JP2010235854A - Modified polytetramethylene ether glycol, method for producing the same and polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane resin which is excellent in durability such as heat and light resistance while ensuring good mechanical property and flexibility, and to provide a modified polytetramethylene ether glycol suitable for use as a raw material of the polyurethane resin. <P>SOLUTION: The modified polytetramethylene ether glycol is produced by reacting a compound containing an ethylenically unsaturated bond with a polytetramethylene ether glycol under the presence of a radical initiator. The polyurethane resin is obtained by reacting the obtained modified polytetramethylene ether glycol, a polyisocyanate and a chain extender. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a modified polytetramethylene ether glycol, a method for producing the same, and a polyurethane resin.

A polyol is widely known as a polyurethane raw material for reacting with a polyisocyanate to obtain a polyurethane resin.
Of these, polyether polyols are widely used in various fields where such physical properties are required because they have excellent flexibility and good elongation at break. However, the polyether polyol may not have sufficient durability such as heat resistance.

Therefore, in order to improve the durability, for example, polyoxypropylene diol is reacted with n-butyl methacrylate (n-butyl methacrylate) in the presence of 1,1-di (t-butylperoxy) cyclohexane. Thus, it has been proposed to obtain an n-butyl methacrylate grafted polyether polyol (see, for example, Patent Document 1).
Patent Document 1 proposes to obtain a cured polyurethane resin by reacting the obtained n-butyl methacrylate graft polyether polyol with 1,3-bis (isocyanatomethyl) cyclohexane.

International Publication No. 2007/026798 (Examples 5 and 6 in Table 2)

However, the molded article of the polyurethane resin may require further durability than the cured polyurethane resin described in Patent Document 1.
An object of the present invention is to provide a polyurethane resin excellent in durability such as heat resistance while securing good mechanical properties and flexibility, and a modified polytetramethylene ether glycol suitable as a raw material thereof.

In order to achieve the above object, the modified polytetramethylene ether glycol of the present invention is obtained by reacting a polytetramethylene ether glycol with an ethylenically unsaturated bond-containing compound in the presence of a radical reaction initiator. It is a feature.
In the modified polytetramethylene ether glycol of the present invention, it is preferable that the ethylenically unsaturated bond-containing compound contains a vinyl monomer.

In the modified polytetramethylene ether glycol of the present invention, it is preferable that the ethylenically unsaturated bond-containing compound contains a (meth) acrylic acid ester.
In the modified polytetramethylene ether glycol of the present invention, it is preferable that the ethylenically unsaturated bond-containing compound contains methyl (meth) acrylate.
In the modified polytetramethylene ether glycol of the present invention, it is preferable that the radical reaction initiator contains an alkyl peroxide.

In the modified polytetramethylene ether glycol of the present invention, it is preferable that the radical reaction initiator contains peroxyketals.
In the modified polytetramethylene ether glycol of the present invention, it is preferable that the number of moles of the radical reaction initiator is 0.55 mol or less with respect to 1 mol of the hydroxyl group of the polytetramethylene ether glycol.

The polyurethane resin of the present invention is characterized by being obtained by reacting the above-described modified polytetramethylene ether glycol, polyisocyanate and a chain extender.
The method for producing a modified polytetramethylene ether glycol of the present invention is characterized in that an ethylenically unsaturated bond-containing compound is reacted with polytetramethylene ether glycol in the presence of a radical reaction initiator.

  The polyurethane resin of the present invention obtained by reacting the modified polytetramethylene ether glycol of the present invention, polyisocyanate, and a chain extender is excellent in flexibility, heat resistance and mechanical properties.

The modified polytetramethylene ether glycol of the present invention can be obtained by reacting polytetramethylene ether glycol with an ethylenically unsaturated bond-containing compound in the presence of a radical reaction initiator.
Polytetramethylene ether glycol (polyoxybutylene glycol) is a linear polyether glycol having primary hydroxyl groups at both ends, and can be obtained, for example, by ring-opening polymerization of tetrahydrofuran.

The hydroxyl value of polytetramethylene ether glycol is, for example, 35 to 200 mgKOH / g, preferably 37 to 140 mgKOH / g, and more preferably 45 to 112 mgKOH / g.
The hydroxyl value of polytetramethylene ether glycol can be calculated by, for example, a known hydroxyl value measuring method such as acetylation method or phthalation method.

The number average molecular weight of the polytetramethylene ether glycol is, for example, 800 to 3000, preferably 900 to 2800, and more preferably 1000 to 2500.
When the hydroxyl value or number average molecular weight of polytetramethylene ether glycol is within the above-described range, the mechanical properties and heat resistance can be improved.

In the present invention, the radical reaction initiator is a radical generator for modifying an ethylenically unsaturated bond-containing compound into polytetramethylene ether glycol, and examples thereof include peroxide compounds and azo compounds. Preferably, a peroxide compound is used.
Examples of such peroxide compounds include inorganic peroxides (inorganic peroxide compounds) and organic peroxides (organic peroxide compounds), preferably organic peroxides.

Examples of the organic peroxide include alkyl peroxides (alkyl peroxide compounds).
Examples of the alkyl peroxide include di-t-butyl peroxide, di-t-hexyl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5- Dialkyl peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexane and t-butylcumyl peroxide, such as t-butylperoxyneodecanoate, t-butylperoxypivalate, t Peroxyesters such as butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxybenzoate, t-butyl peroxyacetate, such as 1,1-bis (t -Butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) ) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1 -Bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, 2,2-bis (t-butylperoxy) butane, n-butyl-4,4- And peroxyketals such as bis (t-butylperoxy) valerate.

The alkyl peroxide is preferably peroxyketals, more preferably 1,1-bis (t-butylperoxy) cyclohexane.
By using peroxyketals, it is possible to obtain a modified polytetramethylene ether glycol that can provide a polyurethane resin that is transparent at the melting point or higher and that has excellent mechanical properties and heat resistance.

These radical reaction initiators can be used alone or in combination of two or more.
In the present invention, the ethylenically unsaturated bond-containing compound is a compound having one or more ethylenically unsaturated double bonds in one molecule, and examples thereof include a vinyl monomer.
In the present invention, the vinyl monomer is a monomer having a vinyl group, and (meth) acrylic acid ester is preferable.

  The (meth) acrylic acid ester is an acrylic acid ester and / or a methacrylic acid ester. For example, a (meth) acrylic acid ester represented by the following general formula (1) or a hydroxyl group represented by the following general formula (2) Examples thereof include (meth) acrylic acid esters.

(Wherein R1 represents a hydrogen atom or methyl, and R2 represents an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)

(In the formula, R 3 represents a hydrogen atom or methyl, and R 4 represents an alkylene group having 1 to 18 carbon atoms.)
In the general formula (1), R1 is preferably methyl.
In the general formula (1), examples of the alkyl group having 1 to 18 carbon atoms represented by R2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n- Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n -Linear or branched alkyl such as heptadecyl and n-octadecyl. Preferably, methyl and n-butyl are mentioned.

  Examples of the aralkyl group having 7 to 18 carbon atoms represented by R2 include benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyl, diphenylmethyl, o, m or p-methylbenzyl, o, m or p-ethylbenzyl, o, m or p-isopropylbenzyl, o, m or pt-butylbenzyl, 2,3,4-, 3,4,5- or 2,4,6-trimethyl Examples include benzyl.

  Specific examples of the (meth) acrylic acid ester represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic Acid n-heptyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid n-decyl, (meth) acrylic acid n -Undecyl, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pe (meth) acrylate Tadecyl, n-hexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate, n-octadecyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate (1- or 2-phenyl) Ethyl), phenylpropyl (meth) acrylate (1-, 2- or 3-phenylpropyl), diphenylmethyl (meth) acrylate, methylbenzyl (meth) acrylate (o, m or p-methylbenzyl), ( Ethyl benzyl acrylate (o, m or p-ethyl benzyl), isopropyl benzyl (meth) acrylate (o, m or p-isopropyl benzyl), t-butyl benzyl (meth) acrylate (o, m or p) -T-butylbenzyl), trimethylbenzyl (meth) acrylate (2,3,4) , 3,4,5 or 2,4,6-trimethyl-benzyl) and the like.

In the general formula (2), R3 is preferably methyl.
In the general formula (2), examples of the alkylene group having 1 to 18 carbon atoms represented by R4 include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n -Heptylene, n-octylene, 2-ethylhexylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, Examples include n-octadecylene. Preferably, methylene is used.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester represented by the general formula (2) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (HEMA), and (meth) acrylic acid. Examples include 3-hydroxypropyl, 1-methyl-2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

These (meth) acrylic acid esters can be used alone or in combination of two or more.
As the (meth) acrylic acid ester, preferably, (meth) acrylic acid ester containing methyl (meth) acrylate, represented by the above general formula (1), and having R2 having 1 to 4 carbon atoms is mentioned. Preferably, it is represented by the above general formula (1), and the R2 carbon number is (meth) acrylic acid ester (methyl (meth) acrylate) and the above general formula (1), and the carbon number of R2 And (meth) acrylic acid ester (butyl (meth) acrylate) of 4 is mentioned.

When the (meth) acrylic acid ester contains methyl (meth) acrylate, mechanical properties and heat resistance are improved.
Moreover, when (meth) acrylic acid ester contains methyl (meth) acrylate, the mixing ratio of methyl (meth) acrylate is, for example, with respect to 100 parts by mass of the total amount of (meth) acrylic acid ester. 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and usually 90 parts by mass or less.

  Moreover, when (meth) acrylic acid methyl ester and (meth) acrylic acid butyl are used together as (meth) acrylic acid ester, those compounding ratios are (meth) acrylic acid methyl and (meth) acrylic acid. For example, 10 to 95 moles, preferably 25 to 85 moles, and more preferably 40 to 75 moles of methyl (meth) acrylate with respect to a total amount of 100 moles with butyl.

If the blending ratio of methyl (meth) acrylate exceeds the above range, the viscosity may become high and the processability may be reduced, and if it is less than the above range, the mechanical properties and heat resistance of the resulting polyurethane resin will be reduced. There is a case.
In addition to the above vinyl monomer ((meth) acrylic acid ester), other vinyl monomers are used in combination as the vinyl monomer. Examples of such other vinyl monomers include acrylonitrile, styrene, acrylamide, vinyl acetate and the like. And vinyl ethers such as ethyl vinyl ether. These other vinyl monomers can be used alone or in combination of two or more.

These ethylenically unsaturated bond-containing compounds can be used alone or in combination of two or more.
As an ethylenically unsaturated bond containing compound, Preferably, a vinyl monomer, More preferably, (meth) acrylic acid ester is mentioned.
In order to obtain the modified polytetramethylene ether glycol of the present invention, for example, the above-described polytetramethylene ether glycol is mixed with a radical reaction initiator and an ethylenically unsaturated bond-containing compound and reacted. Specifically, a monomer solution containing a radical reaction initiator and an ethylenically unsaturated bond-containing compound is blended with polytetramethylene ether glycol and reacted.

The monomer solution can be prepared by dissolving these radical reaction initiator and the ethylenically unsaturated bond-containing compound in a solvent (monomer solution preparation solvent).
Examples of the solvent (solvent for preparing the monomer solution) include hydrocarbon solvents, and specifically, aliphatic hydrocarbon solvents such as n-hexane and octane, for example, alicyclic rings such as cyclohexane and methylcyclohexane. Group hydrocarbon solvents, for example, aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene, and petroleum hydrocarbon solvents such as mineral terpenes and mineral spirits.

  In the reaction, as a blending method of polytetramethylene ether glycol, a radical reaction initiator and an ethylenically unsaturated bond-containing compound, for example, a batch charging method in which a monomer solution is batch charged with respect to polytetramethylene ether glycol, for example, Examples include a split charging method in which a monomer solution is divided and charged with respect to polytetramethylene ether glycol, for example, a dropping method in which the monomer solution is dropped with respect to polytetramethylene ether glycol.

In addition, without using a solvent, a radical reaction initiator and an ethylenically unsaturated bond-containing compound are blended with polytetramethylene ether glycol as they are to prepare a mixed solution containing them, and then they are reacted. You can also
The number of moles of the radical reaction initiator (purity 100%) in the above reaction is, for example, 0.55 mol or less, preferably 0.40 mol or less, based on 1 mol of the hydroxyl group of polytetramethylene ether glycol. Preferably, it is 0.20 mol or less, usually 0.005 mol or more. That is, the blending ratio of the radical reaction initiator (purity 100%) depends on the molecular weight of the radical reaction initiator and the number average molecular weight of the polytetramethylene ether glycol, but with respect to 100 parts by mass of the polytetramethylene ether glycol, for example, 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 11 parts by mass or less, still more preferably 6 parts by mass or less, and usually 0.1 parts by mass or more.

  When the number of moles of the radical reaction initiator exceeds 0.55 moles relative to 1 mole of the hydroxyl group of polytetramethylene ether glycol, the modified polytetramethylene ether glycol (for example, polytetramethylene ether glycol is not ethylenic). The number of modification points (for example, graft points, that is, branch points) in the graft polyol obtained by graft polymerization of the saturated bond-containing compound) is increased, and the side chain of the modified ethylenically unsaturated bond-containing compound polymer is shortened. There may be a problem that the mechanical properties and heat resistance of the resulting polyurethane resin are lowered.

Moreover, the blending ratio of the ethylenically unsaturated bond-containing compound depends on the molecular weight of the ethylenically unsaturated bond-containing compound and the number average molecular weight of the polytetramethylene ether glycol, but with respect to 100 parts by mass of the polytetramethylene ether glycol, For example, 0.01 to 150 parts by mass, preferably 1 to 100 parts by mass.
When the blending ratio of the ethylenically unsaturated bond-containing compound to the polytetramethylene ether glycol is less than the above range, the length of the side chain of the polymer of the modified ethylenically unsaturated bond-containing compound is polytetramethylene ether glycol. In contrast, the mechanical properties and heat resistance of the polyurethane resin may decrease. When the blending ratio of the ethylenically unsaturated bond-containing compound to the polytetramethylene ether glycol exceeds the above range, the length of the side chain of the polymer of the modified ethylenically unsaturated bond-containing compound becomes polytetramethylene ether. In some cases, the resulting modified polytetramethylene ether glycol is excessively long relative to the glycol, and the processability of the resulting modified polytetramethylene ether glycol is reduced due to high viscosity.

In addition, the compounding mole number of an ethylenically unsaturated bond containing compound can also be set to 1-2000 mol with respect to 1 mol of radical reaction initiators, Preferably, it is 10-1000 mol.
In that case, when methyl (meth) acrylate and butyl (meth) acrylate are used in combination as (meth) acrylic acid ester, their blending ratio is ( The methyl (meth) acrylate is, for example, 0.05 to 1900 mol, preferably 0.5 to 950 mol, and the butyl (meth) acrylate is, for example, 0.05 to 1900 mol, preferably 0. 5 to 950 mol.

  The reaction conditions and the like are appropriately selected. For example, when a dropping method is used, for example, under normal pressure, the reaction temperature is, for example, 90 to 200 ° C., preferably 100 to 180 ° C., more preferably. 110 to 160 ° C., the dropping time is, for example, 5 to 600 minutes, preferably 60 to 450 minutes, more preferably 120 to 300 minutes, and the reaction time after dropping is, for example, 5 to 600. Minutes, preferably 60 to 450 minutes, more preferably 120 to 300 minutes.

In addition, after the reaction, the unreacted ethylenically unsaturated bond-containing compound and the solvent can be removed. In order to remove the unreacted ethylenically unsaturated bond-containing compound and the solvent, for example, the mixture is heated to 60 to 160 ° C. under a reduced pressure of 0.01 to 10 kPa. At this time, when the viscosity is high and foam removal (solvent removal efficiency) is not good, an antifoaming agent may be added.
Thereby, the modified polytetramethylene ether glycol of the present invention can be obtained.

  The modified polytetramethylene ether glycol of the present invention thus obtained has a hydroxyl value of, for example, 1 to 600 mgKOH / g, preferably 2 to 300 mgKOH / g, more preferably 2 to 200 mgKOH / g, particularly preferably. Is 2 to 110 mg KOH / g. When the hydroxyl value is outside the above range, the viscosity of the modified polytetramethylene ether glycol is remarkably increased and the processability is lowered, or the polyurethane resin obtained by the reaction of the modified polytetramethylene ether glycol and polyisocyanate has sufficient mechanical properties. In addition, heat resistance may not be exhibited. The hydroxyl value is determined by the same method as described above.

The viscosity at 25 ° C. is, for example, 75000 mPa · s or less, preferably 50000 mPa · s or less, and more preferably 30000 mPa · s or less.
The viscosity at 70 ° C. can be, for example, 40000 mPa · s or less, preferably 25000 mPa · s or less, and more preferably 15000 mPa · s or less.

When the viscosity is out of the above range, the polyisocyanate and the polyurethane resin may be increased in viscosity to lose fluidity and processability may be deteriorated.
The average number of functional groups of the modified polytetramethylene ether glycol is, for example, 1.5 to 2.5, preferably 1.7 to 2.3, and more preferably 1.9 to 2.1. An average molecular weight is 1000-5000, for example, Preferably, it is 1500-4000.

The polyurethane resin of the present invention can be obtained by reacting the above-described modified polytetramethylene ether glycol, polyisocyanate, and a chain extender.
As the polyisocyanate, a known polyisocyanate usually used for polyurethane resins can be used. Examples of such polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and the like.

  Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (1,5-pentane diisocyanate), 1,2-propylene diisocyanate, 1,2-, 2, 3- or 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, 2,2,4-trimethylhexamethylene diisocyanate ( TMDI).

Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexyl. Methane diisocyanate or its mixture (H ₁₂ MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or its mixture (hydrogenated xylylene diisocyanate, H ₆ XDI), 2,5- or 2,6 -Bis (isocyanatomethyl) norbornane or a mixture thereof (NBDI), 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, Examples include methyl-2,6-cyclohexane diisocyanate and dimer acid diisocyanate (DDI).

Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and ω, ω′-diisocyanato-1,4-diethylbenzene.
Aromatic polyisocyanates include, for example, 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4′-diphenyl diisocyanate, 4, Examples thereof include 4'-diphenyl ether diisocyanate and 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI).

  The polyisocyanate includes, for example, the above-described polyisocyanate multimer (for example, dimer, trimer, etc.), the biuret modified product produced by the reaction of the above polyisocyanate or multimer with water, Modified allophanate produced by reaction with polyhydric alcohol (described later), modified oxadiazine trione produced by reaction with carbon dioxide, or modified polyol produced by reaction with the above-described polyhydric alcohol (described later) Etc. are included.

These polyisocyanates can be used alone or in combination of two or more.
Of these polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates are preferable. More preferably, an aliphatic polyisocyanate is mentioned.
The chain extender is a compound containing two or more active hydrogen groups containing active hydrogen such as a hydroxyl group and an amino group, and examples thereof include polyols and polyamines.

Examples of the polyol include polyhydric alcohols.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, , 6-hexanediol, neopentyl glycol, 3-methylpentanediol (eg, 3-methyl-1,5-pentanediol, etc.), 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, alkane (7-22) diol, diethylene glycol, tri Ethylene glycol, dipropylene glycol Any dihydric alcohol, for example, trihydric alcohols such as glycerin and trimethylolpropane, for example, tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, for example, pentahydric alcohols such as xylitol, such as sorbitol, mannitol, etc. , Polyhydric alcohols such as hexahydric alcohols such as allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, for example, 7-valent alcohols such as perseitol, and octahydric alcohols such as sucrose (preferably average molecular weight) Less than 400 polyhydric alcohols). Moreover, the alkylene oxide addition product etc. which added alkylene oxides, such as ethylene oxide and a propylene oxide, to the above-mentioned polyhydric alcohol are mentioned.

These polyhydric alcohols can be used alone or in combination of two or more.
Examples of the polyamine include aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, and 1,6-hexamethylenediamine, such as 1,4-cyclohexanediamine, 3 -Aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane Alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane, such as o, m or p-tolylenediamine (TDA, OTD), 3,3′-dichloro-4,4′-diaminodiphenylmethane ( MOCA) and other diamines such as hydrazine.

Further, aliphatic triamines such as diethylenetriamine, for example, aliphatic polyamines having 4 or more amino groups such as triethylenetetramine and tetraethylenepentamine are exemplified. These polyamines can be used alone or in combination of two or more.
Examples of the chain extender include, for example, an alkylene oxide adduct of polyhydric alcohol, dimethylol alkanoic acid, and an active hydrogen group capable of forming a salt such as carboxylate and sulfonate, and Also included are nonionic group-containing compounds (nonionic internal emulsifiers) containing a nonionic group such as an oxyethylene group in the side chain, and hydroxyl group-containing polyamines.

As the chain extender, specifically, when the polyurethane resin is prepared as a thermoplastic polyurethane resin (described later), a dihydric alcohol is preferably used.
As the chain extender, specifically, when the polyurethane resin is prepared as a thermosetting polyurethane resin (described later), it is preferable that the number of functional groups is 2 or more and the number average molecular weight is 500 or less. A trihydric alcohol (for example, 1,4-butanediol (glycol), etc.), a trihydric alcohol (for example, glycerin, trimethylolpropane, etc.), an alkylene oxide adduct of pentaerythritol, bisphenol A alkylene oxide adduct of A or a mixture thereof) and aromatic diamines (for example, 3,3′-dicyclo-4,4′-diaminodiphenylmethane (MOCA) and the like).

  As the chain extender, specifically, when the polyurethane resin is prepared as a segmented polyurethane urea (described later), an aliphatic polyamine, an alicyclic polyamine, and the like are preferable. These are polymerized by carrying out a chain extension reaction in a polar solvent (for example, N, N′-dimethylacetamide, dimethylsulfoxide, methyl ethyl ketone, etc.).

  As the chain extender, specifically, when the polyurethane resin is prepared as a water-dispersed polyurethane resin (described later), preferably, an aliphatic polyamine is used, and in addition, dimethylolalkanoic acid, Or a nonionic internal emulsifier is mentioned. In the dimethylol alkanoic acid or nonionic internal emulsifier, the carboxyl group or oxyethylene group becomes a hydrophilic group, and the polyurethane particles can be stably dispersed in water.

And in order to obtain the polyurethane resin of this invention, said each component (namely, modified | denatured polytetramethylene ether glycol, polyisocyanate, and chain extender) is carried out by synthetic methods, such as a one shot method and a prepolymer method, for example. React.
In the one-shot method, the modified polytetramethylene ether glycol, the polyisocyanate, and the chain extender are mixed with the isocyanate group of the polyisocyanate with respect to the active hydrogen group (hydroxyl group or amino group) of the modified polytetramethylene ether glycol and the chain extender. The equivalent ratio (isocyanate group / active hydrogen group: NCO index) is, for example, 0.9 to 1.2, and preferably 0.95 to 1.15, and they are simultaneously mixed and stirred and mixed.

In this stirring and mixing, for example, under an inert gas (for example, nitrogen) atmosphere, the reaction temperature is, for example, 40 to 280 ° C., preferably 60 to 260 ° C., and the reaction time is, for example, 30 seconds to 1 hour. Implement at a degree.
Further, at the time of stirring and mixing, a catalyst and a solvent (polyurethane preparation solvent) can be added at an appropriate ratio, if necessary.

Examples of the catalyst include metal compounds such as tin compounds (for example, dibutyltin dilaurate), lead compounds, and bismuth compounds, such as amine compounds.
Examples of the solvent (polyurethane preparation solvent) include, in addition to the hydrocarbon solvent described above, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone, such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. Alkyl esters such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate and the like, such as diisononyl adipate (DINA) Adipates such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodine Halogenated aliphatic hydrocarbons such as methylene chloride and dichloroethane, such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), N, N′-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) An organic solvent.

In the prepolymer method, first, a modified polytetramethylene ether glycol and a polyisocyanate are reacted to synthesize an isocyanate group-terminated prepolymer, and then the isocyanate group-terminated prepolymer and a chain extender are reacted.
In order to synthesize an isocyanate group-terminated prepolymer, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the modified polytetramethylene ether glycol (isocyanate group / hydroxyl group: NCO index) exceeds 1.0. For example, it mix | blends in the ratio of 1.01-4.00 simultaneously, and stirs and mixes and makes it react.

  In this reaction, for example, in an inert gas (for example, nitrogen) atmosphere, the reaction temperature is 40 to 150 ° C., the reaction time is about 30 seconds to 8 hours, the modified polytetramethylene ether glycol, polyisocyanate, Are mixed with stirring. In the reaction, the above-mentioned catalyst and solvent can be added as necessary. Further, after the reaction, unreacted polyisocyanate is removed by distillation or the like, if necessary.

Next, the isocyanate group-terminated prepolymer and the chain extender have an equivalent ratio of isocyanate group of the isocyanate group-terminated prepolymer to the active hydrogen group (hydroxyl group or amino group) of the chain extender (isocyanate group / active hydrogen group: NCO index). However, it mix | blends in the ratio used as 0.9-1.2, for example, Preferably 0.95-1.15, and stir-mixes.
This stirring and mixing is performed, for example, at a reaction temperature of, for example, 40 to 280 ° C., preferably 60 to 260 ° C., and for a reaction time of, for example, about 30 seconds to 1 hour. Moreover, at the time of stirring and mixing, the above-described catalyst and solvent can be added at an appropriate ratio, if necessary.

  The polyurethane resin of the present invention is prepared as TPU (thermoplastic polyurethane resin), TSU (thermosetting polyurethane resin), SPU (segmented polyurethane urea), PUD (water-dispersed polyurethane resin), etc. Used in industrial applications, for example, in applications such as paints, adhesives, sealants, and elastomers, which are excellent in durability such as heat resistance.

The paint is used as, for example, a one-pack type or a two-pack type, and as a one-pack type, for example, for vehicles (automobiles), for floors, for ships, for transparent outdoors, for anticorrosion, for factory floors or concrete, industrial Used for painting, wire coating, impregnating varnish, etc. Further, as a two-pack type, for example, it is used for chemical resistant coating, rubber, wear resistance, anticorrosion and the like.
The adhesive is used, for example, as a one-pack type or a two-pack type. Specifically, the adhesive or pretreatment of clothing such as synthetic (artificial) leather, fiber, food packaging, medical materials, wood, rubber, metal, etc. Used as (primer).

The sealant is used, for example, as a one-pack type or a two-pack type, and specifically, expansion joint materials such as vehicles (automobiles), civil engineering and building structures, ships, roads, airports, bridges, aircraft, and equipment parts. It is used for special sealing materials such as earth pipes, gas pipes, and sewer pipe joint seals.
Elastomers include, for example, synthetic (artificial) leather, sheets, films, printing doctors, hard rolls, bearings, couplings, hammers, anti-vibration materials, liners, gears, pump membrane rings, diaphragms, air brakes, screws, air springs. , Bushes, wipers, packing, shoe soles, heel tops, electric wires, elastic fibers, and the polyurethane resin described above are formed into particles and used for automobile interior skin materials obtained by slush molding.

  For polyurethane resins, known additives such as heat stabilizers, light stabilizers, plasticizers, antiblocking agents, mold release agents, antioxidants, ultraviolet absorbers, pigments are used according to the respective applications described above. , Dyes, lubricants, fillers, hydrolysis inhibitors, rust inhibitors, fillers, and the like can be added. These additives may be added at the time of synthesizing each component, or may be added at the time of mixing each component.

  Then, by reacting the modified polytetramethylene ether glycol of the present invention, polyisocyanate, and a chain extender, the polyurethane resin of the present invention is excellent in durability such as heat resistance while ensuring good mechanical properties. Can be obtained.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.
Example 1
(Production of modified polytetramethylene ether glycol)
In a 2 L separable flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, in a nitrogen atmosphere, polytetramethylene ether glycol (average functional group number: 2, number average molecular weight: 2000, trade name: PTG2000SN (Hodogaya Chemical Co., Ltd.) 880.0 parts by mass was charged and heated to 120 ° C. in an oil bath. Subsequently, 110.0 parts by mass of methyl methacrylate, 88.0 parts by mass of n-butyl methacrylate, 22.0 parts by mass of n-butyl acrylate, and perhexa C (S) (1,1 as a radical reaction initiator) -A monomer solution in which 169.1 parts by mass (purity conversion value: 118.37 parts by mass) of a 70% by mass hydrocarbon solution of di (t-butylperoxy) cyclohexane (manufactured by NOF Corporation) was added over 4 hours. Was added dropwise to the separable flask at a uniform rate. In addition, the compounding mole number of a radical reaction initiator is 0.5166 mole with respect to 1 mole of hydroxyl groups of polytetramethylene ether glycol, and the compounding mole number of methyl methacrylate, n-butyl methacrylate, and n-butyl acrylate. Were 2.42 mol, 1.36 mol, and 0.38 mol, respectively, with respect to 1 mol of the radical reaction initiator.

Then, it was made to react for 4 hours. Then, unreacted methyl methacrylate, n-butyl methacrylate, n-butyl acrylate and the solvent were removed by reducing the pressure at 120 ° C. and 1.3 kPa for 4 hours. Thereafter, this was cooled to room temperature to obtain a modified polytetramethylene ether glycol (A).
(Production of isocyanate group-terminated prepolymer)
In a 2 L separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a water-cooled condenser, 556.3 parts by mass of modified polytetramethylene ether glycol (A) and 1,6-hexamethylene diisocyanate (product) Name: Takenate 700, HDI, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd. 75.5 parts by mass (equivalent ratio (isocyanate group of 1,6-hexamethylene diisocyanate / hydroxyl group in modified polytetramethylene ether glycol): 1.99) Prepared. Thereafter, the temperature was raised to 75 ° C. in an oil bath while introducing nitrogen, and then the reaction was continued until a predetermined isocyanate group content (see Tables 1 and 2) was approximately reached. )

(Manufacture of polyurethane resin)
In a 500 ml SUS cup, 200.0 parts by mass of an isocyanate group-terminated prepolymer (A) previously adjusted to 80 ° C., heat resistance stabilizer (trade name: Irganox 1135, manufactured by Ciba Specialty Chemicals) 0.62 parts by mass , 0.05 parts by weight of a solution obtained by diluting a catalyst (dibutyltin dilaurate, DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.) to 4% by weight using diisononyl adipate (trade name: DINA, manufactured by DIP Corporation), and an antifoaming agent (Product name: AC-1190, manufactured by Kyoeisha Chemical Co., Ltd.) 1,4-butanediol charged with 0.06 parts by mass, stirred and mixed for 1 minute while adjusting the temperature to 80 ° C., and then adjusted to 80 ° C. in advance (Wako Pure Chemical Industries, Ltd.) 5.76 parts by mass (equivalent ratio (isocyanate group / 1,4-butyl group in isocyanate group-terminated prepolymer) Hydroxyl groups in Njioru): 1.11) were charged and stirred well until the entire further about 2 minutes is uniform.

  The mixture was then transferred to a plastic cup and vacuum degassed at 80 ° C. for 3 minutes. Immediately after defoaming (while still having fluidity), the mixture was poured into a mold heated to 100 ° C. in advance, and the mixture was put into an oven at 100 ° C. and reacted for 22 hours to be cured. . Then, after taking out from the oven and removing the mold, the polyurethane resin (A) was obtained by further curing at room temperature for 7 days.

Example 2
The modified polytetramethylene ether glycol-modified polytetrafluoroethylene was treated in the same manner as in Example 1 except that the amount of the radical reaction initiator was changed to 54.6 parts by mass (purity conversion value: 38.22 parts by mass). Methylene ether glycol (B) was obtained. In addition, the compounding mole number of a radical reaction initiator is 0.1668 mol with respect to 1 mol of hydroxyl groups of polyester polyol A, and the compounding mole number of methyl methacrylate, n-butyl methacrylate, and acrylic acid n-butyl is: The amounts were 7.49 mol, 4.22 mol, and 1.17 mol, respectively, with respect to 1 mol of the radical reaction initiator.

Next, the isocyanate group-terminated prepolymer (B) was produced in the same manner as in Example 1 in accordance with the formulation of Table 1, and then treated in the same manner as in Example 1 in accordance with the formulation of Table 1. A polyurethane resin (B) was obtained.
Example 3
The modified polytetramethylene ether glycol-modified polytetratetrafluoroethylene was treated in the same manner as in Example 1 except that the amount of the radical reaction initiator was changed to 15.0 parts by mass (equivalent purity value: 10.05 parts by mass). Methylene ether glycol (C) was obtained. In addition, the compounding mole number of radical reaction initiator is 0.0458 mol with respect to 1 mol of hydroxyl groups of polyester polyol A, and the compounding mole number of methyl methacrylate, n-butyl methacrylate, and acrylic acid n-butyl is: They were 27.25 mol, 15.35 mol, and 4.26 mol, respectively, with respect to 1 mol of the radical reaction initiator.

Next, the isocyanate group-terminated prepolymer (C) was produced in the same manner as in Example 1 in accordance with the formulation of Table 1, and then treated in the same manner as in Example 1 in accordance with the formulation of Table 1. A polyurethane resin (C) was obtained.
Example 4
The modified polytetramethylene ether glycol (D) was treated in the same manner as in Example 1 except that the amount of the radical reaction initiator was changed to 191.0 parts by mass (purity conversion value: 133.7 parts by mass). Got. In addition, the compounding mole number of a radical reaction initiator is 0.5835 mol with respect to 1 mol of hydroxyl groups of polyester polyol A, and the compounding mole number of methyl methacrylate, n-butyl methacrylate, and acrylic acid n-butyl is: They were 2.14 mol, 1.21 mol, and 0.33 mol, respectively, with respect to 1 mol of the radical reaction initiator.

Next, the isocyanate group-terminated prepolymer (D) was produced in the same manner as in Example 1 according to the formulation of Table 1, and then treated in the same manner as in Example 1 according to the formulation of Table 1. A polyurethane resin (D) was obtained.
Comparative Example 1
The polytetramethylene ether glycol (average functional group number: 2, number average molecular weight: 2000, trade name: PTG2000SN, manufactured by Hodogaya Chemical Co., Ltd.) was used as a sample of Comparative Example 1 as it was.

Next, the isocyanate group-terminated prepolymer (E) was produced according to the formulation of Table 2 in the same manner as in Example 1, and then treated in the same manner as in Example 1 according to the formulation of Table 2. A polyurethane resin (E) was obtained.
Comparative Example 2
In a 2 L separable flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, in a nitrogen atmosphere, polypropylene glycol (average functional group number: 2, number average molecular weight: 2000, trade name: Actol DIOL) -2000, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 880.0 parts by mass were charged and heated to 120 ° C. in an oil bath. Subsequently, 110.0 parts by mass of methyl methacrylate, 88.0 parts by mass of n-butyl methacrylate, 22.0 parts by mass of n-butyl acrylate, and perhexa C (S) (1,1 as a radical reaction initiator) -A monomer solution obtained by mixing 54.60 parts by mass (purity conversion value: 38.22 parts by mass) of a 70% by mass hydrocarbon solution of di (t-butylperoxy) cyclohexane (manufactured by NOF Corporation) over 4 hours. Was added dropwise to the separable flask at a uniform rate. In addition, the compounding mole number of a radical reaction initiator is 0.1668 mol with respect to 1 mol of hydroxyl groups of polypropylene glycol, and the compounding mole number of methyl methacrylate, n-butyl methacrylate, and acrylic acid n-butyl is a radical. The amounts were 7.49 mol, 4.22 mol, and 1.17 mol, respectively, with respect to 1 mol of the reaction initiator.

Then, it was made to react for 4 hours. Then, unreacted methyl methacrylate, n-butyl methacrylate, n-butyl acrylate and the solvent were removed by reducing the pressure at 120 ° C. and 1.3 kPa for 4 hours. Thereafter, this was cooled to room temperature to obtain a modified polypropylene glycol.
Next, the isocyanate group-terminated prepolymer (F) was produced in the same manner as in Example 1 according to the formulation of Table 2, and then treated in the same manner as in Example 1 according to the formulation of Table 2. A polyurethane resin (F) was obtained.

Comparative Example 3
A modified polypropylene glycol was obtained in the same manner as in Comparative Example 2 except that the amount of the radical reaction initiator was changed to 15.0 parts by mass (purity conversion value: 10.50 parts by mass). In addition, the compounding mole number of a radical reaction initiator is 0.0458 mole with respect to 1 mole of hydroxyl groups of polypropylene glycol, and the compounding mole number of methyl methacrylate, n-butyl methacrylate, and acrylic acid n-butyl is a radical. They were 27.25 mol, 15.35 mol, and 4.26 mol, respectively, with respect to 1 mol of the reaction initiator.

Next, the isocyanate group-terminated prepolymer (G) was produced according to the formulation of Table 2 in the same manner as in Example 1, and then treated in the same manner as in Example 1 according to the formulation of Table 2. A polyurethane resin (G) was obtained.
Comparative Example 4
The polypropylene glycol (average functional group number: 2, number average molecular weight: 2000, trade name: Actol DIOL-2000, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was used as it was as a sample of Comparative Example 4.

Next, the isocyanate group-terminated prepolymer (H) was produced in the same manner as in Example 1 in accordance with the formulation of Table 2, and then treated in the same manner as in Example 1 in accordance with the formulation of Table 2. A polyurethane resin (H) was obtained.
Evaluation <Evaluation of modified polytetramethylene ether glycol, modified polypropylene glycol and macropolyol>
The modified polytetramethylene ether glycol and modified polypropylene glycol obtained in each example and each comparative example, and the macropolyol (polytetramethylene ether glycol and polypropylene glycol) used in each example and each comparative example are as follows. The evaluation items were evaluated according to the following procedure. The results are shown in Tables 1-2.
1) Appearance Visual observation was performed at room temperature (25 ° C.).
2) Viscosity Viscosity was measured according to a measuring method using a Brookfield type rotational viscometer of JIS K1557-5 (2007 edition).
3) Hydroxyl value It measured based on the phthalation method of JIS K1557-1 (2007 edition).
<Evaluation of isocyanate group-terminated prepolymer>
About the isocyanate group terminal prepolymer obtained by each Example and each comparative example, the following evaluation items were evaluated in accordance with the following procedure. The results are shown in Tables 1-2.
1) Appearance Visual observation was performed at room temperature (25 ° C.).
2) Viscosity Viscosity was measured at room temperature (25 ° C.) according to a measuring method using a Brookfield rotary viscometer of JIS K1557-5 (2007 edition).
3) Isocyanate group content Measured according to the di-n-butylamine method of JIS K-1556 (2006 edition).
<Evaluation of polyurethane resin>
The following evaluation items were evaluated according to the following procedures for the polyurethane resins obtained in each Example and each Comparative Example. The results are shown in Tables 1-2.
1) Stress at break (tensile strength)
Measured using the No. 3 dumbbell-shaped test piece described in Section 5.3 “Test Piece” in accordance with Section 5 “Tensile Test” of JIS K7312 (1996 edition). Based on the description of “tensile strength”, the stress at break (tensile strength) was calculated.
2) Stress increase rate at break (tensile strength) Polyurethane resin formed from macropolyol (ie, unmodified macropolyol) used in the production of modified polyols (modified polytetramethylene ether glycol and modified polypropylene glycol) The increase rate of the stress at break (tensile strength) of the polyurethane resin formed from the modified polyol with respect to the stress at break (tensile strength) of was determined.

In Comparative Examples 2 and 5, since the unmodified macropolyol was used as it was as a sample, the rate of increase in stress at break (tensile strength) was 0%.
3) Elongation at break (elongation at cutting)
Measured using the No. 3 dumbbell-shaped test piece described in Section 5.3 “Test Piece” in accordance with Section 5 “Tensile Test” of JIS K7312 (1996 edition). Based on the description of “elongation at break”, elongation at break (elongation at break) was calculated.
4) Elongation rate at break (elongation at break) Macropolyol used for production of modified polyols (modified polytetramethylene ether glycol and modified polypropylene glycol) (ie, unmodified macropolyols of Comparative Examples 2 and 8) The elongation at break (elongation at break) of the polyurethane resin formed from the modified polyol relative to the elongation at break (elongation at break) of the polyurethane resin formed from (1) was determined.

In Comparative Examples 2 and 5, since the unmodified macropolyol was used as a sample as it was, the elongation increase at break (elongation at break) was 0%.
5) Heat resistance The test piece of polyurethane resin was allowed to stand in an oven at 120 ° C. and left for 14 days. The shape change of the polyurethane resin (sheet-like) was observed and evaluated according to the following criteria.

○: No change in shape or elution.
Δ: No change in shape and elution, but brittleness.
X: Change in shape and elution.

Claims (9)

  A modified polytetramethylene ether glycol obtained by reacting a polytetramethylene ether glycol with an ethylenically unsaturated bond-containing compound in the presence of a radical reaction initiator.   The modified polytetramethylene ether glycol according to claim 1, wherein the ethylenically unsaturated bond-containing compound contains a vinyl monomer.   The modified polytetramethylene ether glycol according to claim 1, wherein the ethylenically unsaturated bond-containing compound contains a (meth) acrylic acid ester.   The modified polytetramethylene ether glycol according to any one of claims 1 to 3, wherein the ethylenically unsaturated bond-containing compound contains methyl (meth) acrylate.   The modified polytetramethylene ether glycol according to claim 1, wherein the radical reaction initiator contains an alkyl peroxide.   The modified polytetramethylene ether glycol according to any one of claims 1 to 5, wherein the radical reaction initiator contains peroxyketals.   The number of moles of the radical reaction initiator blended is 0.55 moles or less with respect to 1 mole of hydroxyl groups of the polytetramethylene ether glycol. Tetramethylene ether glycol. The modified polytetramethylene ether glycol according to any one of claims 1 to 7,
A polyurethane resin obtained by reacting a polyisocyanate with a chain extender.   A method for producing a modified polytetramethylene ether glycol, comprising reacting a polytetramethylene ether glycol with an ethylenically unsaturated bond-containing compound in the presence of a radical reaction initiator.