阅读说明：本技术 紫外线吸收化合物及其应用 (Ultraviolet absorbing compounds and uses thereof ) 是由 曲清蕃 张玮骏 吴皇旻 黄怡硕 于 2019-05-16 设计创作，主要内容包括：本发明提供一种紫外线吸收化合物及其应用,其中该化合物具下式I的结构：[式I]<Image he="222" wi="700" file="DDA0002061286890000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>于式I中,R各自独立为H、C<Sub>1</Sub>-C<Sub>20</Sub>烷基、缩水甘油醚基或-(CH<Sub>2</Sub>CH<Sub>2</Sub>O)<Sub>m</Sub>-(CH<Sub>2</Sub>)<Sub>p</Sub>-CH<Sub>3</Sub>,m为1至20的整数,p为0至20的整数,且n为0至3的整数。(The invention provides an ultraviolet absorbing compound and application thereof, wherein the compound has a structure shown in the following formula I: [ formula I ]] In formula I, R is each independently H, C 1 ‑C 20 Alkyl, glycidyl ether or- (CH) 2 CH 2 O) m ‑(CH 2 ) p ‑CH 3 M is an integer of 1 to 20, p is an integer of 0 to 20, and n is an integer of 0 to 3.)

1. An ultraviolet absorbing compound having the structure of formula I:

[ formula I ]

In formula I, R is each independently C₁-C₆Alkyl or- (CH)₂CH₂O)_m-(CH₂)_p-CH₃Wherein m is an integer of 1 to 6, p is an integer of 0 to 6, and n is 2 or 3.

2. The compound of claim 1, wherein each R is independently C₁-C₆Alkyl, and n is 2.

3. The compound of claim 2, having the structure of formula Ia or Ib:

[ formula Ia ]

[ formula Ib ]

4. A compound according to any one of claims 1 to 3 for use as a uv absorber.

5. A uv-resistant material comprising a base material and a compound according to any one of claims 1 to 3 as a first uv absorber.

6. The UV-resistant material of claim 5, further comprising a second UV-absorber selected from the group consisting of: benzotriazoles, benzoxazinones, triazines, and combinations thereof.

7. The UV-resistant material of claim 5 or 6, wherein the base material is a polymer material.

8. The UV resistant material of claim 7, wherein the base material is a polymeric material selected from the group consisting of: polyethylene terephthalate, polycarbonate, polypropylene, polyethylene, polyamide, and combinations thereof.

9. The UV-resistant material of claim 5 or 6, further comprising a component selected from the group consisting of: antioxidants, antistatic agents, hydrolysis resistance agents, toughening agents, colorants, fillers, flame retardants, and combinations thereof.

Technical Field

The invention relates to a light-colored ultraviolet-absorbable compound with excellent thermal stability and application thereof, and particularly relates to the technical field with ultraviolet resistance requirements such as but not limited to sunscreen products, plastic materials, rubber materials, coatings, dyes and the like.

Background

Ultraviolet absorbers are widely used to absorb ultraviolet light (UV) that is harmful in sunlight and easily causes degradation of materials such as polymers. Common commercially available uv absorber products are mainly Benzotriazoles (benzotriazines), Benzophenones (Benzophenones) and Triazines (Triazines). However, these ultraviolet absorbers are generally used to absorb ultraviolet rays mainly in the wavelength range of 260 to 360 nm, and cannot effectively absorb ultraviolet rays in the wavelength range of 350 to 400 nm (i.e., UV-a wavelength range). Therefore, articles using these ultraviolet absorbers, such as transparent plastic containers for holding food or medicine, are still gradually degraded by the ultraviolet rays in the near visible wavelength range of 350 to 400 nm. Although there are complex structures of triazines and benzotriazoles that absorb UV light up to 400 nm, their cost and other factors greatly limit their application.

U.S. Pat. No. 3,989,698 describes a UV absorber (corresponding to Cyasorb UV-3638) which is also a benzoxazinone (benzoxazinone) and can be added to a container made of a plastic such as polyethylene terephthalate (PET) or Polycarbonate (PC) to block the penetration of UV rays below 370 nm and protect UV-sensitive components in the container. However, because of the many nutrients and natural dyes that are still sensitive to UV radiation at 370-400 nm, there is a need for UV absorbers that can absorb UV radiation at 400 nm and even 420 nm.

U.S. Pat. No. 4,617,374 describes a Methine (Methine) -containing compound having the structure:

the compound can be used as a chain terminator to react on polyester and polycarbonate polymers and endow the polymers with the function of shielding ultraviolet rays. However, the compound can shield ultraviolet rays only at 320 to 380 nm, and still cannot cover all near visible light band ultraviolet rays at 350 to 400 nm.

US 6,596,795B 2 also describes a vanillin-modified UV absorber (corresponding commercial product: Clearshield 390) having the formula:

in the above formula, a is a polyether polyol group. Although the UV absorber has a UV absorption range of 320-400 nm. However, the UV absorbers are liquid, have a dark initial color and poor thermal stability, and are therefore unsuitable for product applications requiring high color or high processing temperatures. In addition, the structure of the ultraviolet absorbent is modified with polyether polyol groups with large molecular weight, which inevitably reduces the ultraviolet absorption effect of the ultraviolet absorbent per unit weight, so that the dosage of the ultraviolet absorbent must be increased to achieve the desired protection effect, resulting in an increase in product cost.

WO 2010/056452 a2 further improves the uv absorbers described in US 6,596,795B 2, and proposes uv absorbers (1) and (2) having the following structures:

(1)

and

(2)

the UV absorber (1) is an ester-linked dimer, and the UV absorber (2) is an ether-linked dimer, which covers a UV absorption range of 320-400 nm. However, the blending test of these UV absorbers with polypropylene (PP) revealed that the overall test piece still exhibited a yellowish color, which was even more severe than the addition of the same amount of Clearshield 390, indicating that although the UV absorbers (1) and (2) increased the molecular weight by means of a dimer, the thermal stability exhibited still did not reach a satisfactory level.

Disclosure of Invention

In view of the above-mentioned technical problems faced by the conventional uv absorbers, the present invention provides a uv absorbing compound which is a light yellow solid at normal temperature and pressure, and has the advantages of reducing color, improving purity and improving compatibility of plastic film applications by crystallization purification compared to a liquid uv absorber. The ultraviolet absorbing compound can be used as an ultraviolet absorber, and the ultraviolet absorption range can cover the UV-A wave band of 320-400 nm. In addition, the ultraviolet absorbing compound can be applied to engineering plastics (such as PET, PC, Polyamide (PA) and the like) with high processing temperature due to excellent thermal stability, and can further unexpectedly improve the thermal yellowing condition after the plastics are processed. Accordingly, the present invention is directed to at least the objects of the invention described below.

It is an object of the present invention to provide an ultraviolet absorbing compound having the structure of formula I:

[ formula I ]

In formula I, R may each independently be H, C₁-C₂₀Alkyl, glycidyl ether or- (CH)₂CH₂O)_m-(CH₂)_p-CH₃Wherein m may be an integer of 1 to 20, p may be an integer of 0 to 20, and n is an integer of 0 to 3. More particularly, R may each independently be C₁-C₆Alkyl or- (CH)₂CH₂O)_m-(CH₂)_p-CH₃Wherein m may be an integer of 1 to 6, p may be an integer of 0 to 6, and n is 2 or 3.

In some embodiments of the invention, each R is independently C₁-C₆Alkyl, and n is 2.

In some embodiments of the invention, the UV absorbing compound has the structure of formula Ia or Ib:

[ formula Ia ]

And [ formula Ib ]

Another object of the present invention relates to the use of the aforementioned uv-absorbing compounds as uv-absorbers.

It is still another object of the present invention to provide a UV-resistant material, which comprises a base material and the above-mentioned UV-absorbing compound, wherein the UV-absorbing compound is used as a first UV-absorber.

In some embodiments of the present invention, the uv-resistant material may further comprise a second uv absorber selected from the group consisting of: benzotriazoles (Benzotriazoles), benzoxazinones (benzoxazinones), Triazines (Triazines), and combinations thereof.

In some embodiments of the present invention, the base material in the uv-resistant material is a polymer material, such as a polymer material selected from the group consisting of: polyethylene terephthalate, polycarbonate, polypropylene, Polyethylene (PE), polyamide, and combinations thereof.

In some embodiments of the present invention, the uv-resistant material may further comprise a component selected from the group consisting of: antioxidants, antistatic agents, hydrolysis resistance agents, toughening agents, colorants, fillers, flame retardants, and combinations thereof.

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, some embodiments accompanied with figures are described in detail below.

Drawings

Fig. 1 shows a photograph comparing the appearance of the ultraviolet absorbing compound Ia according to the present invention with that of clearshird 390 after heating at a temperature of 240 ℃ for 10 minutes.

Detailed Description

Some specific embodiments according to the present invention will be specifically described below; the invention may, however, be embodied in many different forms without departing from the spirit thereof, and the scope of the invention should not be construed as limited to the specific embodiments set forth herein.

As used in this specification and the appended claims, unless otherwise indicated, the singular forms "a", "an", and "the" include plural referents.

Unless otherwise indicated, the terms "first," "second," and the like, as used herein (and in the claims) are used solely to distinguish one element or component from another as described and are not necessarily meant to imply a sequence or order.

Unless otherwise indicated, in the present specification (especially in the claims), the alkyl group includes various alkyl groups having a structure of linear, branched, cyclic, or a combination thereof. In the present specification, the carbon-carbon double bond configuration described is selected for convenience of description only and is not intended to be limited to a specific configuration. Thus, configurations of carbon-carbon double bonds shown as (Z) type are intended to encompass (Z) type, (E) type, or combinations thereof.

Ultraviolet absorbing compounds

The ultraviolet absorbing compounds of the present invention have the structure shown in formula I below:

[ formula I ]

In formula I, R is each independently H, C₁-C₂₀Alkyl, glycidyl ether or- (CH)₂CH₂O)_m-(CH₂)_p-CH₃Wherein m is an integer of 1 to 20, p is an integer of 0 to 20, and n is an integer of 0 to 3. In terms of the thermal stability of the ultraviolet absorbing compound and the ultraviolet absorbing effect provided by the unit ultraviolet absorbing compound, R is preferably each independently C₁-C₂₀Alkyl, more preferably C₁-C₆An alkyl group.

In some embodiments of the invention, each R is independently C₁-C₆Alkyl or- (CH)₂CH₂O)_m-(CH₂)_p-CH₃Wherein m is an integer of 1 to 6,p is an integer of 0 to 6, and n in formula I is 2 or 3. In a specific embodiment of the following examples, the ultraviolet light absorbing compound has the structure of formula Ia or Ib:

[ formula Ia ]

And

[ formula Ib ]

The synthesis of the UV-absorbing compounds of the present invention will be described in detail in the following examples, which are not repeated herein.

Use of UV-absorbing compounds

The ultraviolet absorbing compound of the present invention has an ability to absorb ultraviolet rays, can be used as an ultraviolet absorber to improve the ability of an applied material to withstand ultraviolet rays, and can be used alone or in combination with other ultraviolet absorbers. Therefore, the ultraviolet absorbing compound of the present invention can be applied to the technical field with ultraviolet resistance requirement, including but not limited to sunscreen products, plastic materials, rubber materials, paints, dyes, etc.

In some embodiments of the present invention, there is provided a uv resistant material comprising a base material, a compound of formula I as described above as a first uv absorber, and optionally a second uv absorber.

The base material is not particularly limited, and may be, for example, a general polymer material including polyethylene terephthalate (PET), Polycarbonate (PC), polypropylene (PP), Polyethylene (PE), Polyamide (PA), and the like. The use of polyethylene terephthalate is exemplified in the examples that follow.

The kind of the second ultraviolet absorber is not particularly limited, and those skilled in the art can select the second ultraviolet absorber according to the needs. For example, the second UV absorber may include, but is not limited to, Benzotriazoles (Benzotriazoles), benzoxazinones (Benzoxazinones), Triazines (Triazines), and combinations of the foregoing.

In the uv-resistant material of the present invention, the amount of the first uv-absorber and the optional second uv-absorber is not limited in principle, and can be adjusted by one of ordinary skill in the art according to the knowledge and the description of the present specification, for example, according to the degree of uv resistance, cost, and other factors. For general applications, the first uv absorber may be present in an amount of 0.01 wt% to 5 wt%, such as 0.05 wt%, 0.1 wt%, 0.15 wt%, based on the total weight of the base material and the first uv absorber, for example, using the first uv absorber alone. In some embodiments of the present invention, the first uv absorber is present in an amount of 0.075 to 0.5 wt%, based on the total weight of the base material and the first uv absorber.

In the ultraviolet ray-resistant material of the present invention, the first ultraviolet ray absorber and, if necessary, the second ultraviolet ray absorber may be added to the base material in any manner as long as the purpose of imparting the ultraviolet ray-resistant ability to the base material can be achieved. For example, the light-receiving surface of the base material may be coated with the first ultraviolet absorber and the optional second ultraviolet absorber directly or through a medium, or the first ultraviolet absorber and the optional second ultraviolet absorber may be mixed between molecules of the base material. For example, if the base material is a polymer material, the base material can be mixed and processed in a mixer together with the first ultraviolet absorber and optionally the second ultraviolet absorber to obtain the ultraviolet-resistant material of the present invention. With respect to the specific addition manner of the first ultraviolet absorber and the optional second ultraviolet absorber, after those skilled in the art of the present invention understand the content of the present specification, particularly after the following specific examples are illustrated, the present invention can be implemented based on the known knowledge, and further details are not described herein.

The uv-resistant material of the present invention may optionally further comprise one or more additives to improve the physicochemical properties of the base material. Examples of such additives include, but are not limited to, antioxidants, antistatic agents, hydrolysis resistance agents, toughening agents, colorants, fillers, and flame retardants. The selection, addition mode and amount of the additive are the ordinary techniques known to those skilled in the art, and are not the technical focus of the present invention, and thus are not described herein.

The invention will now be further illustrated by the following specific embodiments.