阅读说明：本技术 一种含有受阻胺的液体紫外吸收剂及制备方法 (Hindered amine-containing liquid ultraviolet absorbent and preparation method thereof ) 是由 刘辉 丁录元 蔡智奇 于 2020-12-31 设计创作，主要内容包括：本发明提供了一种含有受阻胺的液体紫外吸收剂及制备方法；本发明步骤包括：步骤1,向反应器内加入UV-3、四甲基哌啶醇烷基化物和溶剂；步骤2,升温至120℃,加入催化剂,保温反应,分出反应生成的乙醇,反应时间10h；步骤3,降温至80℃,向反应器中加入溶剂,水,搅拌1h静置分液,将上层有机相负压浓缩至不出流,放料,得到无色透明液体。本发明克服了现有工艺中固体紫外吸收剂和光稳定剂需要助溶剂高温溶解并搅拌均匀才能添加到聚合物中的缺点；本发明制备得到的产品具有良好的光稳定性、热稳定性和高效的光吸收性,使得添加量减少,大大降低了生产成本。本发明方法简单,重复率高,安全。(The invention provides a liquid ultraviolet absorbent containing hindered amine and a preparation method thereof; the method comprises the following steps: step 1, adding UV-3, tetramethyl piperidinol alkylate and a solvent into a reactor; step 2, heating to 120 ℃, adding a catalyst, carrying out heat preservation reaction, separating out ethanol generated by the reaction, and reacting for 10 hours; and 3, cooling to 80 ℃, adding the solvent and water into the reactor, stirring for 1h, standing for liquid separation, concentrating the upper organic phase under negative pressure until no flow exists, and discharging to obtain colorless transparent liquid. The invention overcomes the defect that the solid ultraviolet absorbent and the light stabilizer can be added into the polymer only by dissolving the cosolvent at high temperature and stirring uniformly in the prior art; the product prepared by the invention has good light stability, thermal stability and high-efficiency light absorptivity, so that the addition amount is reduced, and the production cost is greatly reduced. The method is simple, high in repetition rate and safe.)

1. A liquid uv absorber containing a hindered amine characterized by: the structural formula (1) is as follows:

in the formula (1), R is C1-C13 alkane.

2. A method for preparing a hindered amine-containing liquid uv absorber according to claim 1, comprising the steps of: and (3) putting the ultraviolet absorbent uv-3, the tetramethyl piperidinol alkylate and the catalyst into a reaction kettle, carrying out heat preservation reaction, washing and separating liquid, and concentrating the solvent to obtain the product.

3. The method for preparing a hindered amine-containing liquid ultraviolet absorber according to claim 2, comprising the specific steps of:

step 1, adding uv-3, a tetramethyl piperidinol alkylate and a solvent 1 into a reactor, wherein the molar ratio of uv-3 absorbent to the tetramethyl piperidinol alkylate is 1:0.55, and the mass ratio of the solvent amount to the uv-3 absorbent is 1: 1;

step 2, heating to 120 ℃, separating out water in the system, adding a catalyst, keeping the mass ratio of the catalyst to UV absorbent uv-3 at 1:1000, reacting at a constant temperature, separating out ethanol generated by the reaction, and reacting for 10 hours;

and 3, cooling to 80 ℃, adding a solvent 2 with the mass one time of uv-3 and water with the mass one time of uv-3 into the reactor, stirring for 1h, standing, separating liquid, concentrating the upper organic phase under negative pressure until no flow flows out, and discharging to obtain colorless transparent liquid.

4. The method for preparing a hindered amine-containing liquid uv absorber according to claim 2, wherein the solvent 1 is one or more of toluene, xylene, cyclohexane and methylcyclohexane; the solvent 2 is one or a mixture of toluene, xylene, cyclohexane and methylcyclohexane.

5. The method of claim 2 wherein the catalyst is one or more of methane sulfonic acid, zinc chloride, and tetraisopropyl titanate.

Technical Field

The invention belongs to the field of chemical industry; in particular to a liquid ultraviolet absorbent containing hindered amine and a preparation method thereof.

Background

Solid uv absorbers and hindered amines have long been used to protect polymers from uv light. When the solid ultraviolet absorbent and hindered amine are used, the solid ultraviolet absorbent and hindered amine must be dissolved by a high-boiling-point organic solvent and a cosolvent, stirred uniformly and dispersed in gelatin solution before being added into the polymer, so that the operation is inconvenient and the defects are numerous.

Disclosure of Invention

The invention aims to provide a liquid ultraviolet absorbent containing hindered amine and a preparation method thereof.

The invention is realized by the following technical scheme:

in a first aspect, the present invention is directed to a liquid UV absorber containing a hindered amine, formula (1) as follows:

in the formula (1), R is C1-C13 alkane.

In a second aspect, the present invention also relates to a method for preparing the liquid ultraviolet absorbent containing hindered amine, which comprises the following steps: and (3) putting the ultraviolet absorbent uv-3, pentamethylpiperidinol and the catalyst into a reaction kettle, carrying out heat preservation reaction, washing and separating liquid, and concentrating the solvent to obtain the product.

Preferably, the method comprises the following specific steps:

step 1, adding uv-3, a tetramethyl piperidinol alkylate and a solvent 1 into a reactor, wherein the molar ratio of uv-3 absorbent to the tetramethyl piperidinol alkylate is 1:0.55, and the mass ratio of the solvent amount to the uv-3 absorbent is 1: 1;

step 2, heating to 120 ℃, separating water in the system by using a water separator, adding a catalyst after water separation is finished, keeping the mass ratio of the catalyst amount to uv-3 of the ultraviolet absorbent at 1:1000, reacting at a constant temperature, continuously separating ethanol generated by the reaction, and reacting for 10 hours;

and 3, cooling to 80 ℃, adding a solvent 2 with the mass one time that of uv-3 into the reactor, adding water with the mass one time that of uv-3, stirring for 1h, standing, separating liquid, concentrating the upper organic phase under negative pressure until no flow flows out, discharging, and obtaining colorless transparent liquid.

Preferably, the solvent 1 is one or more of toluene, xylene, cyclohexane and methylcyclohexane, and the solvent 2 is one or more of toluene, xylene, cyclohexane and methylcyclohexane.

Preferably, the catalyst is one or more of methane sulfonic acid, zinc chloride and tetraisopropyl titanate.

The reaction formula of the invention is as follows:

the invention has the following advantages:

(1) the invention overcomes the defect that the solid ultraviolet absorbent and the light stabilizer can be added into the polymer only by dissolving the cosolvent at high temperature and stirring uniformly in the prior art;

(2) the product prepared by the invention has good light stability, thermal stability and high-efficiency light absorptivity, so that the addition amount is reduced, and the production cost is greatly reduced.

(3) The method is simple, high in repetition rate and safe.

Detailed Description

The present invention will be described in detail with reference to specific examples. It should be noted that the following examples are only illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

The embodiment relates to a preparation method of a liquid ultraviolet absorbent containing hindered amine, which comprises the following steps: placing ultraviolet absorbent uv-3, pentamethylpiperidinol and a catalyst into a reaction kettle, carrying out heat preservation reaction, washing and separating liquid, and concentrating a solvent to obtain a product; the method comprises the following specific steps:

adding 100g (0.23mol) of uv-3, 83.51g (0.48mol) of pentamethylpiperidinol and 100g of toluene into a reactor with a water separator, a condenser tube and a stirrer, heating to 120 ℃, separating water in raw materials by using the water separator, adding 0.1g of tetraisopropyl titanate after water separation is finished, continuously separating ethanol generated by reaction, cooling to 80 ℃ after 10 hours of reaction, adding 100ml of toluene and 100ml of water, stirring for 1 hour, standing for liquid separation, concentrating organic phase under reduced pressure until no flow is generated, obtaining colorless transparent uv-3N, wherein the weight is 134.50g, and the yield is 85.00%.

The hindered amine-containing liquid UV absorber prepared in this example has the following structural formula (1):

in the formula (1), R is C1 alkane.

Example 2

The embodiment relates to a preparation method of a liquid ultraviolet absorbent containing hindered amine, which comprises the following steps: placing ultraviolet absorbent uv-3, pentamethylpiperidinol and a catalyst into a reaction kettle, carrying out heat preservation reaction, washing and separating liquid, and concentrating a solvent to obtain a product; the method comprises the following specific steps:

adding 100g (0.23mol) of uv-3, 83.51g (0.48mol) of pentamethylpiperidinol and 100g of toluene into a reactor with a water separator, a condenser tube and a stirrer, heating to 120 ℃, separating water in raw materials by using the water separator, adding 0.1g of zinc chloride after water separation is finished, continuously separating ethanol generated by reaction, cooling to 80 ℃ after 10 hours of reaction, adding 100ml of toluene and 100ml of water, stirring for 1 hour, standing for liquid separation, and concentrating organic phase under reduced pressure until no flow is generated to obtain colorless transparent uv-3N, wherein the weight is 139.10g, and the yield is 88.00%.

The raw material information used is shown in table 1 below:

TABLE 1

Raw materials	Manufacturer of the product	Production batch number
			UV-3	Hengjing of Hubei chemical Co., Ltd	20201015
Pentamethylpiperidinol	Hubei Jusheng science and technology Co., Ltd	20200910
			Tetra-isopropyl titanate	Jinan Shuangying chemical Co Ltd	20200915
Toluene	SINOPHARM CHEMICAL REAGENT Co.,Ltd.	20201020
			Zinc chloride	Henan Raent Biotech Ltd	20200815

The hindered amine-containing liquid UV absorber prepared in this example has the following structural formula (1):

in the formula (1), R is C1 alkane.

The raw material uv-3 related to the embodiment of the invention is N, N' -bis (4-ethoxyformylphenyl) -N-benzylformamidine;

and (3) application performance testing: aging test

The UV aging sample comparison test was carried out on the UV aging sample prepared in example 1 and example 2 by compounding UV-3N, the product prepared in the method of the invention, UV absorber uv-3 and light stabilizer 292 (the light stabilizer 292 is a mixture of (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate and 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate), the dosage is 0.5 percent of polyurethane, the radiation degree is 0.76W/(m2 nm) @340nm, the illumination period is 24h, 60 ℃, the test standard is ISO4892-3, the aging time of the test Yellowness Index (YI) > 3, and the test results are shown in Table 2:

TABLE 2

Ultraviolet absorber	Yellowness index of sample yellowing time
		Is free of	3h
uv-3 and light stabilizer 292 are compounded	10h
		uv-3N	24h

As shown by the data in Table 2, it can be understood that uv-3 prepared by the method of the invention alone has a far better light stabilizing effect than a product compounded by uv-3 and a light stabilizer 292.

Compared with the prior art, the invention overcomes the defect that the solid ultraviolet absorbent and the light stabilizer can be added into the polymer only by dissolving the cosolvent at high temperature and stirring uniformly in the prior art; the product prepared by the invention has good light stability, thermal stability and high-efficiency light absorptivity, so that the addition amount is reduced, and the production cost is greatly reduced. The method is simple, high in repetition rate and safe.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.