JP2705924B2 - Method for producing block polyurethane polyol - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a block polyurethane polyol, and more particularly, to a two-component polyurethane adhesive used for bonding, for example, a polypropylene material to a flexible PVC sheet material. The present invention relates to a method for producing a block polyurethane polyol useful as one of the main components of the invention. 2. Description of the Related Art Deposited materials such as polypropylene materials, noryl resin materials, composite materials containing polyolefin fibers or powders (bundressers, woodlenes), etc. have low polarities, and are particularly polar. Different materials
(PVC sheet etc.) is considered difficult. Conventionally, a two-component polyurethane adhesive using a thermoplastic polyester urethane rubber as a main component and a polyisocyanate compound as a cross-linking agent has been used for this bonding.However, in order to exhibit sufficient adhesive strength, In addition, surface treatment of the adherend by primer treatment (use of chlorinated polyolefin or the like) or plasma or corona discharge treatment is required.
An object of the present invention is to provide a method for producing a block polyurethane polyol, which can improve the adhesive strength by blending the two-component polyurethane adhesive with a thermoplastic polyester urethane rubber. In order to achieve this object, the present inventors have made a specific hydrogenated polybutadiene-based polyol react with a highly polar polyisocyanate and another polyol sequentially to form a block. Then, they found that a block polyurethane polyol with improved intended adhesive strength and good compatibility stability could be obtained, thereby completing the present invention. That is, the present invention relates to a hydrogenated hydroxyl-terminated polybutadiene glycol of the formula: HO-R-OH (wherein R is the residue of a hydrogenated hydroxyl-terminated polybutadiene glycol) (hereinafter referred to as hydrogenated polybutadiene glycol). An excess of the formula OCN-R'-NCO, where R 'is a polyisocyanate residue, is obtained by reacting a polyisocyanate of the formula OCN-R'-NHCOO-R-OOCNH-R' A urethane prepolymer containing from 0.5 to 10% by weight of active isocyanate groups of —NCO 3 (hereinafter referred to as NCO urethane prepolymer), followed by the formula: HO—R ″ —OH (where R ″ is a polyol residue) Is a polyol having two or more hydroxyl groups in the molecule of OH / NCO of 3.
By reacting so as to be 0 to 10.0, the formula: HO-R "-OOCNH-R'-NHCOO-R-OOCNH-R'-NHCOO-R" -OH (wherein R, R ' And R "have the same meanings as defined above.) The present invention provides a method for producing a block polyurethane polyol characterized by obtaining a block polyurethane polyol represented by the following formula: It can be manufactured by the following procedure.
The hydrogenated polybutadiene glycol and the polyisocyanate are reacted with the hydroxyl group (OH) of the hydrogenated polybutadiene glycol based on the active isocyanate group (NC) of the polyisocyanate.
O) is reacted in excess to obtain an NCO urethane prepolymer. This reaction is carried out, if necessary, using a suitable reaction solvent.
(Hexane, toluene, heptane, cyclohexane, xylene, methylene chloride, carbon tetrachloride, etc.) at room temperature to 100 ° C. The reaction is carried out when the active NCO content of the resulting NCO urethane prepolymer is between 0.5 and 10
It is prepared so as to be% by weight. Preferably 1 to 5% by weight
To In the reaction, a catalyst such as dibutyltin laurate, triethylamine, or lead octylate may be used.
Next, a polyol having two or more hydroxyl groups in the molecule or a solvent solution thereof (toluene, hexane, heptane, cyclohexane, xylene, methylene chloride, carbon tetrachloride, or the like as a solvent) is added to the NCO urethane prepolymer, and the mixture is cooled to room temperature. React at a temperature of １００100 ° C. In this case, the reaction ratio between the NCO urethane prepolymer and the polyol is selected so that OH / NCO becomes 3.0 to 10.0. By such a two-stage reaction, a target block polyurethane polyol is obtained. The hydrogenated polybutadiene glycol is obtained by hydrogenating a hydroxyl-terminated polybutadiene glycol, and has a polybutadiene structure of 1,2-
Vinyl structure or 1,4-trans structure alone, or 1,2-vinyl structure and 1,4-trans structure, 1,2-
It has a vinyl structure, a 1,4-trans structure, a 1,4-cis structure, and a mixed structure of a 1,4-trans structure and a 1,4-cis structure, and any of them can be used. There is no limitation on the ratio of each structure in the mixed structure. Hydrogenation may be performed using an appropriate organic solvent (hexane,
Heptane, cyclohexane, toluene, etc.) in the presence of a metal catalyst such as nickel, cobalt, platinum, palladium, ruthenium and the like, at normal pressure to high pressure. Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate. Such as alicyclic polyisocyanates, tolylene diisocyanate (TDI), diphenylmethane diisocyanate
(MDI), aromatic polyisocyanates such as naphthylene diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, and tris (4-phenyl isocyanate) thiophosphate. One or a mixture of two or more of these is used. To serve. Examples of the polyol include polyalkylene alkyl ether polyols, polyester polyols, acrylic polyols, polycarbonate polyols, and the like, and one or a mixture of two or more of these may be used. Next, the present invention will be described more specifically with reference to Reference Examples and Examples. Reference Example 1 (Production of hydrogenated polybutadiene glycol) 100 parts of hydroxyl-terminated polybutadiene glycol [manufactured by Idemitsu Petrochemical Co., Ltd., Poly bd R-45HT, 80% of 1,4-bond and 20% of 1,2-bond, molecular weight 2800] (100 parts) Parts by weight, hereinafter the same) was dissolved in 1000 parts of toluene, 10 parts of 10% palladium / carbon catalyst was added thereto, and the mixture was stirred in a hydrogen stream for 10 hours, and hydrogenation was performed. Toluene is obtained to obtain solid hydrogenated polybutadiene glycol. Melting point 60-70 ° C, iodine value (g / 10
0 g) <5. Reference Example 2 In Reference Example 1, a hydroxyl-terminated polybutadiene glycol [Nisso PB2000 G, 1,2-manufactured by Nippon Soda Co., Ltd.]
90% of bond and 10% of 1,4-bond, molecular weight 2000]
A liquid hydrogenated polybutadiene glycol is obtained in the same manner except that 100 parts are used. Iodine value (g / 100g) <
5. Examples 1 to 6 Hydrogenated polybutadiene glycol in the number of parts shown in Table 1 and MD
I (NCO / OH = 2.3) in 70% toluene
The mixture was reacted at 0 ° C. for 5 hours to obtain a toluene solution of NCO urethane prepolymer.
A 0% toluene solution is added (OH / NCO = 6) and reacted at 80 ° C. for 5 hours to obtain a block polyurethane polyol. [Table 1]

Claims (1)

(57) [Claims] Formula: HO-R-OH (where R is the residue of hydrogenated hydroxyl-terminated polybutadiene glycol) and an excess of hydrogen-terminated polybutadiene glycol of the formula: OCN-R'-NCO (wherein R ′ is a polyisocyanate residue) containing 0.5 to 10% by weight of active isocyanate groups of the formula: OCN—R′—NHCOO—R—OOCNH—R′—NCO 2 And a polyol having two or more hydroxyl groups in a molecule of the formula: HO-R "-OH (where R" is a polyol residue).
By reacting so as to be 0 to 10.0, a block polyurethane polyol represented by the formula: HO-R "-OOCNH-R'-NHCOO-R-OOCNH-R'-NHCOOR-R" -OH is obtained. A method for producing a block polyurethane polyol, comprising: