JPS6331490B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a modified polyurethane stabilized against the effects of light by introducing a specific piperidine derivative into the molecule. Stericly hindered piperidine compounds are useful as light stabilizers for organic materials, and are particularly effective as light stabilizers for synthetic resins such as polyolefins and polyurethanes, and various derivatives are added to various synthetic resins. These piperidine compounds include 2, 2, 6,
Ethers, esters, carbamates of 6-tetraalkyl-4-hydroxypiperidine, 2,
Examples include amides of 2,6,6-tetraalkyl-4-aminopiperidine and polyhydric alcohol ketals of 2,2,6,6-tetraalkyl-4-piperidone. However, these additive-type light stabilizers are often extracted by solvents, volatilized during processing, or bleed or bloom from molded products, resulting in a rapid decline in the light resistance of plastic materials, making them impractical for practical use. is often unsatisfactory. In order to eliminate these drawbacks, Japanese Patent Application Laid-Open No. 53-1294
No. 2, 2, 6,
It has been proposed to attach 6-tetraalkylpiperidine groups to polyurethane molecules. According to the methods described in these publications, extractability, volatility, migration, etc. can be reduced to some extent, but the photostability is still insufficient, and a relatively large amount must be combined into polyurethane. . However, when a large amount of the 2,2,6,6-tetraalkylpiperidine group described in these publications is bonded to polyurethane, the physical properties of polyurethane (elongation, strength, etc.) often deteriorate, and it is still insufficient for practical use. It was hot. As a result of extensive studies in view of the current situation, the present inventors have found that when manufacturing polyurethane, a compound represented by the following formula () is used as a part of the raw material, and a group represented by the following formula () is added to the polyurethane molecule. The present inventors have discovered that a polyurethane that solves all of the above problems can be obtained by incorporating the above-mentioned polyurethane into the polyurethane. (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an oxygen radical, or an alkyl group. _{R 3} represents an alkylene group having 2 to 10 carbon atoms. _{n 1} and n ₂ are 0 to about
Shows 50. ) The polyurethane stabilized according to the invention is
It can be used in various applications such as foams, elastic fibers, molded products, paints, and lacquers. Polyurethane is produced by the conventional one-shot method, prepolymer method, or pseudo-method, in which polyether polyol and/or polyester polyol (molecular weight approximately 500 to 5000) having a hydroxyl group at the end and polyisocyanate are used together with a chain extender, etc., if necessary. It can be manufactured using a prepolymer method or the like. Examples of polyether polyols include polyoxypropylene glycol, polyoxypropylene-polyoxyethylene glycol, polylene triol, polyoxypropylene triol, and polyoxypropylene tetraol. Polyester polyols are manufactured from polybasic acids and polyhydric alcohols; polybasic acids include succinic acid, adipic acid, sebacic acid, maleic acid, phthalic acid, trimellitic acid, etc., and polyhydric alcohols include ethylene glycol, Propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol,
Examples include trimethylolpropane, trimethylolethane, glycerin, hexanetriol, and pentaerythritol. Polycaprolactone glycol can also be used as the polyester polyol. Examples of chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, and triethylene glycol. Polyhydric alcohols such as methylolpropane and hexanetriol, hydrazine, ethylenediamine, propylene diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, tolylene diamine, 1,
Examples include amines such as 6-hexamethylene diamine, and amino alcohols such as monoethanolamine, diethanolamine, monopropanolamine, and dipropanolamine. Furthermore, as polyisocyanates, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, and trifluorene diisocyanate are used. Examples include enylmethane diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, dimer diisocyanate, phenylene diisocyanate, diphenyl ether diisocyanate, dianisidine diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, and the like. The stabilized polyurethane according to the present invention is produced by using the above-mentioned isocyanate and a piperidine compound represented by the following formula () together when producing the polyurethane. [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an oxygen radical, or an alkyl group. R ₃ represents an alkylene group having 2 to 10 carbon atoms. n ₁ and n ₂ are 0 to approx.
Shows 50. ] In the above formula, the alkyl group represented by R ₁ and R ₂ includes methyl, ethylpropyl, isopropyl,
Examples include butyl, isobutyl, hexyl, octyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxyhexyl, 2-hydroxyoctyl, 2-hydroxy-2-phenylethyl, and the like. In addition, the alkylene group represented by R ₃ is ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, 1,
2-pentylene, 1,5-pentylene, 1,2-
Examples include hexylene, 1,6-hexylene, 1,2-octylene, and 1,2-decylene. The compound represented by the above formula () is, for example, 2,
The 2,6,6-tetramethyl-4-piperidone derivative is easily reacted with dipentaerythritol, and then optionally with an alkylene oxide having 2 to 10 carbon atoms or with a cyclic ether. can be manufactured. In addition, a piperidine compound represented by the above formula () as part or all of the glycol component,
The stabilized polyurethane of the present invention can also be produced by using a polyester polyol produced by reacting with a polycarboxylic acid. The reason why the polyurethane of the present invention has superior stability compared to the conventional polyurethane with piperidine compounds bonded is not clear, but the reason why the polyurethane of the present invention has two piperidine rings bonded by an ether bond is not clear. It is presumed that this is because the conventional piperidine compound forms a soft segment part of polyurethane, whereas the conventional piperidine compound forms a part similar to the soft segment part of polyurethane. According to the present invention, the piperidine derivative can be reacted with an isocyanate component as part or all of the polyol component during the production of polyurethane, and the piperidine derivative can be used as a chain extender or can be used as a chain extender. It can also be used in combination with. Alternatively, the piperidine derivative can be used to prepare a prepolymer and then reacted with other components. Solvents such as benzene, chlorobenzene, tetrahydrofuran, dimethylformamide, etc. can be used in producing the stabilized polyurethane of the present invention. Further, the reaction temperature is appropriately selected from the range of about 20 to 150°C. Moreover, the above formula () in the polyurethane of the present invention
The content of groups represented by is 0.001 in polyurethane.
-10% by weight, preferably 0.01-5% by weight. Various commonly used additives can be added to the polyurethane of the present invention. These additives include, for example, phenolic antioxidants, phosphite compounds, sulfur-containing compounds,
Examples include ultraviolet absorbers, metal soaps, antistatic agents, flame retardants, foaming agents, thixotropic agents, pigments, and fillers. Furthermore, when used in polyurethane paints, lacquers, etc., cellulose derivatives such as cellulose nitrate, cellulose acetate-propionate, and cellulose acetate-butyrate can be added. These additives can be added during the manufacture of the polyurethane, or they can be added before molding. Next, the present invention will be explained in more detail with reference to Examples, but these are not intended to limit the present invention in any way. Example 1 Adipic acid with a molecular weight of 2600 and a hydroxyl value of 44 and 1,
130 g (0.05 mol) of polyester diol from 4-butylene glycol and 17.4 g (0.1 mol) of tolylene diisocyanate were mixed at 100°C under a nitrogen stream for 1.5 g.
Allowed time to react. Then 3.6 g (0.04 mol) of 1,4-butylene glycol and the formula Bis(3-hydroxymethyl-8,
8,10,10-tetramethyl-9-aza-1,5-
Dioxaspiro[5.5]-3-undecylmethyl)
Add 5.3g (0.01 mol) of ether and heat to 100°C for another 1.5
Allowed time to react. After cooling, add 300 g of dimethylformamide to make the product a viscous solution, apply it on aluminum foil, dry it, and thicken it.
A coating film of 0.5 mm was obtained. Examples 2 to 3 and Comparative Example 1 Bis(3-hydroxymethyl-8,8,10,10
Example 1 Using the following piperidine derivative in place of -tetramethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl)ether
Polyurethane is manufactured in the same manner as 0.5 in thickness.
A coating film of mm was obtained. Example 2 Bis(3-hydroxymethyl-8,8,9,
10,10-pentamethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl)ether 5.6 g (0.01 mol) Example 3 Bis(3-hydroxymethyl-7,7,8,
5 mole propylene oxide adduct of 9,9-pentamethyl-8-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl)ether 8,2
g (0.01 mol) Comparative example 1 3,15-bis(2-hydroxyethyl)-2,
2,4,4,14,14,16,16-octamethyl-
3,15-diaza-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]heneicosane 5.0g
(0.01 mol) Comparative Example 2 In the same manner as in Example 1, 4.5 g of 1,4-butylene glycol was added without using a piperidine derivative.
(0.05 mol) of bis(3-hydroxymethyl-8,8,10,10-tetramethyl-9-aza-1,5-dioxaspiro [5.5]) before coating on aluminum foil. 5.3 g of -3-undecylmethyl)ether was added to obtain a coating film with a thickness of 0.5 mm. Example 4 Using the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 described above, changes in elongation at break (%) by irradiation with a high-pressure mercury lamp were measured. Further, a film extracted with methanol for 10 hours was also tested in the same manner. The results are shown in Table 1 below.

[Table] Example 5 100.0 g (0.05 mol) of polytetramethylene ether glycol with a molecular weight of 2000 was mixed with 150 g of chlorobenzene.
Diphenylmethane diisocyanate dissolved in ml
20.0g (0.08mol) was added and reacted at 120°C for 30 minutes. Then 2.25g of 1,4-butylene glycol
(0.025 mol) and bis(3-hydroxymethyl-
8,8,10,10-tetramethyl-9-aza-1,
Add 2.64 g (0.005 mol) of 5-dioxaspiro[5.5]-3-undecylmethyl)ether and heat to 110°C.
It reacted for 2 hours. The resulting solution was dry-spun using a conventional method to obtain a 40-denier elastic yarn. Example 6 and Comparative Example 3 Bis(3-hydroxymethyl-8,8,10,10
A polyurethane elastic thread was obtained in the same manner as in Example 5, except that the following piperidine derivative was used instead of -tetramethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl)ether. Example 6 Bis(3-hydroxymethyl)-8,8,9,
10,10-pentamethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl) ether 2.78 g (0.005 mol) Comparative example 3 3-ethyl-3-hydroxymethyl)-8,
8,10,10-tetramethyl-9-hydroxyethyl-9-aza-1,5-dioxaspiro [5.5]
Undecane 1.50g (0.005mol) Comparative Example 4 A polyurethane solution was produced in the same manner as in Example 5 using 2.7g of 1,4-butylene glycol without using the piperidine derivative, and bis(3-hydroxymethyl-8,8 ,9,10,10-pentamethyl-9
2.78 g of -aza-1,5-dioxaspiro[5.5]3-undecylmethyl)ether was added and spinning was carried out. Example 7 The residual elongation after 72 hours of irradiation was measured using a fade meter using the elastic yarns obtained in Examples 5 and 6 and Comparative Examples 3 and 4. Elastic threads extracted with carbon tetrachloride for 2 hours were also tested in the same manner. The results are shown in Table 2 below.

[Table] Example 8 Polyester 56 g (0.03
mol) and diphenylmethane diisocyanate 15
g (0.06 mol) was heated and stirred at 120°C for 1 hour.
Then bis(3-hydroxymethyl-8,8,
Add 2.11 g (0.004 mol) of 10,10-tetramethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecimethyl)ether and react at 120°C for another hour, then cool.
Diluted with 50g. Add this solution to ethylenediamine
1.56g (0.026mol), dimethylformamide 250
g, and was added dropwise to a suspension of 4 g of dry ice over 30 minutes. The resulting viscous solution was applied onto aluminum foil and dried to obtain a 0.5 mm thick film. Example 9 Polytetramethylene glycol with molecular weight 1010
After heating and stirring 30.3 g and 1,6-hexamethylene diisocyanate 10.08 g (0.06 mol) at 120°C for 1 hour, bis(3-hydroxymethyl-8,8,10,
2.11 g (0.004 mol) of 10-tetramethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl)ether and ethylene glycol
1.61 g (0.026 mol) was added and the reaction was further carried out at 120°C for 1 hour. After cooling, it was dissolved in 150 g of tetrahydrofuran and 150 g of dimethylformamide to form a viscous solution. Apply this solution on aluminum foil and dry it to a thickness
A 0.5 mm film was obtained. Examples 10-11 Bis(3-hydroxymethyl-8,8,10,10
-Tetramethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl) ether, the following piperidine derivative was used, and the same procedure as in Example 9 was performed except that the amount of ethylene glycol used was changed. A film with a diameter of 0.5 mm was obtained. Example 10 3-hydroxymethyl-8,8,10,10-tetramethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl-3-hydroxymethyl-8,8,10,10 -Tetramethyl-9-hydroxyethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecyl methyl ether
2.29g (0.004mol), ethylene glycol 1.49g
(0.024 mol) Example 11 Bis(3-hydroxymethyl-8,8,10,10
-Tetramethyl-9-hydroxyethyl-9-aza-1,5-dioxaspiro[5.5]-3-undecylmethyl)ether 2.46 g (0.004 mol), ethylene glycol 1.36 g (0.02 mol) Comparative Example 5 Example 8 A film with a thickness of 0.5 mm was produced by using the following piperidine derivative in place of the piperidine derivative in . Comparative example 5 1,1'-dihydroxyethyl-4,4'-dihydroxy-2,2,2',2',6,6,6',6'-octamethyl-4-4'-dipiperidyl Comparative example 6 Piperidine Ethylene glycol without derivatives
A polyurethane solution was obtained by reacting in the same manner as in Example 9 except that 1.86 g was used. Add bis(2,2,
2.05 g (0.004 mol) of 6,6-tetramethyl-4-piperidyl) sebacate was added to produce a film with a thickness of 0.5 mm. Example 12 The remaining elongation of the films obtained in Examples 8 and 9 and Comparative Examples 5 and 6 after 144 hours of irradiation was measured using a fade meter. Furthermore, the residual elongation rate of the film after extraction with methanol for 10 hours was also measured. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1. When producing polyurethane, a piperidine compound represented by the following formula () is used as a part of the raw material, and the following formula () is added to the polyurethane.
A method for producing a stabilized polyurethane, the method comprising introducing a group represented by the following. (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an oxygen radical, or an alkyl group. R ₃ has 2 carbon atoms.
~10 alkylene groups are shown. n ₁ and n ₂ are 0 to about 50
shows. )