阅读说明：本技术 一种改性紫外光稳定剂、制备方法及其应用 (Modified ultraviolet light stabilizer, preparation method and application thereof ) 是由 丁鹏 宋玉婷 于 2020-12-07 设计创作，主要内容包括：本发明公开了一种改性紫外光稳定剂,其是以HALS为基体,接枝反应性官能团构成活性基团的改性组合物功能母粒；其中的基体部分用于对废旧塑料进行光稳定作用,活性基团用于脱除或固着废旧塑料高分子发散的刺激性气味。本发明还公开该改性紫外光稳定剂的制备方法,包括以下步骤：(1)将HALS基体以摩尔比1：1溶于碱性化合物；(2)接枝含活性基团的有机溶剂；(3)将混合溶液真空过滤再进行重结晶。本发明还公开了改性紫外光稳定剂用于废旧塑料处理的应用。本发明一方面可起到光稳定作用,同时可以与废旧塑料中残存的、难以去除的挥发性小分子反应,从而降低废旧塑料的气味和VOC散发。本发明可降低废旧塑料处理成本,有利于大面积推广。(The invention discloses a modified ultraviolet light stabilizer, which is a modified composition functional master batch taking HALS as a matrix and grafting reactive functional groups to form active groups; the matrix part is used for carrying out light stabilization on the waste plastic, and the active group is used for removing or fixing pungent odor emitted by the waste plastic macromolecules. The invention also discloses a preparation method of the modified ultraviolet stabilizer, which comprises the following steps: (1) mixing a HALS matrix in a molar ratio of 1: 1 dissolving in an alkaline compound; (2) grafting an organic solvent containing active groups; (3) the mixed solution was vacuum filtered and recrystallized. The invention also discloses application of the modified ultraviolet stabilizer in waste plastic treatment. On one hand, the invention can play a role in light stabilization and can react with volatile micromolecules which are remained in the waste plastics and are difficult to remove, thereby reducing the odor and VOC emission of the waste plastics. The invention can reduce the treatment cost of waste plastics and is beneficial to large-area popularization.)

1. A modified ultraviolet light stabilizer is characterized in that HALS is used as a matrix, and reactive functional groups are grafted to form modified composition functional master batches of active groups; the matrix part is used for carrying out light stabilization on the waste plastic, and the active group is used for removing or fixing pungent odor emitted by the waste plastic macromolecules.

2. A process for preparing the modified ultraviolet light stabilizer of claim 1, comprising the steps of:

(1) mixing a HALS matrix in a molar ratio of 1: 1 dissolving in an alkaline compound to provide alkaline conditions;

(2) adding the mixture into the mixed solution in a molar ratio of 1: 1, adding a certain amount of organic solvent containing active groups, and stirring for 1h at room temperature;

(3) and (3) filtering the mixed solution in vacuum and then recrystallizing to obtain the modified ultraviolet stabilizer capable of removing the pungent smell.

3. The method of claim 2 wherein the HALS base material of step (1) is one or a combination of HALS-944 and HALS-770.

4. The method of claim 2, wherein the basic compound in step (1) comprises NaOH, Ca (OH)₂、NH₃.H₂O、Fe(OH)₃。

5. The method of claim 2, wherein the organic reagent containing a reactive group in the step (2) comprises acetic acid and methylamine.

6. The use of the modified UV stabilizer of claim 1 in waste plastic treatment, which can not only stabilize the light but also react with the volatile small molecules remaining in the waste plastic and difficult to remove, thereby reducing the odor and VOC emission of the waste plastic.

Technical Field

The invention relates to the technical field of waste plastic treatment, in particular to a preparation method of master batches with an odor removal function and light stability.

Background

The garbage in the prior art is also a resource for misplacing. The garbage is recycled and decayed into miraculous, which is scientific and artistic. Waste plastics such as polyolefin (polypropylene, polyethylene and the like) are widely applied in the fields of automobiles, household appliances, medical treatment, buildings, logistics, daily consumer goods and the like, and a large amount of waste plastic garbage is generated. In recent years, the plastic recovery and regeneration market in China develops rapidly, and the capacity and the output continue to increase rapidly. Meanwhile, as the classified recovery of the garbage becomes new and fashionable, the problems of complex components and difficult post-treatment of the urban garbage are solved to a great extent, and certain favorable conditions are provided for the recovery and reutilization of the waste plastics.

The waste plastic treatment has various technical routes, wherein the clean recycling of the plastic is one of the better ways, and the method also promotes the development of the polypropylene renewable material industry supported by national industrial policies to high-tech products and important civil fields. Therefore, the clean recycling of plastics is a 'seemingly traditional, true sun-oriented' industry.

The Chinese patent with the application number of CN03136938.3 discloses a plastic-wood-metal composite structure material and a production method thereof, wherein the plastic-wood-metal composite structure material comprises a base material, reinforcing particles, a metal component and a modifier, wherein the weight ratio of the base material to the reinforcing particles is 90: 10-40: 60. The method realizes the multi-element compounding of the thermoplastic waste plastics, the reinforced powder particles and the metal material, produces the plastic-wood-metal composite structure material with high compression resistance and high bending strength, improves the utilization degree of the thermoplastic waste plastics, is beneficial to solving the white pollution caused by the waste plastics, and has obvious environmental protection benefit.

However, in the prior art, two technical problems are not solved in the recovery and re-modification production process of waste plastics such as polyolefin, namely: at present, no appropriate solution is available for the aging-resistant technology and the odor removal technology of waste plastics.

Disclosure of Invention

The invention aims to solve the problems in the prior art, develop a modified ultraviolet stabilizer and a preparation method thereof, apply the modified ultraviolet stabilizer to waste plastic treatment, and solve the two technical problems through a material grafting modification technology and a preparation process design, so as to effectively reduce the treatment cost of the waste plastic and promote large-area popularization and application of the waste plastic.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a modified ultraviolet stabilizer is characterized in that HALS (hindered Amine Light stabilizer) is taken as a substrate, and a modified composition functional master batch with reactive functional groups formed into active groups is grafted; the matrix part is used for carrying out light stabilization on the waste plastic, and the active group is used for removing or fixing pungent odor emitted by the waste plastic macromolecules.

The preparation method of the modified ultraviolet light stabilizer is characterized by comprising the following steps:

(1) mixing a HALS matrix in a molar ratio of 1: 1 dissolving in an alkaline compound to provide alkaline conditions;

(2) adding the mixture into the mixed solution in a molar ratio of 1: 1, adding a certain amount of organic solvent containing active groups, and stirring for 1h at room temperature;

(3) and (3) filtering the mixed solution in vacuum and then recrystallizing to obtain the modified ultraviolet stabilizer capable of removing the pungent smell.

The HALS matrix material in the step (1) is one or two of HALS-944 and HALS-770.

The alkaline compound in the step (1) comprises NaOH and Ca (OH)₂、NH₃.H₂O、Fe(OH)₃。

The organic reagent containing active groups in the step (2) comprises acetic acid and methylamine.

The application of the modified ultraviolet light stabilizer is characterized in that the modified ultraviolet light stabilizer is used for treating waste plastics, and the modified ultraviolet light stabilizer can play a role in light stabilization on one hand and can react with volatile small molecules which are remained in the waste plastics and are difficult to remove, so that the odor and VOC (volatile Organic compounds) emission of the waste plastics are reduced.

The invention has the beneficial effects that:

(1) according to the modified ultraviolet stabilizer functional master batch material and the preparation method thereof, the active groups are grafted on the matrix material, so that the material has a light stability and a smell removal function, and the material which is low in cost, simple, convenient and easy to implement is provided for recycling and processing waste macromolecules.

(2) The modified ultraviolet stabilizer functional master batch material and the preparation method thereof provided by the invention have the advantages that the adopted material is low in price, the preparation process is simple, the cost of recycling waste polymers is greatly saved, and the large-scale popularization and application are facilitated.

The foregoing is a summary of the technical solutions of the present invention, and the present invention is further described below with reference to specific embodiments.

Detailed Description

Example 1

The modified ultraviolet stabilizer provided by the embodiment of the invention is a modified composition functional master batch taking HALS (hindered Amine Light stabilizer) as a matrix and grafting reactive functional groups to form active groups; the matrix part is used for carrying out light stabilization on the waste plastic, and the active group is used for removing or fixing pungent odor emitted by the waste plastic macromolecules.

A preparation method of the modified ultraviolet light stabilizer comprises the following steps:

(1) mixing HALS substrate HALS-770 in a molar ratio of 1: 1 dissolving in an alkaline compound NaOH to provide alkaline conditions;

(2) adding the mixture into the mixed solution in a molar ratio of 1: 1, adding a certain amount of organic solvent (acetic acid) containing active groups, and stirring for 1h at room temperature;

(3) and (3) filtering the mixed solution in vacuum and then recrystallizing to obtain the modified ultraviolet light stabilizer capable of removing the pungent odor, namely the carboxyl modified HALS-770.

The HALS matrix material in the step (1) is one or two of HALS-944 and HALS-770; in this example HALS-770.

The alkaline compound in the step (1) is NaOH, Ca (OH)₂、NH₃.H₂O、Fe(OH)₃In one embodiment, NaOH is used.

The organic reagent containing active groups in step (2) comprises acetic acid and methylamine, and acetic acid is used in the embodiment.

The application of the modified ultraviolet light stabilizer is used for treating waste plastics, and the modified ultraviolet light stabilizer can play a role in light stabilization and can react with volatile small molecules which are remained in the waste plastics and are difficult to remove, so that the odor and VOC (volatile Organic compounds) emission of the waste plastics are reduced.

The invention firstly researches the aging characteristics and mechanism of the polyolefin material, including the changes of microstructure, thermodynamic property, rheological property, degradation behavior and the like in the long-term use process of the polyolefin, deeply understands the source of the performance difference between the recycled plastic and the original resin and the types and sources of volatile matters, and provides support for the preparation of high-quality recycled plastic.

Aiming at the defects of low mechanical property, poor thermal stability, high volatile content and the like of the recycled plastic, the invention researches the influence of the addition of the photo-thermal stabilizer, the odor remover and the like special for the recycled plastic on the material performance and prepares the special functional master batch for the recycled plastic with ultraviolet resistance and odor reduction.

The present inventors have further developed an ultraviolet light stabilizer having a reactive functional group grafted thereto, based on the results of the aforementioned studies. The reactive functional group can be hydroxyl, carboxyl, amino, etc., and the ultraviolet Light aging agent takes HALS (hindered Amine Light stabilizer) as a matrix. The developed novel ultraviolet light aging agent can play a role in light stabilization, and can react with volatile small molecules which are remained in the waste plastics and are difficult to remove, so that the odor and VOC (volatile Organic compounds) emission of the waste plastics are reduced. Compared with the prior art, the method has the same effect, reduces the addition of the auxiliary agent, reduces the cost, and has a promoting effect on the development of the cost-sensitive waste plastic recovery industry.

Example 2

The modified uv stabilizer, the preparation method and the application thereof provided in this example are substantially the same as in example 1, except that:

the base material of the modified ultraviolet light stabilizer is HALS-944, and the alkaline condition is NH₃·H₂O, comprising the following steps:

(1) HALS-944 is added in a molar ratio of 1: 1 in NH₃·H₂O, providing alkaline conditions;

(2) adding the mixture into the mixed solution in a molar ratio of 1: 1, adding quantitative acetic acid, and stirring for 1h at room temperature;

(3) and (3) filtering the mixed solution in vacuum and then recrystallizing to obtain the modified ultraviolet light stabilizer, namely the modified carboxyl modified HALS-944 capable of removing pungent odor.

Example 3

The modified uv stabilizer, the preparation method and the application thereof provided in this example are substantially the same as in examples 1 and 2, except that:

the matrix material of the modified ultraviolet light stabilizer is HALS-770, and the organic reagent is methylamine.

The preparation method of the light stabilizer with the pungent odor removal function comprises the following steps:

(1) HALS-770 is added in a molar ratio of 1: 1 dissolving in NaOH to provide alkaline condition;

(2) adding the mixture into the mixed solution in a molar ratio of 1: 1, adding quantitative methylamine, and stirring for 1h at room temperature;

(3) and (3) filtering the mixed solution in vacuum and then recrystallizing to obtain the modified amino modified HALS-770 capable of removing the pungent odor.

Example 4

The modified UV stabilizer, the preparation method and the application thereof provided in this example are basically the same as those in examples 1, 2 and 3, except that:

the matrix material of the modified ultraviolet light stabilizer is HALS-944, and the organic reagent is methylamine.

The preparation method of the light stabilizer with the pungent odor removal function comprises the following steps:

(1) HALS-944 is added in a molar ratio of 1: 1 in NH₃.H₂O, providing alkaline conditions;

(2) adding the mixture into the mixed solution in a molar ratio of 1: 1, adding quantitative methylamine, and stirring for 1h at room temperature;

(3) and (3) filtering the mixed solution in vacuum and then recrystallizing to obtain the modified ultraviolet light stabilizer, namely the modified amino modified HALS-944 capable of removing pungent odor.

Application example 1

The modified ultraviolet stabilizer functional master batches respectively prepared in the examples 1 to 4 are put into the waste polyolefin with the same volume, and meanwhile, the modified ultraviolet stabilizer functional master batches in the examples 1 and 3, the examples 1 and 4, the examples 2 and 3, and the examples 2 and 4 are also respectively put into four parts of waste polyolefin with the same volume, and gas detection and odor evaluation are carried out on the four parts of waste polyolefin. The test data are shown in table 1 below:

as can be seen from table 1, the modified ultraviolet stabilizer functional masterbatch prepared in each example can significantly reduce the release amount of VOC and other harmful gases, compared with the prior art; the modified ultraviolet stabilizer functional master batch prepared by the two embodiments is combined to further reduce the release amount of VOC and other harmful gases.

The invention provides a functional master batch material which can remove pungent smell and prevent high polymer from photo-aging degradation aiming at the problems of photo-aging and pungent smell release frequently occurring in the recycling of waste and old high polymers and a preparation method thereof.

In the embodiments of the present invention, each specific component and the matching are not listed one by one, and in other embodiments, specific selection can be performed according to the range and the actual requirement recorded in the present invention, so that the technical effects recorded in the present invention can be achieved.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.