JPH0781068B2 - Stable alkylene oxide polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition of an alkylene oxide polymer,
In particular, it relates to a stable alkylene oxide polymer composition which is prevented from deterioration due to contamination with heavy metal ions such as copper.

(Prior Art) Among alkylene oxide polymers, polymers of propylene oxide and ethylene oxide are polyoxypropylene glycol, polyoxyethylene glycol or polyoxyalkylene glycol as polyurethane elastomers, paints, adhesives, mount materials, sealants. ,
It is used for forms.

Further, the alkylene oxide polymer is aminated at the terminal to form a so-called polyether diamine, which is used as a cross-linking agent for epoxy resin and polyurethane. It is also used as a sealing material as a modified silicone resin by silylating the terminal of a polymer.

Other polyoxyalkylene glycols are used as modifiers for water-soluble polyester paints, lubricants for electronic parts, hydraulic oils, etc.

Further, high molecular weight polymers such as propylene oxide and butylene oxide are being developed for use as elastomers.

(Problems to be solved by the invention) Thus, when the alkylene oxide polymer is used as a molded article, an adhesive, a paint, a sealing material, etc., heavy metals in contact, particularly copper, are eluted into the polymer. The problem is to cut and degrade the polymer.

(Means for Solving Problems) As a result of various studies to prevent deterioration of the alkylene oxide polymer due to heavy metal ions and enable long-term use, it was discovered that a hydrazine derivative having an antioxidant action is effective. The present invention has been reached.

That is, the present invention relates to an alkylene oxide polymer and the general formula (I): [In the formula, R ₁ is hydrogen or a C ₁ -C ₄ alkyl group, and n is 2-
Indicates an integer of 10. Disalicyloylhydrazide, represented by] (2) In formula _{(II): R 3 -S-} X-COOR 2 (II) [wherein X is an alkylene group of C ₁ -C _3, R ₂ is C ₈ -C ₂₀ alkyl group, R ₃ is a C ₈ -C ₂₀ alkyl group or the general formula (II
I): —X—COOR ₄ (III) (wherein X represents a C _{1 to} C ₃ alkylene group, and R ₄ represents a C _{8 to} C ₂₀ alkyl group). An alkyl ester of a mercapto fatty acid represented by the above, and (3) an alkylene oxide polymer composition comprising melamine, which is stable against heavy metal ions.

Examples of the C ₁ -C ₄ alkyl group represented by R ₁ in the general formula (I) of the present invention include methyl, ethyl, i-propyl, n-butyl, t-butyl, i-amyl and the like.
X is an integer of 2 to 10, and the dihydrochloric acid group bonded to the two salicyloylhydrazines in the general formula (I) is succinic acid, adipic acid, sebacic acid, decamethylenedicarboxylic acid. Specific examples of the compound represented by the general formula (I) include, for example, disalicyloyl hydrazide succinate, di (3-methylsalicyloyl) succinate hydrazide, disalicyloyl hydrazide adipic acid, and di (3 adipic acid). -T
-Butylsalicyloyl) hydrazide, sebacic acid disalicyloyl hydrazide, sebacic acid di (3-i-propyl salicyloyl) hydrazide, decamethylene dicarboxylic acid disalicyloyl hydrazide, decamethylene dicarboxylic acid di (3-ethyl) Salicyloyl) hydrazide, decamethylene dicarboxylic acid di (3-t-butyl salicyloyl) hydrazide and the like.

These salicyloyl hydrazides are used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total composition.

C _{1 to} C ₃ represented by X in the general formulas (II) and (III)
The alkylene group of is a methylene, ethylene or i-propylene group. Examples of the C _{4 to} C ₂₀ alkyl group represented by R ₂ , R ₃ and R ₄ include butyl, amyl, hexyl, octyl, 2-ethylhexyl, lauryl, myristyl, palmityl and stearyl groups.

Specific examples of the mercapto fatty acid alkyl ester represented by the general formula (II) include dioctyl thiodiacetate,
Dilauryl thiodiacetate, dilauryl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl thiodipropionate, octyl palmityl thiodipropionate, distearyl thiodipropionate, β,
β′-dihexyl thiodibutyrate β, β′-thiodibutyrate distearyl, butyl (octylthio) acetate, amyl (laurylthio) propionate, stearyl (butylthio) propionate, butyl β- (laurylthio) butyrate and the like.

These mercapto fatty acid alkyl esters are used in an amount of 0.5 to 2.5 parts by weight based on 100 parts by weight of the total composition.

Melamine is used in an amount of 0.5 to 2.5 parts by weight based on 100 parts by weight of the total composition.

Metals in which these compounds exhibit the effect of preventing the decomposition of the alkylene oxide polymer are copper, iron, nickel, cobalt, manganese, titanium, vanadium, chromium, cadmium and the like, and among them, particularly effective for copper. These compounds prevent decomposition of the alkylene oxide polymer by reacting with metal ions to form a complex.
In addition, the phenol group contained prevents the alkylene oxide polymer from deteriorating due to its antioxidant effect.

The alkylene oxide of the present invention is ethylene oxide,
Propylene oxide, butylene oxide and tetrahydrofuran. When polymerizing these alkylene oxides, homopolymerization or copolymerization of two or more kinds is performed.

The polymer of alkylene oxide is usually referred to as polyether polyol, and is a liquid or waxy substance having a molecular weight of 200 to 10,000. More specifically, water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,2- Hexylene glycol, 1,10-decanediol, 1,2-cyclohexanediol, 2-butene, 1,4-diol, 3-cyclohexane-1,1-dimethanol, 4-methyl-3-cyclohexane-1,1 -Dimethanol, 3-methylene-1,5-pentanediol, (2-hydroxyethoxy) -1-propanol-4- (2-hydroxyethoxy) -1-butanol, 5- (2-hydroxypropoxy) -1- Pentanol, 1- (2-hydroxypropoxy) -2-
Octanol, 3-allyloxy-1,5-pentanediol, 2-allyloxymethyl-2-methyl-1,3-pentanediol [(4,4-pentyloxy) -methyl] -1,3-
Propanediol, 3- (o-propenylphenoxy)
-1,2-propanediol, 2,2'-diisopropylidene bis (p-phenyleneoxy) diethanol, glycerin, 1,2,6-hexanetriol, 1,1,1-trimethylolethane, 1,1, 1-trimethylolpropane, 3- (2
-Hydroxyethoxy) -1,2-propanediol, 3
-(2-Hydroxypropyl) -1,2-propanediol, 2,4-dimethyl-2- (2-hydroxyethoxy)
-Methylpentanediol-1,5,1,1,1-tris [(2
-Hydroxy) methyl] -ethane, 1,1,1-tris [(2-humanroxypropoxy) -methyl] propane,
Pentaerythritol, sorbit, sucrose, lactose, α
-Methyl glucoside, α-hydroxyalkyl glucoside, novolac resin, phosphoric acid, benzene phosphoric acid, polyphosphoric acid (eg tripolyphosphoric acid and tetrapolyphosphoric acid)
Polyhydroxy compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, methyleneorthochloraniline, 4,4'-diphenylmethanediamine, 2,4-tolylenediamine, polyamines such as 2,6-tolylenediamine, triethanol Alkanolamines such as amine and diethanolamine are added to ethylene oxide, propylene oxide, butylene oxide,
1 or 2 such as tetrahydrofuran or styrene oxide
Polyether polyols obtained by adding one or more species, or polytetramethylene ether glycol.

Further, polyether amines or polyether mercaptans obtained by NH ₂ conversion or SH conversion of a part or 50% or more of the terminal OH groups of these polyether polyols can also be used. In addition, it is possible to use a polyoxyalkylene in which the terminal OH group of the polyether polyol is intramolecularly dehydrated to form a double bond. Further, it is described in JP-A-50-156599 obtained by reacting this with a hydrosilicon compound. Modified silicone resin can also be used.

The compound of the present invention is used by adding a required amount to these alkylene oxide polymers in admixture.

Various methods are used to cure the alkylene oxide polymer. That is, the polyether polyol is the third
The primary amine and / or the organometallic compound is used as a catalyst to react with the polyisocyanate. Polyether mercaptan uses metal oxides such as lead dioxide, chromates, and organic hydroperoxides as vulcanizing agents. Polyoxyalkylene having a terminal double bond is cured by moisture in the air using nitrile oxide and barium oxide. The modified silicone resin is cured by moisture in the presence of a catalyst such as a fatty acid salt of tin, lead or iron, or a titanate ester as a catalyst.

The polyisocyanate used for curing the polyether polyol is, for example, 2,4-tolylene diisocyanate (2,4
-TDI), 2,6-tolylene diisocyanate (2,6-TD
I), a mixture of both isocyanates in an 80/20 weight ratio (80
/ 20-TDI), 65/35 weight ratio mixture (65 / 35-TDI), crude tolylene diisocyanate (crude TDI), diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2. , 4'-diisocyanate (2,4'-MD
I), diphenylmethane-2,2'-diisocyanate (2,
2'-MDI) and mixtures thereof (MDI), polymethylene polyphenyl polyisocyanate (crude MDI), toluidine diisocyanate (TODI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (H
DI), isophorone diisocyanate, dicyclohexylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), and other polyisocyanates.

These polyisocyanates can be used as they are, or can be used as a prepolymer with the following polyol, a carbodiimide modified product, a dimer, a trimer, a buret modified product, or a phenol block product. These polyisocyanates may be used alone or in 2
Use as a mixture of two or more species.

When the polyisocyanate is reacted to cure the polyether polyol, a crosslinking agent is used if necessary. Crosslinking agents include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, monomer polyols such as 1,3- and 1,4-butanediol, alkanolamines such as triethanolamine and diethanolamine. Aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine,
Aliphatic polyamines such as piperidine and its derivatives, methylene orthochloraniline, 4,4'-diphenylmethanediamine, aniline, 2,4-tolylenediamine, 2,6-
Aromatic polyamines such as tolylenediamine, and hydroxyl values obtained by adding ethylene oxide, propylene oxide, etc. to these active hydrogen compounds, 200 mgK
It is a compound of OH / g or more.

In addition, a compound having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide and / or propylene oxide to hydroquinone, resorcin, aniline or the like can also be used.

Further, polyether amine obtained by converting the terminal OH group of the polyether polyol into NH ₂ and moisture in the air can also be used as the crosslinking agent. Further, enamines which are hydrolyzed by moisture in the air to form an active hydrogen-containing compound as described in JP-A-47-34305 can also be used in the present invention.

Equivalent ratio (NCO / H) of NCO group in polyisocyanate to active hydrogen in polyether polyol and cross-linking agent is 0.70
The amounts of polyisocyanate, polyether polyol and cross-linking agent used are adjusted so as to be about 1.40.

Among the catalysts that accelerate the reaction of polyether polyol and polyisocyanate, the tertiary amines include triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N- Ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, diethylenetriamine, N, N, N ',
N'-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethyl-
1,3-butanediamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N -Dimethylcyclohexylamine, N, N, N ',
N ", N" -pentamethyldiethylenetriamine, triethylenediamine, triethylenediamine formate and other salts, oxyalkylene adducts of amino groups of primary and secondary amines, aza rings such as N, N-dialkylpiperazines Compounds, various N, N ', N "-trialkylaminoalkylhexahydrotriazines, β of JP-B-52-43517
-Aminocarbonyl catalyst, β-aminonitrile catalyst of Japanese Patent Publication No. 53-14279, and the like.

As the organometallic urethane-forming catalyst, tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, naphthene. For example, cobalt acid. These catalysts are used alone or as a mixture, and the amount used is a compound having active hydrogen.
It is 0.0001 to 10.0 parts for 100 parts.

Various organic and inorganic fillers can be used in the present invention.

Among these, examples of inorganic substances include calcium carbonate,
Talc, clay, mica, graphite, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, calcium sulfate, zinc oxide, calcium oxide, aluminum oxide, titanium oxide, iron oxide, silicic acid anhydride, glass flakes, carbon black, silica stone, There are rock wool etc. These shapes are powdery, scale-like, or fibrous and can be used as they are, but the physical properties of the product can be improved by subjecting the surface thereof to titanium treatment, silicon treatment or the like in advance.

The organic substances include bitumen, pine resin, resin powder, wood powder, animal and vegetable fibers, artificial fibers and the like.

In addition to the above, minute hollow spheres such as silica balloons, glass balloons, phenol resin balloons, vinylidene chloride resin balloons, shirasu balloons, and pearlite can also be used.

In the present invention, a plasticizer or a flame retardant can be used. These plasticizers and flame retardants include, for example, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (2,3-chloropropyl) phosphate, tris (2). , 3-dibromopropyl) phosphate, dioctyl adipate, dibutyl sebacate, decabromodiphenyl ether, antimony oxide and the like.

Further, in the present invention, in order to increase the durability of the product, one or more heat stabilizers, antioxidants, ultraviolet absorbers and ultraviolet stabilizers can be used as stabilizers.

As the heat stabilizer, tetramethyl thiuram disulfide, copper dimethyl dithiocarbamate or the like is used.

Position-disordered phenols are used as antioxidants,
For example, product name Irganox 1010, Irganox 1076
(Manufactured by Ciba Geigy) and product name Yoshinox BHT,
Yoshinox BB and Yoshinox GSY-930 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) correspond to this.

As the ultraviolet absorber, for example, benzotriazoles such as TINUVIN P, TINUVIN 327, and TINUVIN 328 (manufactured by Ciba Geigy), or benzophenones such as TOSISOP 800 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) can be used.

As an ultraviolet stabilizer, for example, trade name SANOL LS77
0, Sanol LS744, Tinuvin 144 (Ciba Geigy)
Positionally disturbed amines such as, or product name Tinuvin 12
0, Irgastab 2002 (manufactured by Ciba Geigy) and the like are preferable.

In addition to the various additives described above, a silicon or titanium coupling agent may be added to increase the affinity of the filler for the alkylene oxide polymer, thereby improving the physical properties. A defoaming agent, a surface modifier, etc. can also be added.

If necessary, a solvent may be used to improve processability, and a foaming agent and a foam stabilizer may be used to form a foam.

Suitable solvents include, for example, aromatic hydrocarbons such as toluene and xylene, aliphatically added hydrogen such as hexane, heptane and octane, and petroleum solvents such as gasoline to kerosene fraction.

In carrying out the present invention, a method of reacting a polyether polyol with a polyisocyanate and curing the same is roughly classified into the following two methods. One is to add and mix a crosslinking agent, a tertiary amine as a catalyst and / or an auxiliary agent such as an organometallic compound, a filler, a plasticizer, etc. to a polyether polyol to prepare a resin solution, which is then mixed with a polyisocyanate for reaction. It is a method of curing. The other is a method of reacting a polyether polyol with a polyisocyanate in advance to prepare a prepolymer, and then reacting it with various crosslinking agents to cure it.

When preparing the prepolymer, in addition to polyether polyol, polyester polyol, polybutadiene diene, castor oil polyol, etc. are added with propylene glycol, dipropylene glycol, bisphenol A, and 2 to 5 moles of propylene oxide. NCO / OH ratio of 1.5-1
5. React for several hours at a reaction temperature of 60-120 ° C. The free NCO group content of the obtained prepolymer is 1 to 30%.

(Action and Effect) By adding the compound of the present invention, the alkylene oxide polymer can be prevented from being deteriorated by heavy metal ions such as copper.

Therefore, when the alkylene oxide polymer is cured and used as a paint, an adhesive, a mount material, a sealant, a foam or the like in contact with a metal, it can be used for a long time.

(Examples) Examples of the present invention will be shown below.

Preparation of prepolymers and metal stability tests in the following examples were conducted as follows.

Synthesis of prepolymer A polyol with a molecular weight of 3000 obtained by addition-polymerizing propylene oxide with ethylene glycol, a polyol with a molecular weight of 5000 obtained by addition-polymerizing propylene oxide with glycerin and 4,4'-diphenylmethane diisocyanate are mixed, and a nitrogen stream is mixed. The reaction was carried out at 90 ° C for 6 hours. The obtained prepolymer had an NCO group content of 1.3% by weight.

Metal Stability Test Deterioration due to heavy metal ion contamination was measured as follows. Copper plate specified in JIS H3100 (C1100P) (0.3 x 70 x
150 mm) was coated with a one-pack type polyurethane resin composition to a thickness of 1 mm and completely cured in a standard state.

After curing, it was allowed to stand in a hot air dryer whose internal temperature was set to 100 ° C., and it was observed whether or not the cured product melted.

Example 1 20 parts by weight of fully dried calcium carbonate, 6 parts by weight of titanium oxide, 25 parts by weight of dioctyl phthalate (DOP), 35 parts by weight of prepolymer, and 2 parts by weight of ultrafine silica (erosil) in a high-viscosity mixing mixer. Part, 1 part by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (CDA-6),
Charge 0.5 part by weight of dilauryl thiopropionate (DLTDP) and 0.5 part by weight of melamine and stir uniformly. After being uniformly dispersed, 11 parts by weight of dehydrated xylene was added and uniformly dispersed to obtain an alkylene oxide polymer composition of the present invention.

As a result of conducting a deterioration test of the above composition due to copper ion contamination, as shown in Table-1, it was confirmed that the cured product was not deteriorated to copper ions and was stable for one week or more.

Example 2 In Example 1, 1.0 part by weight of butyl octylthioacetate (BOTA) was used instead of dilaurylthiodipropionate, and 0.5 part by weight of decamethylenedicarboxylic acid disalicyloyl hydrazide (CDA-6) was used. Was treated as in Example 1.

As shown in Table 1, the metal stability test result of the cured product was stable for 1 week or longer.

Example 3 In Example 1, 2 parts by weight of decamethylenedicarboxylic acid disalicyloyl hydrazide (CDA-6), 0.3 part by weight of dilauryl thiodipropionate (DLTDP) and melamine were added.
The same process as in Example 1 was carried out except that 0.3 part by weight was used.

As shown in Table 1, the metal stability test result of the cured product was stable for 1 week or longer.

Comparative Example 1 The same treatment as in Example 1 was carried out except that the decamethylene dicarboxylic acid disalicyloyl hydrazide was not used in Example 1.

As shown in Table 1, the cured product was deteriorated by copper ions and melted the next day.

Comparative Example 2 The same treatment as in Example 2 was carried out except that the decamethylene dicarboxylic acid disalicyloyl hydrazide was not used in Example 2.

As shown in Table 1, the cured product was deteriorated by copper ions and melted the next day.

Claims (1)

[Claims] 1. An alkylene oxide polymer and: 1) General formula (I): [In the formula, R ₁ is hydrogen or a C ₁ -C ₄ alkyl group, and n is 2-
Indicates an integer of 10. Disalicyloylhydrazide represented by], 2) the general formula _{(II): R 3 -S-} X-COOR 2 (II) [wherein X is an alkylene group of C ₁ -C _3, R ₂ is C ₄ - A C ₂₀ alkyl group, R ₃ represents a C ₄ -C ₂₀ alkyl group or the general formula (II
I): —X—COOR ₄ (III) (wherein X represents a C ₁ -C ₃ alkylene group, and R ₄ represents a C ₄ -C ₂₀ alkyl group). The mercapto fatty acid alkyl ester shown, and 3) an alkylene oxide polymer composition comprising melamine, which is stable against heavy metal ions.