WO1998027133A1

WO1998027133A1 - Polyurethane

Info

Publication number: WO1998027133A1
Application number: PCT/JP1997/004582
Authority: WO
Inventors: Shigeru Murata; Shigeo Hosokawa; Yukio Inaba
Original assignee: Kyowa Yuka Co., Ltd.
Priority date: 1996-12-17
Filing date: 1997-12-12
Publication date: 1998-06-25
Also published as: AU5411098A; JP3980068B2

Abstract

A polyurethane having in the molecule polycarbonate polyol moieties comprising structural units of general formula (I) (wherein R1 and R2 are each independently lower alkyl); and a polycarbonate polyol comprising the above structural units and useful as the raw material of the polyurethane.

Description

Specification

Polyurethane

Technical field

The present invention has excellent balance of hydrolysis resistance, heat resistance and low-temperature flexibility, and can be used for extrusion molding materials such as hoses, tubes, films, sheets, belts, rolls, etc., packing materials, machine parts, automobile parts, etc. injection molding materials, artificial leather, ₃ relates to a polycarbonate polyol is a useful Poriuretan and material as a coating material for paint or the like, etc.

Background technology

Polyurethane is a polyester polyol, a polyether polyol, or a polyol such as a polycarbonate polyol and a polysocyanate, and if necessary, a chain extender such as a low molecular weight diol or diamine. It is produced by polymerization in the presence of Polyurethanes using polyester polyols are inferior in hydrolysis resistance compared to polyurethanes using polyether boryls, while polyurethanes using polyester terboliols have problems with heat resistance, etc. Limited Polyurethane using conventional polycarbonate polyols (polycarbonate-based polyurethane) has been improved in the above-mentioned disadvantages, but has a problem in low-temperature flexibility, and its use is limited.

Polyurethane using 3-methyl-1,5-pentanediol is a conventional polyurethane-polyethylene urethane which has relatively good low-temperature flexibility. However, its low-temperature flexibility is not practically satisfactory.

Disclosure of the invention

The present invention provides a compound represented by the formula (I): (I)

One O— CH ₂ -CH— CH ₂ -CH-CH ₂ -O

(Wherein, and R ₂ are the same or different and each represents a lower alkyl), and has a polycarbonate carbonate moiety comprising a structural unit represented by the formula:

The present invention also provides a polycarbonate polyol having a structural unit represented by the formula (I) in a molecule which is a raw material of the polyurethane.

In the definition of the group of the formula (I), lower alkyl includes straight-chain or branched mono-elements having 1 to 8 such as methyl, ethyl, propyl, isopropyl, butynole, isoptinole, sec-butyl, tert-butizole, Pentinole, isoamyl, neopentyl, 2-pentyl, 3-bentyl, hexyl, heptyl, octyl and the like.

The method for producing the polycarbonate polyol which is a raw material of the polyurethane of the present invention is not particularly limited. For example, 2,4-dialkyl-1,5-pentandiol, which is a component of the structural unit represented by the formula (I), and a carbonate compound are combined with a plastic material course 5 “Polycarbonate resin” (published by Nikkan Kogyo Shimbun). , Pp. 62-63, 1969), transesterification by a known method described in JP-A-4-31418, JP-A-60-195117, etc. It can be produced by reacting.

Specific examples of 2,4-dialkyl-1,5-pentanediol used in the polycarbonate polyol of the present invention include 2,4-dimethyl-11,5-pentanediole and 2-ethyl-4-methyl-11,5. —Bentanediol, 2 —Methinole _ 4-Bropyryl 1,5—Bentandiole, 2,4-Jetgray 1,5 _Bentandiole, 2 —Echinolé 4 —Bro Pinole _1,5—Bentane Dionole, 2,4-dipropyl-1,5-pentanediol, 2-isopropyl-1 4-methinole 1,5-pentandiolone, 2-ethyl

Two 4-Isopropinole 1,5—Bentanediol, 2,4-Diisopropyl-1,5—Pentane mono, 2-Isopropinole 1 4-Propyl_1,5 Pentane mono, 2,4, Dibutyl mono 1,5-pentanitol, 2,4-dipentinole-1,5-ventenole, 2,4-dihexynole-1,5-pentanediol, etc. Among them, 2,4-dimethyl-11,5 —Pentanediol, 2,4—getinole 1,5—pentanedoneole, 2,4-dipropyl —1,5—ventandole, etc. are preferred. The joule can be produced according to the method described in JP-A-8-48642. The diols may be used alone or in combination of two or more types. C The diols can also be used as a mixture with known diols. In this case, the proportion of the diol is at least 20%, preferably at least 30% of the total diol. If it is less than 20%, the resulting polyurethane will have poor hydrolysis resistance, heat resistance and low-temperature flexibility. Preferred examples of other known diols that may be used in combination include ethylene glycol, propylene glycol, tetramethylene glycol cornole, diethylene glycol cornole, 1,6-hexaneglycol, and 2-pentinole_2- 1,3-Pronodiol, 3-methino-1,5-pentanediol, 1,4-bis (] 3-hydroxyethoxy) benzene, and the like.

Specific examples of the carbonate compound used in the production of the polycarbonate polyol of the present invention include dialkyl carbonates such as getyl carbonate, and diaryl carbonates such as diphenyl carbonate. The carbonate compound may be used alone or in combination of two or more.- The number average molecular weight of the polycarbonate of the present invention is preferably from 400 to 8,000, More preferably, it is 700 to 4,000.

The polyurethane of the present invention can be produced using a known method. That is, the polycarbonate vorol obtained above and, if necessary, a low-molecular compound (chain extender) having two or more active hydrogen atoms are uniformly mixed, and preheated to about 60 ^EC . Number of active hydrogen atoms and isosia The polyisocyanate was added in such an amount that the molar ratio of the nate groups became 0.95 to 1: 1.05, and the mixture was supplied to a continuous polymerization apparatus having a twin-screw screw while stirring with a rotary mixer for a short time. Polyurethane of the present invention can be obtained by random polyaddition. Alternatively, it can be obtained by preliminarily reacting polycarbonate diol and polyisocyanate, and via a prepolymer having terminal isocyanate groups. These reactions are usually carried out without solvent, but can also be carried out in a solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, toluene and the like. These solvents may be used alone or in combination of two or more. Examples of the polyisocyanate include 4,4′-diphenylmethane diisocyanate and 2,4-tolylene diisocyanate Aromatic diisocyanate, etc., alicyclic diisocyanate such as isophorone diisocyanate, and aliphatic diisocyanate such as hexamethylene diisocyanate. These polyisocyanates alone can be used. It can be used or two or more types can be used together.

Examples of chain extenders include ethylene glycol, propylene glycol, tetramethylene glycol, di- / ones such as 1,6-hexanediol, diamines such as pyrene diamine and isophorone diamine. May be used alone or in combination of two or more. Further, if necessary, a monovalent low molecular weight alcohol such as methanol or ethanol, or a monovalent low molecular weight amine such as methylamine or ethylamine is used as a denaturant. Can also be added.

The weight average molecular weight of the polyurethane is preferably 40,000 to 500,000, more preferably 60,000 to 200,000 ₌ molecular weight 4 Below 0, 000, the mechanical properties of the polyurethane deteriorate. On the other hand, if it is larger than 500,000, the molding processability of the polyurethane decreases. If the _c- polymerization reaction is carried out without a solvent, the obtained polyurethane can be immediately subjected to molding after polymerization. If the unreacted polyisocyanate remains in an amount of 0.2% by weight or more due to polymerization conditions, if necessary, aging is performed at 60 to 80 ⁼ C for 4 to 30 hours to complete the reaction. Subject to molding If carried out in solvent can be ₌ the polymerization reaction, a non-solvent for the poly urethane, For example, hexane, heptane, octane, nonane, carbon number 6-1 0 decane aliphatic saturated hydrocarbons, methanol, ethanol Polyurethane is coagulated and precipitated by adding and mixing alcohols, etc., filtered, separated and dried, and then subjected to molding.

The obtained polyurethane can be formed by various methods. Examples of the molding method include extrusion molding at 150 to 230, preferably 170 to 220 ° C, injection molding, calendar molding, blow molding (plastic processing). Technical Handbook, Hon Kogyo Shimbun, p. 125, p. 213, p. 283, p. 323, p. 196).

Next, the hydrolysis resistance, heat resistance, and low-temperature flexibility of the polyurethane of the present invention will be described with reference to test examples.

Test Example 1 Hydrolysis resistance

Using the polyurethane prepared in Examples 1 and 2 and Comparative Examples 1 to 3 to be described later, a _{c /} extrusion machine was prepared by extrusion to prepare a 300 / im polyurethane sheet under the following conditions: 40 mm single screw extruder LZD = 2 5, compression ratio 1: 2 8 extrusion conditions: temperature ^{1 8 5 = C:. C} 2 1 9 0 C C; C 3 1 9 0 = C;

C 4 195 ^C C: Die 195. C

Screw rotation speed; 25 rpm

Further Poriuretanshi Ichito created, after seven days of immersion in 80 ° warm water, the breaking strength at 2 3 ³ C measured according JISK- 7 3 1 1, was determined breaking strength retention.

Test example 2 heat resistance

Example 1, 2 to be described later, to prepare a Boriuretanshi one bets in the same manner as in Test Example 1 using Helsingborg urethane prepared in Comparative Examples 1 to 3: a further created volume Li urethane sheet, 1 0 0 ⁼ After aging for 7 days in air using a complete gear aging tester (manufactured by Kamishima Seisakusho Co., Ltd.) at C, JISK-731

The breaking strength was measured in accordance with 1 to determine the breaking strength retention.

Test Example 3 Low temperature flexibility Polyurethane sheets were prepared in the same manner as in Test Example 1, using the polyurethanes prepared in Examples 1 and 2 and Comparative Examples 1 to 3 described later. Further, the Ta (tan 6 max) value of the prepared polyurethane sheet was measured at 1 Hz using a DVE Leosbeta Toler (manufactured by Reology Inc.).

Table 1 shows the measurement results of Test Examples 1 to 3.

Table 1

Polyurethane of the present invention, hydrolysis resistance, high breaking strength holding ratio at the heat resistance test, and low tau _alpha value in the low temperature flexibility test, compared with Comparative Example

Excellent in terms of overall hydrolysis resistance, heat resistance, and low temperature flexibility. BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 "Synthesis of polycarbonate polyol"

Under a nitrogen atmosphere, 2,4-getyl-1,5-pentanediol and diphenylcarbonyl of the raw material composition shown in Table 2 were heated at 180 to 190 ° C for 3 hours for transesterification. Was done. Then, gradually raise the temperature to 220 ⁼ C, continue the reaction for 10 hours while gradually reducing the pressure to 5 to 10 mmHg, stop the reaction after removing the phenol in the system, and stop polycarbonate. Voriol A, was manufactured.

"Production of polyurethane"

Polyurethane A was produced from the polycarbonate vorol A obtained above by the solvent-free continuous polymerization method using the raw material composition shown in Table 3 and the following JS synthesis equipment and formulation. Pre-mixing: High-speed rotating mixer, temperature 50-60 ° C

Polymerization equipment: twin screw type reaction extruder, L / D = 42, approx. L O K gZ time

Polymerization time: about 150 seconds

Example 2 "Synthesis of polycarbonate polyol"

In the same manner as in Example 1 except that a mixed diol of 2,4-getyl-1,5-pentanediole and 1,6-hexanediol having a raw material composition shown in Table 2 and diphenyl carbonate were used. Polycarbonate polyol _Bi was produced.

"Production of polyurethane"

Using the polycarbonate polyol B obtained above and the raw material composition shown in Table 3, a polyurethane B was produced in the same manner as in Example 1.

Table 2 shows the raw material composition of the polycarbonate polyols produced in Examples 1 and 2 and the physical properties of the products. The number average molecular weight of the polycarbonate polyol was calculated from the hydroxyl value.

Table 2

X 2, 4—Jetyl-1,5-pentanediol

X 1, 6—Hexanediol ·

X diphenyl carbonate

Table 3 shows the raw material composition of the polyurethanes produced in Examples 1 and 2 and the molecular weight of the product. The weight average molecular weight of the polyurethane was measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

(GPC analysis conditions)

Column: GMHHR—Η [inner diameter 7.8 mm, length 30 cm 2) and G200HHR [inner diameter 7.8 mm, length 30 cm (manufactured by TOSHI CORPORATION)] were connected in series.

Mobile phase: Tetrahydrofuran (flow rate 1 m1 min)

Detector; R I [R I-800 (Tosoichi Co., Ltd.)]

Table 3

Y! : Polycarbonate Polyall

Y: Diphenyl methane diisocyanate

Tetramethylen glycol

Comparative Example 1 "Synthesis of polycarbonate polyol"

A polycarbonate polyol was produced in the same manner as in Example 1 except that 1,6-hexanediol and diphenyl carbonate were used in the raw material compositions shown in Table 4.

"Production of polyurethane"

The polycarbonate polyol C obtained above was used and treated in the same manner as in Example 3 with the raw material compositions shown in Table 5 to produce polyurethane C.

Comparative Example 2 Production of polyurethane J

Using Aderick New Ace F13-35 (tetramethylene adipate, molecular weight 210 13) manufactured by Asahi Denka Kogyo Co., Ltd. and treating in the same manner as in Example 1 with the raw material composition shown in Table 5, the polyurethane D was manufactured.

Comparative Example 3 "Production of polyurethane"

Using PTG 100 (Polytetramethylene ether glycol, molecular weight: 10 13) manufactured by Hodogaya Chemical Industry Co., Ltd. and treating it in the same manner as in Example 1 with the raw material composition shown in Table 5, to produce polyurethane E did.

Table 4 shows the raw material composition of the polycarbonate carbonate and the physical properties of the product produced in Comparative Example 1. The number average molecular weight of polycarbonate polyol is water 98/27133

Calculated from acid value

Table 4

Table 5 shows the raw material composition of the polyurethanes produced in Comparative Example 1 to Comparative Example ³ and the molecular weight of the product. The weight average molecular weight of the polyurethane was measured by gel permeation chromatography (GPC) in terms of standard polystyrene under the same analytical conditions as described above.

Table 5

Z i: Diphenylmethane diisocyanate Z: Tetramethylene glycol Polyester polyol: Asahi Denka Kogyo Co., Ltd. Adderiki New Ace F 13 — 35 Polyether polyol: Hodogaya Chemical Co., Ltd. p TG 1 0 0 0

/ Business availability

According to the present invention, there is provided a polyurethane excellent in a balance between hydrolysis resistance, heat resistance, and low i'ff _L flexibility, and polycarbonate vorol as a raw material thereof.

Claims

Range of request

Formula (I) in the molecule

I I (i)

O— CH ₂ -CH— CH ₂ -CH— CH ₂ -O-

(Wherein, and R ₂ are the same or different and each represents lower alkyl). Polyurethane having a polycarbonate polyol portion comprising a structural unit represented by the formula:

2.2 2,4-Dialkyl-1,5-pentanediol alone or 20% of the diol. / ₀ or more from the mixing diol and a carbonate compound containing obtained from Helsingborg carbonate Helsingborg ol with poly I Société § sulfonates are obtained found請Motomeko 1 Helsingborg urethane according.

3. The polyurethane according to claim 2, wherein the 2,4-dialkyl-1,5-pentanediol is 2,4-diethyl-1,5-pentanediol.

4. The polyurethane according to claim 2, wherein the weight average molecular weight is 40,000 to 500,000.

5.2 Reaction of 2,4-dialkyl_1,5-pentanediol alone or a mixed diol containing at least 20% of the diol with a carbonate compound to obtain a polycarbonate polyol, and then the polycarbonate polyol 2. The method for producing a polyurethane according to claim 1, wherein the polyisocyanate is reacted with a polyisocyanate.

6. Formula (I) in the molecule

Polycarbonate toboliol having a structural unit represented by:

7. The polycarbonate diol according to claim 6, which is obtained from a 2,4,4-dialkyl-1,5-pentanediol alone or a mixed diol containing at least 20% of the diol and a carbonate compound.

8. 2,4-Dialkyl_1,5_pentanediol is 2,4-diethyl 8. The polycarbonate topolol according to claim 7, which is rou 1,5-pentanediol.

9. The polycarbonate boryl according to claim 7, which has a number average molecular weight of 400 to 8,000.

7. The polycarbonate polyol according to claim 6, wherein a polycarbonate compound is reacted with 10.2,4-dialkyl-1,5-pentanediol alone or a mixed diol containing at least 20% of the diol. Manufacturing method.