Use of polymerizable ultraviolet absorber in polyurethane and composition for preparing polyurethane comprising the same

Abstract

A use of a polymerizable ultraviolet absorber is disclosed, which is applied to a polyurethane preparation. The polymerizable ultraviolet absorber is obtained by reacting an UV absorber having a reactive hydrogen group with a polyisocyanate having three NCO groups. In addition, a composition for forming polyurethane comprising the aforementioned polymerizable ultraviolet absorber is also disclosed.

Claims

1. A use of a polymerizable ultraviolet absorber, which is applied to a process for preparing polyurethane, wherein the polymerizable ultraviolet absorber is obtained by reacting an UV absorber having a reactive hydrogen group with a polyisocyanate having three NCO groups.

2. The use of claim 1, wherein a weight average molecular weight of the polymerizable ultraviolet absorber is less than 5,000.

3. The use of claim 1, wherein the reactive hydrogen group as a functional group comprised in the UV absorber is selected from the group consisting of OH, NH.sub.2 and NH.

4. The use of claim 1, wherein the UV absorber is selected from the group consisting of: a benzotriazole UV absorber, a benzophenone UV absorber, a triazine UV absorber, an oxanilide UV absorber and a cyanoacrylate UV absorber.

5. The use of claim 1, wherein the polyisocyanate is selected from the group consisting of: hexamethylene diisocyanate trimer (HDI TRIMER), hexamethylene diisocyanate biuret (HDB) and a mixture thereof.

6. The use of claim 1, wherein the polymerizable ultraviolet absorber is obtained by reacting the UV absorber having the reactive hydrogen group with the polyisocyanate having the three NCO groups and a diol or a polyol.

7. The use of claim 6, wherein the diol or the polyol is selected from the group consisting of an anionic diol, an anionic polyol, a cationic diol, a cationic polyol, a nonionic diol, a nonionic polyol, and a mixture thereof.

8. The use of claim 7, wherein the anionic diol or the anionic polyol is selected from the group consisting of: 2,2-bis(hydroxymethyl)butyric acid (DMBA), 2,2-bis(hydroxymethyl)propionic acid (DMPA), 1,4-butanediol-2-sodium or a mixture thereof.

9. The use of claim 7, wherein the cationic diol or the cationic polyol is selected from the group consisting of N-methyldiethanolamine (MDEA), triethanolamine or a mixture thereof.

10. The use of claim 7, wherein the nonionic diol is selected from the group consisting of ethylene glycol (EG), propylene glycol (PG), butylene glycol (BD), hexalene glycol (HD), diethylene glycol (DEG), dipropylene glycol (DPG), neopentyl glycol (NPG) and a mixture thereof, the nonionic polyol is a nonionic polyether polyol or a nonionic polyester polyol, the nonionic polyether polyol is selected from the group consisting of polytetramethylene ether glycol (PTMEG), polyethylene glycol (PEG), polypropylene glycol (PPG) and a copolymer thereof, the nonionic polyester polyol is a polyol formed by an esterification-polymerization of a diacid and a diol, the diacid is selected from the group consisting of adipic acid (AA), sebacic acid (SA), terephthalate acid (TPA), isophthalic acid (IPA), phthalic anhydride (PA) and a mixture thereof, and the diol is selected from the group consisting of EGQ PCG BD, HD, DEG, DPG, NPG and a mixture thereof.

11. The use of claim 1, wherein the polyurethane is reactive polyurethane or thermoplastic polyurethane.

12. A composition for forming polyurethane, comprising: a monomer, an oligomer or a polymer containing at least two NCO groups; and a polymerizable ultraviolet absorber, which is obtained by reacting an UV absorber having a reactive hydrogen group with a polyisocyanate having three NCO groups.

13. The composition of claim 12, wherein a content of the polymerizable ultraviolet absorber is ranged from 1 wt % to 30 wt % based on a total weight of the composition.

14. The composition of claim 12, wherein a weight average molecular weight of the polymerizable ultraviolet absorber is less than 5,000.

15. The composition of claim 12, wherein the reactive hydrogen group as a functional group comprised in the UV absorber is selected from the group consisting of OH, NH.sub.2 and NH.

16. The composition of claim 12, wherein the UV absorber is selected from the group consisting of: a benzotriazole UV absorber, a benzophenone UV absorber, a triazine UV absorber, an oxanilide UV absorber and a cyanoacrylate UV absorber.

17. The composition of claim 12, wherein the polyisocyanate is selected from the group consisting of: HDI TRIMER, HDB or a mixture thereof.

18. The composition of claim 12, wherein the polymerizable ultraviolet absorber is obtained by reacting the UV absorber having the reactive hydrogen group with the polyisocyanate having the three NCO groups and a diol or a polyol.

19. The composition of claim 18, wherein the diol or the polyol is selected from the group consisting of an anionic diol, an anionic polyol, a cationic diol, a cationic polyol, a nonionic diol, a nonionic polyol, and a mixture thereof.

20. The composition of claim 18, wherein the anionic diol or the anionic polyol is selected from the group consisting of: DMBA, DMPA, 1,4-butanediol-2-sodium or a mixture thereof.

21. The composition of claim 18, wherein the cationic diol or the cationic polyol is selected from the group consisting of MDEA, triethanolamine or a mixture thereof.

22. The composition of claim 18, wherein the nonionic diol is selected from the group consisting of EG, PG, BD, HD, DEG, DPG, NPG and a mixture thereof, the nonionic polyol is a nonionic polyether polyol or a nonionic polyester polyol, the nonionic polyether polyol is selected from the group consisting of PTMEG PEG, PPG and a copolymer thereof, the nonionic polyester polyol is a polyol formed by an esterification-polymerization of a diacid and a diol, the diacid is selected from the group consisting of AA, SA, TPA, IPA, PA or a mixture thereof, and the diol is selected from the group consisting of EG, PG, BD, HD, DEG, DPG, NPG and a mixture thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG. 1 is a diagram showing the relation between the UVA effective amount and the anti-yellowing level when different ultraviolet absorbers were added into reactive polyurethane.

[0020] FIG. 2 is a diagram showing the relation between the UVA effective amount and the anti-yellowing level when different ultraviolet absorbers were added into thermoplastic polyurethane.

[0021] FIG. 3 is a diagram showing the relation between the UVA effective amount and the anti-yellowing level when different amounts of ultraviolet absorbers were added into thermoplastic polyurethane.

DETAILED DESCRIPTION OF THE EMBODIMENT

[0022] The following embodiments when read with the accompanying drawings are made to clearly exhibit the above-mentioned and other technical contents, features and/or effects of the present disclosure. Through the exposition by means of the specific embodiments, people would further understand the technical means and effects the present disclosure adopts to achieve the above-indicated objectives. Moreover, as the contents disclosed herein should be readily understood and can be implemented by a person skilled in the art, all equivalent changes or modifications which do not depart from the concept of the present disclosure should be encompassed by the appended claims.

[0023] Unless specified otherwise, singular words a and the used in the present specification and claims include one or plural objects.

[0024] Unless specified otherwise, term or used in the present specification and claims include meaning of and/or.

[0025] The term weight average molecular weight here is a Mw value of an object measured by using gel permeation chromatography (GPC) with tetrahydrofuran (THF) as a solvent, and using Mw value of polystyrene as a standard.

[0026] The methods of preparation are described by the following embodiments in details, and the similar methods of embodiments can be used to prepare said polymerizable ultraviolet absorber. The methods of preparing polymerizable ultraviolet absorber (such as synthetical method, reaction condition, and sequences) and the used materials are not limited to the present disclosure.

[0027] The present disclosure is explained by the following embodiments, which are not used to limit the scope of the present disclosure. Unless specified otherwise, % used herein for indicating the amount of the contents or the objects in the following embodiments are weight percentage.

##STR00002##

[0028] 620 g of -[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]--hydroxypoly(oxo-1,2-ethanediyl) (Eversorb 80 (EV80), Everlight Chemical Industrial Corporation) was placed in a flask, and water was removed using a vacuum system. After the temperature was reduced to 60 C., 504.6 g of THDI (HDI trimer, CORONA HX; TOSOH) was added into the flask, the temperature was increased to 7075 C. at a nitrogen atmosphere to perform the reaction. When the NCO groups were titrated till the end of the reaction (free NCO %=6.530.65%), the reaction was completed and Compound 1 was obtained.

##STR00003##

[0029] 620 g of EV80 and 150 g of PEG-300 (ORIENTAL UNION CHEMICAL CO.) were respectively placed into two flasks, and water was removed using a vacuum system. After the temperature was reduced to 60 C., 504.6 g of THDI (CORONA HX; TOSOH) was added into the flask containing EV80, the temperature was increased to 7075 C. at a nitrogen atmosphere to perform the reaction. When the NCO groups were titrated till free NCO % was around 6.53%, PEG-300 was further added therein to perform the reaction. When the NCO groups were titrated till the end of the reaction (free NCO %=3.760.37%), the reaction was completed and Compound 2 was obtained.

##STR00004##

[0030] 620 g of EV80 was placed in a flask, and water was removed using a vacuum system. After the temperature was reduced to 60 C., 423.4 g of Hexamethylene diisocyanate biuret (HDB-100; AN FONG) was added into the flask, the temperature was increased to 7075 C. at a nitrogen atmosphere to perform the reaction. When the NCO groups were titrated till the end of the reaction (free NCO %=6.530.65%), the reaction was completed and Compound 3 was obtained.

[0031] Preparation of Reactive Polyurethane (PUR)

[0032] 700 g of polyol including 200 g of DAHINOL P-213 (ZAND SHIN POLYMER Co.) and 500 of AR-U2010B1 (YONG SHUN CHEMICAL Co.) were mixed and placed in a flask, and water was removed using a vacuum system after mixing well. Next, 300 g ofisocyanate including 50 g of Desmodur 44M (covestro) and 250 g of TAKENATE D-110N (Mitsui Chemicals) was added therein, and the temperature was increased to 6085 C. at a nitrogen atmosphere to perform the reaction. When the NCO groups were titrated till the end of the reaction (free NCO %=3.60.4%), the reaction was completed. Finally, Compound 1, Compound 2 or Compound 3 was added therein and mixed well to obtain the product.

[0033] Herein, the obtained PUR was irradiated by UV light and analyzed with chromatic aberration analysis to evaluate the anti-yellowing effect thereof. The irradiation condition of the UV light was: UVA-340 nm, 60 C., 0.89 W/m.sup.2/nm and 20 hours. In addition, the obtained PUR was also analyzed with migration test, wherein the obtained PUR was immersed in toluene, ultra-sonication was performed thereon for 1 hour, and then UV light irradiation and chromatic aberration analysis were performed by the same method illustrated above to evaluate the anti-yellowing effect thereof.

[0034] The results of the migration test and the anti-yellowing evaluation are shown in the following Table 1 and FIG. 1. FIG. 1 shows the evaluation results of Comparative example 1-1, Comparative example 1-2 and Example 1-1 with Compound 1.

TABLE-US-00001 TABLE 1 Comparative Comparative Example Example Example Example example 1-1 example 1-2 1-1 1-2 1-3 1-4 Amount of Tinuvin 0 5 384 (wt %) Amount of Compound 0 5 20 1 (wt %) Amount of Compound 0 20 2 (wt %) Amount of Compound 0 5 3 (wt %) UVA effective amount 0 5 2.65 10.60 9.11 2.65 (%) E 22.01 2.72 1.56 0.48 0.32 0.64 Level 1 3-4 4 4-5 4-5 4-5 Migration Test E 14.16 12.36 1.62 1.33 Level 1 1 4 4

[0035] Preparation of Thermoplastic Polyurethane (TPU)

[0036] 2000 g of polyol (TERATHANE 2000 (INVISTA)) and 4.5 g of chain extender (1,4-Butanediol) were mixed and placed in a flask, 125 g of isocyanate (Desmodur 44M (covestro)) was placed in another flask, and water in these two flasks was removed using a vacuum system after mixing well. After water removing, nitrogen was introduced therein, an ice water bath was prepared, and the flasks were placed adjacent to a mixing apparatus to perform the reaction. First, the polyol and the chain extender were added. Then, Desmodur 44M was added by three times in the ice water bath, and Compound 2 was added together with Desmodur 44M in the first time and second time of adding Desmodur 44M. The sample was placed in a container to perform a post backing, and then placed in 60 C. oven overnight to obtain TPU block.

[0037] The obtained TPU block was crushed, melted, and injection molded to obtain a TPU specimen.

[0038] Herein, the UV light irradiation, chromatic aberration analysis and migration test were performed by the same method illustrated above. The results of the migration test and the anti-yellowing evaluation are shown in the following Table 2, FIG. 2 and FIG. 3. FIG. 2 shows the evaluation results of Comparative example 2-2 and Example 2-2 with Compound 2.

TABLE-US-00002 TABLE 2 Comparative Comparative Exam- Exam- Exam- example 2-1 example 2-2 ple 2-1 ple 2-2 ple 2-3 Amount of 0 5 Tinuvin 384 (wt %) Amount of 0 2 5 15 Compound 2 (wt %) UVA effective 0 5 0.91 2.28 6.84 amount (%) E 12.41 1.49 4.16 1.83 1.36 Level 1 4 2-3 4 4 Migration Test E 12.66 7.81 3.59 Level 1 2 3

[0039] In Table 1 and Table 2, the used Tinuvin 384 in Comparative examples 1-2 and 2-2 has the following structure.

##STR00005##

[0040] As shown in Table 1, Table 2 and FIGS. 1 to 3, from the results of the UV light irradiation and chromatic aberration analysis, when 5 wt % of Compound 1, Compound 2 or Compound 3 (polymerizable ultraviolet absorber) or 5 wt % of small molecular UVA (Tinuvin 384) were added into PUR or TPU, the anti-yellowing levels of PUR or TPU can be effectively increased to 3.5 or more. From the results of migration test, after immersing in a solvent and ultra-sonication, the PUR or TPU added with 5 wt %/o of Compound 1, Compound 2 or Compound 3 (polymerizable ultraviolet absorber) has anti-yellowing levels of 3 or more, but the PUR or TPU added with 5 wt % of small molecular UVA has anti-yellowing levels of 2 or less. The above results indicate that when the polymerizable ultraviolet absorber was added into PUR or TPU, the anti-yellowing of PUR or TPU can be significantly improved. In addition, the polymerizable ultraviolet absorber of the present disclosure further has low migration.

[0041] The polymerizable ultraviolet absorber of the present disclosure not only can be applied to the aforesaid PUR or TPU, and also can be used in other polyurethane, for example, polyurethane foam. In addition, the application fields of the polymerizable ultraviolet absorber of the present disclosure are not particularly limited, and can be applied to resins for coating, adhesion, sealing or elastomer or other fields using polyurethane.

[0042] Although the present disclosure has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the disclosure as hereinafter claimed.