JPH02240124A - Polyurethane - Google Patents

Abstract

PURPOSE:To obtain a polyurethane having excellent chemical stability and good elastic recovery by reacting a specified aliphatic polyether carbonate polyol with a polyisocyanate. CONSTITUTION:A polyurethane comprising a polymer polyol, a polyisocyanate and optionally a chain extender having at least two active hydrogen atoms reactive with the polyisocyanate, wherein the polymer polyol is an aliphatic polyether carbonate polyol comprising at least one kind of repeating units (A) of formula I, repeating units (B) of formula II and repeating units (C) of formula III and having such a composition that the total or (A) and (B) is at least 90%, the total or at least one kind of (C) is at most 10%, and the (A)/(B) ratio is 1/9-9/1 (these percentages and ratio are those in terms of the numbers of the repeating units). In this formulas, R' and R'' are each a 1-10C alkylene, a cycloalkylene, a derivative thereof, a group of a structural formula of formula IV or its isomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyurethane that has excellent hydrolysis resistance, light resistance, oxidative deterioration resistance, and good elastic recovery.

Polyurethane is used in a wide range of applications, including thermosetting and thermoplastic urethane elastomers such as flexible or rigid foams, paints, binders, elastic sealants, coating materials, casting materials, and RIM. (Prior Art) First, polyurethane is synthesized from polyisocyanate, a polymer polyol, and optionally a chain extender having at least two active hydrogen atoms capable of reacting with the polyisocyanate. For example, JP-A-59-100778 and JP-A-57-
As disclosed in Japanese Patent No. 100779, polyester polyols and polyether polyols are mainly used. Among these, polyester polyols represented by adibate have poor hydrolysis resistance, so for example,
Polyurethane using this material is subject to considerable limitations in terms of use, such as cracks occurring on the surface in a relatively short period of time.

On the other hand, polyether polyols have good hydrolysis resistance, but have the disadvantage of poor light resistance and oxidative deterioration resistance. These drawbacks are due to the presence of ester groups and ether groups in the polymer chains, respectively.

Polycarbonate polyol of 1,6-hexanediol is commercially available as a polymer polyol with excellent hydrolysis resistance, light resistance, and oxidation resistance, but this is because the carbonate bonds in the polymer chain are chemically extremely stable. Therefore, it exhibits the above-mentioned features.

[Problem that the invention seeks to solve]

However, polyurethanes using polycarbonate polyols such as 1,6-hexanediol have significantly lower elastic recovery than urethanes using other polyols, such as polyether polyols. Furthermore, when producing polyurethane fibers, they lack spinnability and are difficult to spin. For this reason, attempts have been made to overcome this drawback by introducing ether bonds into the polycarbonate polyol (Japanese Unexamined Patent Publication Nos. 63-3051.27 and 59-66577). It still wasn't enough.

An object of the present invention is to provide a polyurethane that has excellent chemical stability such as hydrolysis resistance, light resistance, and oxidative deterioration resistance, and has good elastic recovery properties.

[Means for solving problems]

As a result of extensive research, the present inventors found that the repeating units of the polymer polyol are as follows: and Il! (C) MOOR'1 (1-
R"-OC→(R',R: alkylene having 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and the compound represented by -CH2C}IClIzU and its isomer), and its composition However, the total of (^) and (B) is 90% or more, the total of one or more types of (C) is 10% or less, and the ratio of (^) and (B) is 1/9 to 9 /l (however, the % and the ratio indicate the number of repeating units) is chemically stable and exhibits excellent elastic recovery properties. This finding led to the present invention.

That is, the present invention provides a polyurethane comprising a polymer polyol, a polyisocyanate, and optionally a chain extender having at least two active hydrogens capable of reacting with the polyisocyanate, in which the polymer polyol is used as a repeating unit (A) 1,000 (CI!z)i QC→, (B)
+0 (C}I 2) S? R', R''i consists of alkylene having 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and -C11 (!}l -cH, U and its isomers), and its composition However, if the sum of (A) and (B) is 90% or more, 1 of (C)
The total of the species or two or more species is 10% or less, (^)
The polyurethane is an aliphatic polyether carbonate in which the ratio of (B) and (B) is 179 to 9/1 (however, the percentage and the percentage indicate the number of repeating units).

The present invention will be explained in detail below.

The aliphatic polyether carbonate polyol used in the present invention is described by Schell, Polymer Review, Vol. 9, Vol.
~20 (1964), 0C→ 1.6-hexanediol, 1.5-pentanediol and HO-R'-0-R''-OH (R', R'' are It is synthesized from alkylene having 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and its derivatives, and ether diols represented by the structural formula (υ).

Moreover, when a method of transesterifying 1.5-pentanediol, 1.6-hexanediol and ethylene carbonate is used, +0 + CHz-h is produced in polycarbonate diol by thermal decomposition of ethylene carbonate.
O + CL +s QC→ and O t-0 +CI! h O + CB! -h This is convenient because a unit expressed in QC dimensions is introduced.

The ether diols used in the present invention include dihydroxymethane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tetrapropylene glycol, 1,5-pentanediol, neopentyl glycol, 3- Methyl 1,5-pentanediol, 1.
6-hexanediol, 1,7-hebutanediol, 1
．． 8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol,
1.3-cyclohexanediol, 1.4-cyclohexanediol, 2.2'-bis(4-hydroxycyclohexyl)propane, 2-methyl-1.8-octanediol, 1.9-nonanediol, p- Xylene diol, p-tetrachloroxylene diol, 1.4-
One or two diols selected from dimethylolcyclohexane and bishydroxymethyltetrahydrofuran are etherified by a known method in the presence of an acid catalyst.

Repeating unit O O in the polymer and one or more (C) {-OR'-0
-R"-QC→(R',R": Alkylene having 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and its derivatives, and whose structural formula is 1 GHz CH
The ratio of (A) (B
) is 90% or more, and type 1 or 2 of (c)
It is necessary that the total of the species or more is 10% or less, and the ratio of (^) and ([l) is 179 to 9/1 (however, the % and the ratio are the number of repeating units).

If each repeating unit deviates from this ratio, the elastic recovery properties or light resistance will deteriorate, which is not preferable. Such a repeating unit (A). (B). No one could have imagined that polyurethane using a specific proportion of aliphatic polyether carbonate diol (C) is chemically stable and also has excellent elastic recovery and light resistance. Such polyurethanes, which have been long awaited by the industry, can be used in a wide range of fields.

The range of the average molecular weight of the aliphatic ether polycarbonate polyol used in the polyurethane of the present invention varies depending on the use, but is usually 500 to 30.00 in terms of number average molecular weight.
0, preferably 600 to 20,000, more preferably 700 to 6,000, and it is desirable that substantially all of the terminal ends of the polymer are hydroxyl groups.

The present invention provides 1,6-hexanediol, 1,5-pe97
'; All and 80-R'-0-R"-OH (R', R
``: Alkylene having 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and those represented by υ and its isomers) In addition to ether diols, compounds having 3 or more hydroxyl groups in one molecule, For example, polyurethanes using polycarbonates that are polyfunctionalized by using small amounts of trimethylolethane, trimethylolbroban, hexanetriol, pentaerythritol, etc. are also included.Furthermore, in the aliphatic polyether carbonate polyol used in the present invention, , 1,6-hexanediol,
1,5-pentanediol and }10-R'-0-R"
In addition to the ether diol represented by -OH (R', R'': alkylene having 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and υ and its isomers), 2 Compounds with the above hydroxyl groups, such as ethylene glycol, 1.3-propanediol, 1.4-butanediol, 1.7-heptanediol, 1.8-octanediol, 2-ethyl-1.6-hexane Diol, 2-methyl-l,3-
Propanediol, neopentyl glycol, 3-methyl-1.5-bentanediol, 1.3-cyclohexanediol, 1.4-cyclohexanediol, 2.2
'-bis(4-hydroxycyclohexyl)propane,
2-Methyl-1,8-octanediol, 1,9-nonanediol, p-xylene diol, p-tetrachloroxylene diol, 1,4-dimethylolcyclohexane, bishydroxymethyltetrahydrofuran, di(2
- A small amount of a diol such as dimethylhydantoin, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polybrobylene glycol, polytetramethylene glycol, thioglycol, etc., within a range that does not impair the effects of the present invention. It may be used as a cobolimer component. Examples of the polyisocyanate used in the present invention include 2.4-}lylene diisocyanate, 2.6-}lylene diisocyanate, and mixtures thereof (TDI), and diphenylmethane-4,4'-diisocyanate (MDI).
), naphthalene-1,5-diisocyanate (NDI)
, 3.3'-dimethyl-4.4'-biphenylene diisocyanate (TODI), 11i11TDI, polymethylene polyphenylisocyanate, crude MDI; known aromatic diisocyanates such as xylylene diisocyanate (XDI), phenylene diisocyanate, etc. Aromatic alicyclic diisocyanates}: 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MD!), hexamethylene diisocyanate} (HMDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI), etc. These are known aliphatic diisocyanates and modified products of these isocyanates such as isocyanurate modified products, carbodiimidated modified products, and uret modified products. In addition, in the present invention, suitable chain extenders that may be used as necessary include chain extenders commonly used in the polyurethane industry.Recent Polyurethane Application Technology CMC I985 No. 25-27, supervised by Keiji Iwata.
This includes water, low-molecular polyols, polyamines, etc., which are listed on the page. Along with the aliphatic polyether carbonate polyol used in the present invention, a known polyol may be used in combination, depending on the use of the polyurethane, within a range that does not impair the effects of the present invention. As a known polyol, Yoshio Imai, Polyurethane Foam, Kobunshi Publishing Society, 1987, No. 12-23
There are known polyols such as polyesters and polyether polycarbonates described on p. As a method for producing polyurethane, a urethanization reaction technique known in the polyurethane industry is used. For example, the polyol and organic polyisocyanate are heated at room temperature to about 2
By reacting at 00°C, NGO-terminated polyurethane prepolymer is produced. These can be used in one-component solvent-free adhesives and sealants that cure by reacting with moisture in the air. This prepolymer, another polyol, and a known crosslinking agent (a low-molecular compound having two or more active hydrogen atoms that can react with isocyanate) can be combined to be used in two-component casting materials. Furthermore, a crosslinked or thermoplastic polyurethane can be produced by using the polyol, polyisocyanate, and, if necessary, a chain extender, using a method such as a one-shot method, a prebolimer method, or a RIM method. In the production of these, known polymerization catalysts such as tertiary amines and organic metal salts such as tin and titanium are used [for example, "Polyurethane Resins" by Keiji Yoshida, published by Nikkan Kogyo Shimbun, Vol.
32 (1969)] can also be used. Moreover, these reactions may be carried out using a solvent,
Preferred solvents include dimethylformamide, diethylformamide, dimethylsulfoxide, dimethylacetamide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, ethyl cellosolve, and the like.

In addition, in producing the polyurethane of the present invention, a compound containing only one active hydrogen that reacts with an isocyanate group,
For example, monohydric alcohols such as ethyl alcohol and probyl alcohol, secondary amines such as hdiethylamine and di-n-propylamine, etc. may be used as the terminal capping agent.

Next, some examples of uses of the polyurethane obtained by the present invention will be described.

(1) Molded products such as elastomer films, sheets, hoses, tubes, rolls, gears, etc. by making substantially linear thermoplastic polyurethane pellets, heating and melting them, and using methods such as injection molding, extrusion molding, and calendering. Manufacture.

(2) A prepolymer having molecular terminal isocyanate groups is produced by reacting the aliphatic polyether carbonate polyol with an organic polyisocyanate, and the prepolymer is cured with moisture or used as a casting material or coating material using a diol or diamine chain extender. Used in applications such as , sealants, and adhesives.

(3) In (1) and (2) above, the polyurethane solution obtained by dissolving the polyurethane raw material in a solvent is used as a coating agent for synthetic leather, artificial leather, fiber, nonwoven fabric, etc., or as a coating agent for magnetic powder, conductive powder, pigment/dye, etc. It is used in magnetic tape, electromagnetic shielding paint, gravure ink, etc. as a coating agent in which it is dispersed.

(4) Heat curing obtained by blending various additives such as a freon foaming agent with the aliphatic polyether carbonate polyol, adding an organic polyisocyanate or a brevolimer having an isocyanate group at the end of the molecule, and foaming with high agitation. Manufactures sex foam products.

(5) Dissolve the molecular terminal isocyanate brevolimer in a solvent, add a known diamine or diol chain extender, etc. to prepare a stable spinning stock solution, and use the wet method, dry method, or extrusion method from this stock solution. Elastic yarn is manufactured by.

More specifically, the polyurethane of the present invention not only has excellent abrasion resistance, impact resistance, hydrolysis resistance, oxidative deterioration resistance, light resistance, low temperature flexibility, and flexibility.
It is a polyurethane with extremely excellent elastic recovery properties, and can cover a wide range of applications for which conventional polyurethanes have been used. For example, open-cell foams (cushioning materials) ranging from rigid to semi-rigid to soft, closed-cell foams (microcellular soles), films, sheets, tubes, hoses, anti-vibration materials, packing materials, adhesives,
Useful for binders, sealants, water stops, flooring materials, casting materials, paints, elastic fibers, etc. [Example] Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples and includes the above-mentioned uses.

In addition, the hydrolysis resistance of polyurethane in the examples is 100μ
A polyurethane film with a thickness of 100° C. was treated in hot water at 100° C. for 12 hours, and the film was evaluated based on the average molecular weight retention rate measured by GPC. The light resistance was evaluated by tensile strength retention after irradiating the above film with 380 nm carbon arc ultraviolet rays for 25 hours using a fade meter. Regarding oxidative deterioration resistance, TGA (in air, 10"C)
The temperature was evaluated based on the thermal decomposition initiation temperature (increase in temperature).

Elastic recovery was evaluated by elongating a 100 μm polyurethane film by 300% in about 90 seconds at room temperature, holding it for about 90 seconds, then contracting it suddenly, measuring the length, and determining the permanent elongation rate. .

Regarding chlorine resistance, the same film was tested in an aqueous solution containing 177 app- of sodium hypochlorite at pH=7.
The film was treated at 0° C. for 16 hours and evaluated based on the retention of tensile strength at break.

Parts in the examples mean parts by weight.

Bo1 Ether Carbonate Bo! Synthesis Example 1 of Oar's Bottom Synthesis 1.6-
472 parts (4.0 mol) of hexanediol and 1.5-
Add 416 parts (4.0 mol) of pentanediol,
At ˜80° C. 1.84 parts (0.08 mol) of sodium metal was added with stirring. After complete reaction of the sodium, 472 parts (8.0 mop.) of diethyl carbonate were introduced. When the reaction temperature was increased to 95-100°C, ethanol began to distill out. Gradually raise the temperature to about 6
The temperature was set at 160°C for an hour. During this time, ethanol containing about 10% diethyl carbonate was distilled out. Thereafter, the pressure in the reactor was further reduced to 10 mm}Ig or less, and under strong stirring 20
The reaction was carried out at 0'C for 4 hours. The produced polymer was cooled, dissolved in dichloromethane, neutralized with dilute acid,
Repeat washing with water several times, dehydrate with anhydrous sodium sulfate, remove the solvent by distillation, and add 2 to 3 mlg, 14
It was dried at 0"C for several hours. The OH value of the aliphatic polyether carbonate diol obtained was 56.0.

Synthesis Example 2 424 parts (4.0 mol) of diethylene glycol synthesized by a conventional method was placed in a reactor equipped with a stirrer, a thermometer, and a distillation tube, and 0.92 parts of metallic sodium (
0.08 mol) was added under stirring.

Then, by performing the same operation as in Synthesis Example 1, OH
A polyether carbonate having a value of 57.0 was obtained.

Synthesis Example 3.4 Table 1 shows the results of synthesizing polyether carbonate in the same manner as in Synthesis Example 2 except that the ether diol shown in Table I was used instead of the ether diol.

Table I Synthesis Example 5 2! Equipped with a stirrer, thermometer, and fractionation tube. 520 g (5 moles) of l,5-pentanediol, 590 g (5 moles) of 1,6-hexanediol, and 880 g (10 moles) of ethylene carbonate were added to a glass flask, and the mixture was stirred at a temperature of 150° C. and a pressure of 20 Torr for 12 hours. The reaction was continued for an additional 4 hours at a temperature of 200° C. and a pressure of 5 Torr. As a result, 980 g of viscous liquid was obtained. A portion of this liquid was taken and hydrolyzed with a KOH ethanol solution, and gas chromatography revealed that its composition was 1.6-hexanediol (49.0 mol%) and 1.5-pentanediol (48.2 mol%). %) }10 + C}
I2−+TO+CflrhOf! (1.1
9 mol%), HO+CI1100-e-CH appearance (1.4
7 mol%), HO + CH thO + CH outOH
; diethylene glycol (0.17 mol%).

This means that 2.8 mol% of repeating units having an ether bond in the molecule is present in the total polymer. Moreover, the OH value was 57. This polyether carbonate diol is abbreviated as PC-^.

Synthesis Example 6 1.6-
Hexanediol 578.2g (4.9 mol), 1
．． 501.3 g (4.82 mol) of 5-pentanediol, 80 {- CH city 0+
CH box Oi+1 9. 3 g (0.119 mol), H
O+CH 0+CH output OH21.8g (0.147mo
l) , 10 Ijl 100 + CHhOH 1.8g
(0.017 mol) and at 70''C to 80'C, 4-6 g (0.2 mol) of metallic sodium was added under stirring.

After the sodium has completely reacted, diethyl carbonate 1
180 g (10 mol) was introduced, and a polyether carbonate diol having an OH value of 57.1 was obtained in the same manner as in Synthesis Example 1. This carbonate is abbreviated as PC-8.

Synthesis Example 7 1000g of polyether carbonate diol produced in Synthesis Example 1 was placed in a flask equipped with a stirrer and a thermometer.Synthesis Example 2
1.65 g of polyether carbonate manufactured in Synthesis Example 3, 6.8 g of polyether carbonate H manufactured in Synthesis Example 3,
Add 9.2 g of polyether carbonate from Synthesis Example 4,
The mixture was stirred at 80°C for 1 hour. This polymer is abbreviated as PC-D.

Synthesis Examples 8 to 22 Polyether carbonate diols were synthesized using various diols in the same manner as in Synthesis Example 1. The conditions and results are shown in Table ■.

In Table H, the amount of metallic Na is 0.08 mol and the amount of diethyl carbonate is 8 mol. Also, 1.6-H in the table
DL is 1,6-hexanediol, 1,5-PDL is 1
, 5-pentanediol, Cz O Ct is diethylene glycol, C4 0 C! is 110+C}l
Fortune 0 {-CIl city OH. , Cs O Cz is ■0
CI2-)-20H, Cb-O-
C, is HO + CHfhO thousand C}! fhOH. C/IE indicates the molar ratio of thiol units to eniterdiol units in the polymer. Cs/Cb
is the 15-pentanediol unit in the polymer and 1.
The molar ratio of 6-hexanediol units is shown.

(Margins below) Table ■ Examples 1 to 4 and Comparative Examples 1-10 PC-Ro1 to E4, PC-Fl, F shown in Table ■
2, PC-GIG2, PC-Hl~H4 and commercially available polytetramethylene glycol (OH value 59.6, P
(abbreviated as TMG), polytetramethylene adipate (OH
58.3, abbreviated as PTA), 3 moles of hexamethylene diisocyanate, and 1 mole of 1,4-butanediol in a mixed solvent of toluene/methyl isobutyl ketone 1:1. The reaction was carried out at 100°C using dibutyl laurate (100 ppm based on solid content) as a catalyst to obtain a 25% polymer solution. The solvent was removed from this under reduced pressure to obtain polyurethane. The evaluation results of various performances of these polyurethanes are shown in Table 3.

(Leaving space below) Table ■ Example 5~lO PC-A, PC-B, PC-D, PC-I
2 moles of any one of polyols f to I3, 3 moles of hexamethylene diisocyanate, and 1 mole of 1,4-butanediol were added. A reaction was carried out at 100° C. in a mixed solvent of toluene/methyl isobutyl ketone 1:1 using diptyltin laurate (100 ppm based on solid content) as a catalyst to obtain a 25% polymer solution. The solvent was removed from this under reduced pressure to obtain polyurethane. The evaluation results of various performances of these polyurethanes are shown in Table 3.

Table ■ Cs/Ci: 1.5-pentanediol and 1.6
- Molar ratio of hexanediol unit C/E j Ratio of diol unit and ether diol unit Examples 11 to 13 and Comparative Examples 11 to 18PC
-El ~E3. PC-Pi. PC-Gl,
PC-}11 to H4. An isocyanate-terminated prepolymer was prepared by reacting 2 moles each of PTMG and PTA with 4 moles of diphenylmethane-4.4'-diisocyanate at 80''C under a nitrogen stream without solvent for 4 hours with stirring, and then cooled to room temperature. Then, sufficiently dehydrated dimethylacetamide was added and dissolved. To this solution, a dimethylacetamide solvent in which 2 moles of ethylenediamine had been dissolved was added all at once, and the mixture was stirred at room temperature for 30 minutes to obtain four types of 30% by weight polyurethane solutions. A portion of the polyurethane solution was cast to obtain a 1ooμ film, with hydrolysis resistance,
In addition to data on light resistance, oxidative deterioration resistance, elastic recovery, and chlorine resistance, we obtained data on tensile elongation and tensile strength at room temperature. The evaluation results are shown in Table ■. Furthermore, we attempted to obtain polyurethane fibers by spinning most of the polyurethane solution using a small spinning device. The results are shown in Table V.

〔Effect of the invention〕

Polyurethane made using the polyether carbonate polyol of the present invention has extremely excellent hydrolysis resistance, light resistance, oxidative deterioration resistance, and elastic recovery properties, and has high chemical stability and excellent rubber properties. This is a high-performance polyurethane that has never existed before.

Claims (1)

[Claims] A polyurethane comprising a polymer polyol, a polyisocyanate, and optionally a chain extender having at least two active hydrogens capable of reacting with the polyisocyanate,
The above-mentioned polymeric polyol has repeating units (A) ▲ has a mathematical formula, chemical formula, table, etc. ▼, (B) ▲ has a mathematical formula, chemical formula, table, etc. ▼, and one or more types of (C) ▲ mathematical formula , chemical formulas, tables, etc. ▼ (R', R'': Alkylene with 1 to 10 carbon atoms, cycloalkylene and its derivatives, phenylene and its derivatives, and their structural formulas ▲ Numerical formulas, chemical formulas, tables, etc.) and its isomers), and its composition is such that the total of (A) and (B) is 90% or more and the total of one or more of (C) is 10% or less, It is an aliphatic polyether carbonate polyol in which the ratio of (A) and (B) is 1/9 to 9/1 (however, the % and the ratio indicate the number of repeating units). polyurethane