JPS63161050A - Metal inactivating alkylene oxide polymer composition - Google Patents

Abstract

PURPOSE:To obtain a metal inactivating alkylene oxide polymer composition preventing deterioration caused by contamination with heavy metallic ions such as especially copper, etc., by blending an alkylene oxide polymer with a specific hydrazine derivative having antioxidant action. CONSTITUTION:(A) An alkylene oxide (e.g. polyol obtained by adding propylene oxide to ethylene glycol) is blended with (B) 0.5-5wt% (based on sum of the composition) dialkanoylhydrazine [e.g. N,N'-bis(3-methyl-4-oxybenzoyl)hydrazine] shown by the formula (R1 is H or 1-5C alkylene; R2 is 1-5C alkyl; n is 0-5), for example, the component A is previously reacted with a polyisocyanate (e.g. 4,4'-diphenylmethane isocyanate) to give a prepolymer, which is mixed with the component B together with any of various crosslinking agents, fillers, stabilizers, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a composition of alkylene oxide polymer,
In particular, the present invention relates to a metal-deactivated alkylene oxide polymer composition that prevents deterioration due to contamination with heavy metal ions such as copper.

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

Furthermore, alkylene oxide polymers are terminally aminated to form so-called polyether diamines, which are used as crosslinking agents for epoxy resins and polyurethanes. Additionally, the terminal end of the polymer is silylated and used as a modified silicone resin in sealing materials.

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

Furthermore, 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) As described above, when alkylene oxide polymers are used as molded products, adhesives, paints, sealants, etc., heavy metals, especially copper, that come into contact with them may be eluted into the polymer. The problem is cutting and degrading the polymer.

(Means for solving the problem) As a result of various studies to prevent alkylene oxide polymers from deteriorating due to heavy metal ions and enable long-term use, it was discovered that hydrazine derivatives with antioxidant effects are effective. We have arrived at the present invention.

That is, the present invention provides alkylene oxide polymers and general formulas: [wherein R1 is H or C+ Cs alkyl group,
R2 represents a C+Cs alkyl group, and n represents an integer of 0-5. ] A metal-deactivated alkylene oxide polymer composition comprising a sialkylhydrazine having the following properties.

C, -C represented by R+ or R2 in this general formula.

Examples of the alkyl group include methyl, ethyl, i-propyl, n-butyl, t-butyl, and i-amyl. Alternatively, n is an integer of 0-5, and the compound represented by this general formula is a hydrazine derivative of an organic acid having a positionally hindered phenol group. As a specific example, for example,
N,N'-bis(3-methyl-4-oxybenzoyl)
Hydrazine, N, N'-bis(3-methyl-5-t-
Butyl-4-oxybenzoyl)hydrazine, N,N”
-bis(3,5-di-t-butyl-4-oxybenzoyl)hydrazine, N, N'-bis((3-t-butyl-4-oxyphenyl)acetyl)hydrazine, N, N
'-bis((3,5-di-t-propyl-4-oxyphenyl)acetyl)hydrazine, N,N''-bis((3
,5-di-t-butyl-4-oxyphenyl)acetyl]hydrazine, N,N″-bis[β-(3-ethyl-4
-oxyphenyl)propionyl]hydrazine, N,
N'-bis[β-(3-t-butyl-4-oxyphenyl)propionyl]hydrazine, N,N'-bis[β-
(3,5-di-t-butyl-4-oxyphenyl)propionyl]hydrazine, N.

N”-bis[β-(3-ethyl-5-t-butyl-4-
oxyphenyl)propionyl]hydrazine, N, N'
-bis[γ-(3-t-butyl-4-oxyphenyl)
butyryl]hydrazine, N,N"-bis[γ-(3,5
-di-t-butyl-4-oxyphenyl)butyryl]hydrazine, N,N'-bis[δ-(3,5-di-t-butyl-4-oxyphenyl)valeryl]hydrazine, and the like. The appropriate amount used is 0.5 to 5% by weight based on the total amount of the composition.The metals with which these compounds exhibit the effect of preventing the decomposition of the alkylene oxide polymer are copper, iron, nickel, cobalt, manganese, titanium, and vanadium. , chromium, cadmium, etc. Among them, it is particularly effective against copper. These compounds prevent the alkylene oxide polymer from decomposing by reacting with metal ions to form a complex. Moreover, the deterioration of the alkylene oxide polymer is prevented by the antioxidant action of the phenol group contained therein.

The alkylene oxide of the present invention is ethylene oxide,
These are propylene oxide, butylene oxide and tetrahydrofuran. When these alkylene oxides are polymerized, homopolymerization or copolymerization of 2M or more is carried out.

Polymers of alkylene oxide are usually called polyether polyols and are liquid or waxy with 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-pencunediol, l
I2-hexylene glycol, 1,10-decanediol, 1,2-cyclohexanediol, 2-butene-1
,4-diol, 3-cyclohexane-1,1-dimetatool, 4-methyl-3-cyclohexane-1,1-dimetatool, 3-methylene-1,5-bentanediol, (2-hydroxyethoxy)-1-propano -Lou 4
-(2-hydroxyethoxy)-1-butanol, 5-
(2-hydroxypropoxy)-1-pentanol, 1
-(2-hydroxypropoxy)-2-octatool,
3-allyloxy-1,5-bentanediol, 2-allyloxymethyl-2-methyl-1,3-bentanediol ((4,4-bentroxy)-methyl)-1,3-propanediol, 3-(0 -propenylphenoxy)
-1,2-propanediol, 2,2°-diisopropylidenebis(p-phenyleneoxy)jetanol, glycerin, 1,2,6-hexanetriol, 1,1.
1-trimethylolethane, 1,1.1-)limethylolpropane, 3-(2-hydroxyethoxy)-1
, 2-propanediol, 3-(2-hydroxypropyl)-L2-propanediol, 2,4-dimethyl-2
-(2-hydroxyethoxy)-methylpentanedio-
Ru 1.5,1,111-tris [(2-hydroxy)
Methyl] ・Ethane, 1,1.1-)lith[(2-hydroxypropoxy)-methyl]propane, benquerythritol, sorbitol, sucrose, lactose, α-methylglucoside alkyl glucoside, novolac resin, phosphoric acid, benzene phosphorus acids, polyhydroxy compounds such as polyphosphoric acids (e.g. tripolyphosphoric acid and tetrapolyphosphoric acid), ethylenediamine, diethylenetriamine, triethylenetetramine, methylene orthochloroaniline, 4,4°-diphenylmethanediamine, 2,4-tolylenediamine ,
2.6-) Polyamines such as lylene diamine and alkanolamines such as triethanolamine and jetanolamine are added with one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, etc. polyether polyols, or polytetramethylene ether glycol, or a portion or more than 50% of the terminal OH groups of these polyether polyols are NO.
Polyether amines or polyether mercaptans obtained by tri- or S)l conversion can also be used. In addition, polyoxyalkylene in which the terminal OH group of a polyether polyol is intramolecularly dehydrated to form a double bond can be used, and the polyoxyalkylene obtained by reacting this with a hydrosilicon compound is described in JP-A-50-156599. Modified silicone resins can also be used.

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

Various methods are used to cure alkylene oxide polymers. That is, the polyether polyol is the third
reaction with polyisocyanate using a class amine and/or an organometallic compound as a catalyst. Polyether mercaptan uses metal oxides such as lead dioxide, chromates, organic hydroperoxides, etc. as vulcanizing agents. In addition, polyoxyalkylenes with terminal double bonds are cured using nitrile oxide and barium oxide with warm air in the air. Modified silicone resins are cured by moisture in the presence of catalysts such as fatty acid salts such as tin, lead, and iron, and titanate esters.

The polyisocyanate used for curing the polyether polyol is, for example, 2.4-)lylene diisocyanate)
(2,4-TD I), 2.6-)lylene diisocyanate (2.6-TD I), a mixture of both these isocyanates in an 80/20 weight ratio (80/20-T
D 1), 65/35 weight ratio mixture (65/35-
TDI) - Crude tolylene diisocyanate (crude TD■), diphenylmethane-4,4"-diisocyanate (4.4'-MDI), diphenylmethane-214
゛-diisocyanate (2,4'-MD I), diphenylmethane-2,2゛-diisocyanate) (2.2
°-MD I), and mixtures thereof (MDI), polymethylene polyphenyl polyisocyanate (crude MD
I),) luidine diisocyanate (TODI), xylylene diisocyanate (XDr), hexamethylene diisocyanate () (DI), isophorone diisonor 2
．． -, dicyclohexylmethane diisocyanate (H
MDI), hydrogenated xylylene diisocyanate (HXD)
I) and other polyisocyanates.

These polyisocyanates can be used as they are, or can be used as prepolymers, carbodiimide-modified products, dimers, trimers, billet-modified products, phenol block products, etc. with the following polyols. Further, these polyisocyanates (g) may be used alone or in combination of two or more.

When curing a polyether polyol by reacting a polyisocyanate, a. A crosslinking agent is used as required.

Crosslinking agents include ethylene glycol, propylene glycol,
Diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1.3
Monomeric polyols such as - and 1,4-butanediol, alkanolamines such as triethanolamine and jetanolamine, and aliphatic polyols such as ethylenediamine, diethylenetriamine, and triethylenetetramine.
7mine, alicyclic polyamines such as piperidine and its BM '1, methylene orthochloroaniline, 4.4
Hydroxyl value 200mgKOH obtained by adding ethylene oxide, propylene oxide, etc. to aromatic polyamines such as '-diphenylmethanediamine, aniline, 2,4-tolylene diamine, and 2,6-)lylene diamine, and to these active hydrogen compounds. /g or more.

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

Further, polyether amine obtained by converting the terminal OiOH group of polyether polyol to NHt and moisture in the air can also be used as a crosslinking agent. Furthermore, enamines which are hydrolyzed by warm air in the air to produce active hydrogen-containing compounds, as described in JP-A No. 47-34305, can also be used in the present invention.

Equivalent ratio of NGO groups in polyisocyanate to active hydrogen in polyether polyol and crosslinking agent (NCo/H)
The amounts of polyisocyanate, polyether polyol, and crosslinking agent used are adjusted so that the ratio is 0.70 to 1.40.

Among the catalysts that promote the reaction between polyether polyol and polyisocyanate, examples of tertiary amines include triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, jetanolamine, triethanolamine, N-methyljetanolamine, N,N-dimethylethanolamine, diethylenetriamine, N,N
, N", N'-tetramethylethylenediamine, N, N
, N', N'-tetramethylpropylenediamine, N,
II, 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, formates and other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, aza rings such as N,N-dialkylpiperazines compounds, various N, N'.

N"-)realkylaminoalkyl hexahydrotriazine neck, β-7minocarbonyl catalyst disclosed in Japanese Patent Publication No. 52-43517, β-amino nitrile catalyst disclosed in Japanese Patent Publication No. 53-14279, and the like.

Examples of organometallic urethanation catalysts include tin acetate, tin octylate, tin oleate, silver laurate, dibutyltin diacetate, diptyltin dilaurate, dibutyltin dichloride, octadecyl, lead naphthenate, nickel naphthenate, and cobalt naphthenate. etc. These catalysts may be used alone or in combination, and the amount used is from o,ooot to 10.0 parts per 100 parts of the compound having active hydrogen.

A variety of 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 anhydride, glass flakes, carbon black, silica stone, There is rock wool, etc. These shapes are powdery, scaly, and fibrous, and can be used as is, but the physical properties of the product can be improved by subjecting the surface to titanium treatment, silicone treatment, etc. in advance.

Organic materials include bitumen, pine resin, resin powder, wood flour, animal and plant fibers, and artificial fibers.

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

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

In the present invention, one or more of heat stabilizers, antioxidants, ultraviolet absorbers, and ultraviolet stabilizers may be used as stabilizers to increase the durability of the product.

As the heat stabilizer, tetramethyl thiuram disulfide, dimethyl dithiocarbamine plated copper, etc. are used.

Positionally hindered phenols are used as antioxidants,
For example, the product names Irganox 1010, Irganox 1076 (manufactured by Ciba Geigy) and the product names Yoshinonx B) IT, Yoshinox BB, Yoshinox GSY
-930 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) corresponds to this.

Examples of the ultraviolet absorber include benzotriazoles such as Tinuvin P1, Tinuvin 327, and Tinuvin 328 (manufactured by Ciba Geigy), or Tomisorp 80, a trade name.
Benzophenones such as 0 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) may be used.

In addition, as a UV stabilizer, for example, Nord LS
Preferred are positionally hindered amines such as 770, Sanol LS744, and Tinuvin 144 (manufactured by Ciba Geigy), or trade names such as Tinuvin 120 and Irgastab 2002 (manufactured by Ciba Geigy).

In addition to the various additives mentioned above, the physical properties can also be improved by adding a silicone or titanium coupling agent to increase the affinity of the filler for the alkylene oxide polymer. Antifoaming agents, surface modifiers, etc. can also be added.

Further, a solvent can be used to improve processability as required, and a foam can be formed using a foaming agent and a foam regulating agent.

Suitable solvents include, for example, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrogens such as hexane, heptano, and octane, and petroleum solvents ranging from gasoline to kerosene fractions.

In carrying out the present invention, methods for curing polyether polyol by reacting with polyisocyanate can be broadly classified into the following two methods.

One is to add and mix auxiliary agents such as a crosslinking agent, a tertiary amine and/or an organometallic compound, a filler, and a plasticizer to polyether polyol to form a resin solution, which is then mixed with polyisocyanate and reacted. This is a method of curing. Another method is to prepare a prepolymer by reacting polyether polyol with polyisocyanate in advance, and then reacting it with various crosslinking agents to cure the prepolymer.

When preparing a prepolymer, add propylene glycol, dipropylene glycol, bisphenol A to polyester polyol, polyether polyol, castor oil polyol, etc. as necessary.
A low-molecular-weight glycol such as glycol with 2 to 5 moles of propylene oxide added to the mixture is mixed, and the NGO10H ratio is 1.
5-15, react for several hours at a reaction temperature of 60-120°C. The free NCO group content of the obtained prepolymer is between 1 and 3.
It is 0%.

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

Therefore, alkylene oxide polymers can be cured to withstand long-term use when used in contact with metals, such as paints, adhesives, mounting materials, sealants, and foams.

(Example) Examples of the present invention are shown below.

In the following examples, prepolymer production and metal stability testing were performed as follows.

Synthesis of prepolymer Molecule 1i3000 polyol obtained by addition polymerization of propylene oxide to ethylene glycol, Molecule 1i obtained by addition polymerization of propylene oxide to glycerin
5,000 polyol and 4,4'-diphenylmethane diisocyanate were mixed and reacted at 90° C. for 6 hours in a nitrogen stream. The obtained prepolymer had an NCO group content of 1% by weight.

Metal stability test Deterioration due to heavy metal ion contamination was measured as follows. A liquid polyurethane resin composition was applied to a thickness of 1 mm on a copper plate (0.3 x 70 x 150 Il 1 m) specified by JIS H3100 (Cl100P) and completely cured under standard conditions.

After curing, it was left in a hot air dryer with an internal temperature of 100° C., and it was observed whether the cured product melted or not.

Example 1 In a mixer for high viscosity, 2 caps of sufficiently dried calcium carbonate (1 part), 6 parts by weight of titanium oxide, 25 parts by weight of dioctyl phthalate (DOP), 35 parts by weight of prepolymer, 2 parts by weight of ultrafine silica (Erosil) , N, N”-bis(
3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine (MD-1024) 0
．． After charging 5 parts by weight and uniformly stirring to uniformly disperse, 11 parts by weight of dehydrated xylene was added and uniformly dispersed to obtain an alkylene oxide polymer composition of the present invention.

After the composition was cured, a deterioration test due to copper ion contamination was conducted, and as shown in Table 1, the cured product was not degraded by copper ions and was stable for a long period of time.

Example 2 In Example 1, sialakaylhydrazine (not
The process was carried out in exactly the same manner as in Example 1, except that 2 parts by weight of 024) was used.

As shown in Table 1, the cured product was stable for a long period of time.

Comparative Example 1 The same process as in Example 1 was carried out except that sialkylhydrazine was not used in Example 1.

The results are shown in Table 1 (Due to deterioration due to copper ions, the cured product melted the next day.

Table-1

Claims (1)

[Claims] (1) Alkylene oxide polymer and general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is H or a C_1-C_5 alkyl group, R_2 is a C_1-C_5 alkyl group, n is 0-5 indicates an integer. ] A metal-deactivated alkylene oxide polymer composition comprising a dialkanoylhydrazine having the following.