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
00 parts by weight can be used. If the amount used is less than this range, it will be difficult to form two-phase separation, and if it is used in excess of this range, there will be little effect. Examples of the paraffin used together with alcohol in the molecular weight fractionation of the present invention include pentane, hexane, heptane,
N-paraffins such as octane, i-paraffins or mixtures containing these can be used. In this case, the blending ratio of alcohol and paraffin can be such that the paraffin content is at most 60% by weight, preferably at most 50% by weight. The amount of this mixed treatment agent used is 10 to 100 parts by weight per 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
Preferably 50 to 500 parts by weight can be used. If the amount used is less than this range, the two layers will be difficult to separate, and if it is used in excess of this range, there will be little effect. The hydroxyl group-containing liquid diene polymer used in the present invention is produced by separating those in the high molecular weight range by specific molecular weight fractionation. The molecular weight-fractionated hydroxyl group-containing liquid diene polymer used as the main raw material for the interior decoration material of the present invention is obtained by adding alcohol or, if necessary, further paraffin to the hydroxyl group-containing liquid diene polymer as the starting material, and then heating it at room temperature to 100%. at a temperature of 0.1 to 300 minutes, preferably 0.5 to 10
Mixed for 0 min, at a temperature of room temperature to 100°C, 0.1
It can be obtained by standing still for 500 hours, preferably 0.5 to 100 hours to form two phases, fractionating the lower phase and distilling off the processing agent under reduced pressure. The polyisocyanate compound used as another main raw material for the interior material of the present invention is an organic compound having two or more incyanate groups in one molecule, which has a hydroxyl group in the hydroxyl group-containing liquid diene polymer. Any material having a reactive incyanate group can be used. Examples of polyisocyanate compounds include the usual aromatic, aliphatic, and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (M
DI), liquid modified diphenylmethane diisocyanate,
Polymethylene polyphenylisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate,
Examples include cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2, diisocyanate, addition reaction products of polypropylene glycol and tolylene diisocyanate, and particularly preferred are MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like. There is no particular restriction on the blending ratio of the above two components used in the interior material of the present invention, but usually the ratio of incyanate groups (NGO) of the polyisocyanate compound to the hydroxyl groups (OH) of the hydroxyl group-containing liquid diene polymer (N COlo H ) should be in a molar ratio of 0.2 to 25, preferably 0.5 to 15. If this molar ratio is outside the above range, curing becomes difficult, which is not preferable. If desired, a polyol compound or a polyamine compound can be added as a strong rice agent, and various other additives can also be added. Polyol compounds used here as desired include:
Any of primary polyol, secondary polyol, and tertiary polyol may be used. Specifically, for example, 1. Topropylene glycol, cyclopylene glycol, 1.
Dobutanediol, 1,3-butanediol, 2,3-
Butanediol, 1.2-bentanediol, 2.3-
Bentanediol, 2.5-hexanediol, 2.4
-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N, N
Low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon, such as -bistohydroxypropylaniline, N,N-bishydroxyisopropyl-2-methylpiperazine, and propylene oxide adduct of bisphenol A. Furthermore, ethylene glycol, 1,3-propylene glycol, l, dobutanediol, 1°5-bentanediol, 1,6-hexanediol, etc., which do not contain hydroxyl groups bonded to secondary carbons, may be used as polyols. can. Diols are usually used as polyols, but triols and tetraamines may also be used, and those having a molecular weight in the range of 50 to 500 can be used.The polyamine compounds optionally added to the present invention include diamines. , triamine, or tetraamine. Furthermore, any of primary polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of such polyamine compounds include aliphatic amines such as hexamethylene diamine, alicyclic amines such as 3,3'-dimethyl and 4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodiphenyl. Aromatic amine, 2,4.6-1-ly(dimethylaminomethyl)
Examples include tetramine such as phenol. In the present invention, when blending these polyol compounds and polyamine compounds, there is no particular restriction on the blending ratio, but usually 1 part of the polyol compound or polyamine compound is added to 100 parts by weight of the above-mentioned hydroxyl group-containing liquid diene polymer. ~1000 parts by weight, preferably 3-2
00 parts by weight can be blended. . Other additives that can be added to the raw materials for the interior material of the present invention, if desired, include mica, rubber, etc. Examples of fillers include phite, heluite, calcium carbonate, and slate powder. Furthermore, plasticizers such as dioctyl phthalate are added as viscosity modifiers, softeners such as aromatic, naphthenic, and paraffinic oils are added, and alkylphenol resins, terpene resins, and terpene resins are added to adjust adhesive strength and adhesive strength. Fumonol resin, xylene formaldehyde resin,
Tackifying resins such as rosin, hydrogenated rosin, coumaron resins, aliphatic and aromatic petroleum resins can also be added. Further, a curing accelerator such as dibutyltin dilaurate, stannous octoate/polyethylenediamine, etc. can also be added. Furthermore, an anti-aging agent can be added to improve weather resistance, and a silicon compound or the like can be added as an antifoaming agent. The composition forming the cured film used in the present invention can be obtained by blending and mixing the above raw materials. There are no particular restrictions on the mixing conditions, but usually 0 to 70°C;
A liquid composition is obtained by stirring and mixing preferably at 15 to 50° C. for 0.5 seconds to 180 minutes, preferably 1 second to 120 minutes. The conditions for the curing treatment for forming the interior material of the present invention are not particularly limited, but are usually 0 to 150°C, preferably 15 to 150°C.
The time is 0.5 to 168 hours, preferably 1 to 72 hours at 20°C. The thickness of the cured film in this case may be determined in consideration of the desired mechanical strength, etc., but it is usually 0.1 to 10 mm, preferably about 0.3 to 5III.

【Example】

The present invention will be explained in more detail with reference to Examples. (Preparation example 1 of liquid diene polymer containing hydroxyl groups) R-45HT (Mn = 2760, MW) manufactured by Idemitsu Arc Co., Ltd.
/ Mn = 2.11 hydroxyl group content = 0.82 mcq
/9, hydroxyl-terminated liquid polybutadiene (abbreviation 1-0) with an unreacted butadiene content of 0.1% by weight or less) was added to the foreground part of 100% ethanol, and was heated in a 31 separatory funnel at 25°C for 5 minutes. A mixture was obtained by shaking. This mixture was allowed to stand at 25°C for 20 hours to separate into two phases, the upper phase was fractionated, and from this liquid at 120°C
Ethanol was distilled off at 111111 Hg for 2 hours to obtain a hydroxyl group-terminated liquid diene polymer (abbreviation 1-A). Hydroxyl-terminated liquid polybutadiene (abbreviation 1-B) was obtained in the same manner from the lower phase fraction, and this was used below. The results are shown in the table below. (Left below) (Preparation example 2 of liquid diene polymer containing hydroxyl groups) Preparation example 1
Hydroxyl-terminated liquid polybutadiene (abbreviation 2-0) used in
To 100 parts by weight, 200 parts by weight of t-butanol and 30 parts by weight of heptane were added, and 25 parts by weight was added in 3 parts by weight.
A mixture was obtained by shaking for 5 minutes at °C. This at 25℃
After standing for 20 hours, the mixture was separated into an upper phase fraction and a lower phase fraction. 12 t-butanol and heptane from both phases, respectively.
Distillation was carried out at 0°C for 2 hours at 1+++aH9 to obtain polybutadiene with hydroxyl group ends (abbreviation 2-A) and polybutadiene with hydroxyl group ends (abbreviation 2-B), respectively. The results are shown in the table below. (Preparation example 3 of hydroxyl group-containing liquid diene polymer) Hydroxyl group-terminated liquid polyisoprene [Mn=3020, MW/Mn-
2,32, hydroxyl group content - 0, 75 meq/ 9, unreacted isoprene content = 0.5% by weight] (abbreviation 3-0) to 100 parts by weight, Impropatool 220 parts by weight, isoparaffin mixture [Idemitsu Petrochemical Co., Ltd. Product Name I
P-1016] 20 parts by weight was added to 15 parts by weight in a separating funnel.
Shake for 5 minutes at 15°C to obtain a mixture and incubate at 15°C for 20
The mixture was allowed to stand for a period of time to separate into two phases. Improper tool and isoparaffin were distilled off from both the upper and lower phases at 120°C and lmmHg for 2 hours to obtain low molecular weight hydroxyl group-terminated liquid polyisoprene (abbreviation 3-A).
and high molecular weight hydroxyl group-terminated liquid polyisoprene (abbreviation 3
-B) was added. The results are shown in the table below. (Preparation example 4 of hydroxyl group-containing liquid diene polymer) Preparation example 1
The same hydroxyl-terminated liquid polybutadiene [However, use one with a butadiene content of 2.0% by weight] (abbreviation 4-0)
100 parts by weight of ethanol was added to 100 parts by weight of O.
, A mixture was obtained by incubating it for 5 minutes at 25 °C in a heat-resistant glass bottle, and standing at 25 °C for 20 hours to form two-phase separation, and the upper and lower phases were collected separately.
Ethanol was distilled off for 2 hours at 120°C and 1+*mHg to produce a low molecular weight hydroxyl group-containing liquid diene polymer (abbreviation 4-A) and a high molecular weight hydroxyl group containing liquid diene polymer (abbreviation 4-B). I got it. The results are shown in the table below. (Preparation example 5 of hydroxyl group-containing liquid diene polymer) Preparation example 3
The same hydroxyl-terminated liquid polyingrene isoprene [However, the one containing 2% by weight of imprene monomer was used]
(Abbreviation 5-0) 220 parts by weight of isopropanol and 20 parts by weight of the same isoparaffin mixture as in Preparation Example 3 were added to 100 parts of ffi, and the mixture was separated in a 31 separatory funnel at 15°C for 5 minutes. A mixture was obtained. This was allowed to stand at 15°C for 20 hours to form two phases, separated into each phase silver, and the processing agent was removed from both phases at 120°C for 1 hour.
It was removed by distillation at a+a+Hy for 2 hours. From the upper phase, a low molecular weight hydroxyl group-containing liquid diene polymer (abbreviation 5-
A) and a high molecular weight hydroxyl group-containing liquid diene polymer (abbreviation 5-B) were obtained. The results are shown in the table below. (Examples 1 to 3 and Comparative Examples 1 to 3) Preparation of composition and evaluation of applicability to water storage tank Display amount of hydroxyl group-containing liquid diene polymer system polymer prepared in Preparation Examples 1 to 5 and display of diphenylmethane diisocyanate and the indicated amount of dibutyltin silaurylate as a curing accelerator, and stirred and mixed at 25° C. for 5 minutes to prepare a liquid polymer composition. This liquid polymer composition was sprayed onto the inner surface of a spherical water tank with a diameter of 2.5 m to a thickness of about 1 mrn and cured at 25° C. for 24 hours to produce a water tank with a hardened film formed on the inner surface. . On the other hand, separately prepare the same liquid polymer composition as above, pour this composition into a mold, press harden it at 120°C for 60 minutes at 200 kg/cm'',
A cured body of 100 x 100 mm was prepared, and a total organic carbon (TOC) extraction test was conducted using this as a test piece. The results are shown in Table 1. (Left below) [Effects of the invention] In the water of the water equipment of the present invention, eluted organic carbon is reduced,
Moreover, it has the advantage that its effect lasts for a long time compared to conventional products, and it can be used as an interior material for water facilities.
It not only has anti-corrosion properties but also solves hygienic problems, making it extremely useful. Patent applicant: Idemitsu Petrochemical Co., Ltd.

Claims (1)

[Claims] 1 Adding alcohol or a mixture of alcohol and paraffin to a hydroxyl group-containing liquid diene polymer having an unreacted monomer content of 1% by weight or less to form two-phase separation,
A water facility in which a cured film of a liquid polymer composition comprising a liquid diene polymer and a polyisocyanate compound obtained by separating the lower phase thereof is formed on the inner surface of a pipe or tank.