阅读说明：本技术 一种受阻胺光稳定剂的制备及应用 (Preparation and application of hindered amine light stabilizer ) 是由 李�杰 夏飞 于 2021-10-12 设计创作，主要内容包括：一种受阻胺光稳定剂的制备方法及应用,具体工艺为由己二酸二甲酯与2,2,6,6-四甲基哌啶醇经酯交换反应制备的己二酸二(2,2,6,6-四甲基哌啶基)酯。将本发明的产物与光稳定剂770分别以一定比例加入聚烯烃中制成不同样品,经光老化加速实验,本发明产物的抗紫外光老化效果优于传统受阻胺光稳定剂770,使其在相关领域具有更好的竞争力。本发明的合成工艺无水洗过程,属环境友好型合成方法,具有良好的工业化生产发展前景。(A hindered amine light stabilizer is prepared by the ester exchange reaction of dimethyl adipate and 2,2,6, 6-tetramethyl piperidinol to prepare bis (2, 2,6, 6-tetramethyl piperidyl) adipate. The product and the light stabilizer 770 are respectively added into polyolefin according to a certain proportion to prepare different samples, and through a photoaging acceleration experiment, the ultraviolet light aging resistant effect of the product is superior to that of the traditional hindered amine light stabilizer 770, so that the product has better competitiveness in related fields. The synthesis process of the invention has no water washing process, belongs to an environment-friendly synthesis method, and has good industrial production development prospect.)

1. A process for preparing a hindered amine light stabilizer characterized in that the process comprises reacting (a) an alkyl-substituted-4-hydroxypiperidine having the formula

With (b) a dicarboxylic acid ester of the formula

Wherein R is H, CH₃、OC₈H₁₇Any one of (1), R^’Is C₁-C₄N is an integer of 1 to 4; the hindered amine light stabilizer is generated by reaction in the presence of a transition metal transesterification catalyst, and the reaction process is not washed by water.

2. The method of claim 1, wherein the alkyl-substituted-4-hydroxypiperidine (a) is 2,2,6, 6-tetramethyl-4-hydroxypiperidine and the dicarboxylic acid ester (b) is one or more esters derived from malonic acid, succinic acid, glutaric acid, or adipic acid.

3. The method of preparing a hindered amine light stabilizer of claim 1 wherein said hindered amine light stabilizer is bis (2, 2,6, 6-tetramethyl-4-piperidinyl) adipate.

4. The method of claim 1, wherein the transition metal transesterification catalyst is a phthalate catalyst, and the phthalate catalyst is one or more of titanium 2-ethyl-1-hexanoate, tetra-n-propyl titanate, polybutyl titanate, titanium amine lactate chelate, and titanium tetra-2-ethyl-1, 3-hexanediol.

5. The method for producing a hindered amine light stabilizer according to claim 4, wherein said alkyl-substituted-4-hydroxypiperidine is mixed with said dicarboxylic acid ester, and the resulting mixture is reacted with heating; firstly heating to 110-120 ℃, then adding the transition metal transesterification catalyst, and continuously heating to 145-160 ℃ for reaction; and continuously bubbling with inert gas under normal pressure, wherein the inert gas is nitrogen or argon.

6. The method of claim 4, wherein the amount of the phthalate ester catalyst is 0.7 to 1.5 mol% per mol of the dicarboxylate, and the molar ratio of the alkyl-substituted-4-hydroxypiperidine to the dicarboxylate is 2 to 2.5: 1.

7. the application of a hindered amine light stabilizer, in particular to the application of the hindered amine light stabilizer in polyolefin resin; wherein the hindered amine light stabilizer is prepared according to any one of claims 1 to 6.

8. The use of a hindered amine light stabilizer according to claim 7 wherein the hindered amine light stabilizer is present in the polypropylene resin or the polyethylene resin in an amount of from 0.1% to 1.5% by weight.

9. The use of a hindered amine light stabilizer according to claim 7, wherein the weight fraction of said hindered amine light stabilizer in the polypropylene resin masterbatch is 20-50%.

10. The use according to claim 7 of a hindered amine light stabilizer, wherein the weight fraction of said hindered amine light stabilizer in the ABS resin is from 0.3% to 5.0%.

Technical Field

The invention relates to the technical field of light stabilizers, and particularly relates to preparation and application of a hindered amine light stabilizer.

Background

Hindered Amine Light Stabilizers (HALS) have become the mainstream products in the light stabilizer consumer market in polyolefin synthetic material auxiliaries due to their superior performance, and dominate the consumer structure in the world light stabilizer market. With the continuous and intensive basic research and application research of light stabilizers, the application range of HALS is expanding, and the HALS covers a plurality of fields such as agricultural films, engineering plastics, fibers, polymer coatings, artificial carpets, and outdoor various plastic products.

A common hindered amine light stabilizer product is Tinuvin 770, which still occupies an important position in the non-polymeric light stabilizer market consumer structure. The invention patent CN1066064A describes a method for synthesizing a hindered amine light stabilizer Tinuvin 770, which greatly improves the speed and conversion rate of ester exchange reaction by a catalyst system consisting of lithium amide and an aprotic polar organic compound. However, after the reaction is finished, the lithium amide must be neutralized and removed by acetic acid, otherwise, the residual lithium amide can influence the quality of the hindered amine light stabilizer.

In addition, the invention patent CN103319398A discloses a preparation method of a hindered amine light stabilizer, which comprises the steps of reacting alkyl-substituted-4-hydroxypiperidine and dicarboxylic acid in solvent oil, and then separating a solvent, washing with water and removing impurities with activated carbon to obtain a product; CN102382039A discloses a synthesis process of a hindered amine light stabilizer Tinuvin-770, namely, tetramethylpiperidinol, sebacic acid, a catalyst and a solvent are mixed and reacted, and a product is obtained through multiple times of water washing. After the synthesis reaction of the hindered amine light stabilizer Tinuvin 770 is completed, a large amount of water washing process is usually adopted to remove reaction impurities and catalysts and improve the product purity. A large amount of waste water discharge can cause the environmental pollution problem, even discharge after waste water reaches standard through environmental protection processing, also can cause the waste of water resource, and waste water treatment also can increase the cost simultaneously.

In order to obtain better reaction speed and conversion rate, and simultaneously reduce the use of water or reaction solvent in the reaction, a proper catalyst and process are selected to solve the problems.

Disclosure of Invention

The invention provides a method for preparing hindered amine light stabilizer, which adopts the technical scheme that:

alkyl-substituted-4-hydroxypiperidine (a) having the following general formula

With (b) a dicarboxylic acid ester of the formula

Wherein R is^’Is C₁-C₄And n is an integer of 1 to 4; the reaction is carried out in the presence of a transesterification catalyst containing a transition metal, the molar ratio of the alkyl-substituted-4-hydroxypiperidine to the dicarboxylic acid ester used being 2-2.5: 1.

Preferably, the alkyl-substituted 4-hydroxypiperidine compound is 2,2,6, 6-tetramethyl-4-hydroxypiperidine.

Suitable dicarboxylic acid esters for use in the present invention are esters derived from malonic acid, succinic acid, glutaric acid or adipic acid;

the transition metal transesterification catalyst suitable for the present invention is any one or more of titanium 2-ethyl-1-hexanoate, tetra-n-propyl titanate, polybutyl titanate, titanium ammonium lactate chelate, and tetra (2-ethyl-1, 3-hexanediol) titanium.

The reaction comprises the following specific steps: mixing the 2,2,6, 6-tetramethyl-4-hydroxypiperidine with the dicarboxylic ester, heating the obtained mixture to 110-120 ℃, adding a phthalate ester transesterification catalyst, continuously heating to 145-160 ℃ for reaction, and continuously bubbling with an inert gas under normal pressure or under vacuum.

Further, the amount of the phthalate ester catalyst is 0.7 to 1.5 mol% per mol of the dicarboxylic acid ester.

The hindered amine light stabilizer is bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate.

Preferably, the transition metal transesterification catalyst is a combination of titanium 2-ethyl-1-hexanoate and titanium tetrakis (2-ethyl-1, 3-hexanediol).

Further, the dicarboxylic acid ester is adipate or dimethyl adipate.

Further, the process removes by-products by inert gas or vacuum.

Further, the inert gas is nitrogen or argon.

Further, when bubbling with an inert gas (e.g., nitrogen) is carried out at normal pressure, the rate is 0.2 to 1 liter/minute.

Further, the reactants are typically stirred at a speed of 350rpm to about 800rpm at laboratory scale.

Further, the use of the hindered amine light stabilizer in a polyolefin resin; wherein the weight percentage of the residual catalyst generated by water washing is 0.05-0.2% in the hindered amine light stabilizer.

Further, the weight percentage of the prepared hindered amine light stabilizer in polypropylene resin or polyethylene resin is 0.1-1.5%.

Further, the weight percentage of the prepared hindered amine light stabilizer in the polypropylene resin master batch is 20-50%.

Further, the weight fraction of the prepared hindered amine light stabilizer in the ABS resin is 0.3-5.0%.

All parts and percentages are by weight unless otherwise indicated.

Principle of

The polymer material loses hydrogen atoms under the combined action of light and oxygen in nature, then reacts with oxygen atoms to generate carbonyl, and the carbonyl is further converted into carboxyl to generate carboxylic acid. The formation of carboxylic acids reduces the activity of the hindered amine light stabilizer.

In the ester exchange reaction, lithium amide is a new species with better catalytic effect in the existing ester exchange catalyst, but the stability of the lithium amide is poor, and ammonia gas is easily decomposed. LiNH₂+H₂O→LiOH+NH₃The use of the stabilizer is affected if the catalyst remains in the stabilizer and is not removed. Therefore, in general, acetic acid is added after the completion of the transesterification reaction to convert the catalyst into lithium acetate and ammonium acetate, and these two products are dissolved in water and removed.

After the synthesis reaction of the titanate catalyst is finished, a small amount of the catalyst can be remained in the auxiliary product without washing. An auxiliary containing a small amount of a catalyst is added to the polyolefin resin. In the aging process of the auxiliary agent, water molecules in nature promote titanate to be slowly decomposed into alpha-titanic acid, the molecular formula of the alpha-titanic acid is Ti (OH)4, and a large number of hydroxyl groups are contained in the molecules, so that the alpha-titanic acid is relatively strong in alkalinity. Alpha-titanic acid formed by a small amount of titanate in the light stabilizer neutralizes partial carboxylic acid generated by polymer degradation, so that the functional group of the hindered amine light stabilizer keeps higher activity than that of the hindered amine light stabilizer without titanate for a longer time, and the lithium amide does not have the application effect of the titanate catalyst.

The catalyst used in the reaction, such as 2-ethyl-1-titanium hexanoate and the like, is liquid at normal temperature, so that the separation of the target product bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate can be realized by cooling crystallization; the absence of water washing of the product leaves a small amount of phthalate catalyst in the crystallized solid product; but the phthalate ester catalyst has less dosage and less residual quantity, which does not affect the appearance and the product performance of the polyolefin product added with the bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate and can simultaneously ensure that the polyolefin product obtains better anti-aging performance. The amount of the phthalate ester catalyst used in the invention is 0.7-1.5% (mol)/per mol of the dicarboxylic acid ester, so that the content of the residual catalyst in the prepared bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate product is 0.05-0.2%, the cleaning treatment process of the residual catalyst can be omitted, and the polyolefin product added with the prepared bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate can obtain certain anti-aging performance.

Technical effects

The phthalate combination catalyst system used in the present invention may be effective in increasing the transesterification reaction rate. Meanwhile, trace residue of the catalyst in the auxiliary agent in the composition can also contribute to improving the ultraviolet light aging resistance of the hindered amine light stabilizer. The process of the invention does not need water washing, which can ensure that a small amount of catalyst remains and can ensure that no water is consumed in the process, thereby greatly reducing the synthesis cost of the hindered amine light stabilizer; the process facilitates removal of the by-product by inert gas or vacuum, preferably the process is carried out under an atmospheric inert gas flow, and the process employs inert gas or vacuum to facilitate removal of the alkanol by-product formed during the transesterification synthesis, avoiding accumulation of the by-product in the relatively viscous reaction medium.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is described in detail below with reference to specific examples and experimental data, and it should be understood that the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention.

Example 1

To a reactor equipped with a mechanical stirrer, thermometer, condenser maintained at 75 ℃, trap, and nitrogen sparge tube was added dimethyl adipate (30 g, 172 mmol), 2,2,6, 6-tetramethyl-4-hydroxypiperidine (54 g, 345 mmol), stirred and heated to 110 ℃, titanium 2-ethyl-1-hexanoate (1.2 mmol, 0.7 g) was added, and the reaction mixture was heated to 145 ℃ for 150 ℃ at normal pressure for 5 hours. During this process, nitrogen was continuously introduced below the liquid surface at a rate of 0.5 liter/min to remove the produced methanol. After the reaction is finished, under the protection of nitrogen, the temperature is reduced to 100 ℃ by cooling, and then the reaction mixture is poured into a tray for crystallization. Gas chromatography analysis showed that the reaction mixture contained 91% bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, 2.6% monomethyl mono (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, and 5% 2,2,6, 6-tetramethyl-4-hydroxypiperidine.

The organic diester compound was analyzed by gas chromatography using model SP-6800A gas chromatography. The column was a 6 "outer diameter stainless steel column packed with 80-100 mesh red diatomaceous earth chromatography support loaded with 3% SE-54, with a thermal conductivity detector, the oven of the column was programmed to heat from 100 ℃ to 320 ℃ at a rate of 10 ℃/min and held at the upper temperature limit for 10 minutes, the composition being determined by calculating the area percentage.

Example 2

To a reactor equipped with a mechanical stirrer, thermometer, condenser maintained at 75 ℃, trap, and nitrogen sparge tube was added dimethyl adipate (30 g, 172 mmol), 2,2,6, 6-tetramethyl-4-hydroxypiperidine (54 g, 345 mmol), stirred and heated to 110 ℃, titanium 2-ethyl-1-hexanoate (0.7 mmol, 0.39 g), titanium tetrakis (2-ethyl-1, 3-hexanediol) (0.5 mmol, 0.17 g) was added and the reaction mixture was heated to 145 ℃ at atmospheric pressure for 5 hours. During this process, nitrogen was continuously introduced below the liquid surface at a rate of 0.5 liter/min to remove the produced methanol. After the reaction is finished, under the protection of nitrogen, the temperature is reduced to 100 ℃ by cooling, and then the reaction mixture is poured into a tray for crystallization. Gas chromatography analysis showed that 96.5% of bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, 0.5% of monomethyl mono (2, 2,6, 6-tetramethyl-4-piperidyl) adipate and 1.5% of 2,2,6, 6-tetramethyl-4-hydroxypiperidine were contained in the reaction mixture.

Example 3

To a reactor equipped with a mechanical stirrer, thermometer, condenser maintained at 75 ℃, collector, and nitrogen sparge tube was added dimethyl adipate (30 g, 172 mmol), 2,2,6, 6-tetramethyl-4-hydroxypiperidine (67.5 g, 430 mmol), stirred and heated to 110 ℃, titanium 2-ethyl-1-hexanoate (0.7 mmol, 0.39 g), titanium tetrakis (2-ethyl-1, 3-hexanediol) (0.5 mmol, 0.17 g) was added and the reaction mixture was heated to 145 ℃ at atmospheric pressure for 5 hours. During this process, nitrogen was continuously introduced below the liquid surface at a rate of 0.5 liter/min to remove the produced methanol. After the reaction is finished, under the protection of nitrogen, the temperature is reduced to 100 ℃ by cooling, and then the reaction mixture is poured into a tray for crystallization. Gas chromatography analysis showed that the reaction mixture contained 95.5% bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, no monomethyl mono (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, and 3.5% 2,2,6, 6-tetramethyl-4-hydroxypiperidine.

Example 4

To a reactor equipped with a mechanical stirrer, thermometer, condenser maintained at 75 ℃, trap, and nitrogen sparge tube was added dimethyl adipate (30 g, 172 mmol), 2,2,6, 6-tetramethyl-4-hydroxypiperidine (59.4 g, 378 mmol), stirred and heated to 110 ℃, titanium 2-ethyl-1-hexanoate (0.7 mmol, 0.39 g), titanium tetrakis (2-ethyl-1, 3-hexanediol) (0.5 mmol, 0.17 g) was added and the reaction mixture was heated to 145 ℃ at atmospheric pressure for 5 hours. During this process, nitrogen was continuously introduced below the liquid surface at a rate of 0.5 liter/min to remove the produced methanol. After the reaction is finished, under the protection of nitrogen, the temperature is reduced to 100 ℃ by cooling, and then the reaction mixture is poured into a tray for crystallization. Gas chromatography analysis showed that the reaction mixture contained 97% bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, no monomethyl mono (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, and 2.2% 2,2,6, 6-tetramethyl-4-hydroxypiperidine.

Example 5

To a reactor equipped with a mechanical stirrer, thermometer, condenser maintained at 75 ℃, trap, and nitrogen sparge tube was added dimethyl adipate (30 g, 172 mmol), 2,2,6, 6-tetramethyl-4-hydroxypiperidine (59.4 g, 378 mmol), stirred and heated to 110 ℃, titanium 2-ethyl-1-hexanoate (1.6 mmol, 0.90 g), titanium tetrakis (2-ethyl-1, 3-hexanediol) (1.0 mmol, 0.34 g) was added and the reaction mixture was heated to 145-. During this process, nitrogen was continuously introduced below the liquid surface at a rate of 0.5 liter/min to remove the produced methanol. After the reaction is finished, under the protection of nitrogen, the temperature is reduced to 100 ℃ by cooling, and then the reaction mixture is poured into a tray for crystallization. Gas chromatography analysis showed that the reaction mixture contained 97.5% bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, no monomethyl mono (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, and 1.8% 2,2,6, 6-tetramethyl-4-hydroxypiperidine.

Example 6

To a reactor equipped with a mechanical stirrer, thermometer, condenser maintained at 75 ℃, trap, and nitrogen sparge tube was added dimethyl adipate (30 g, 172 mmol), 2,2,6, 6-tetramethyl-4-hydroxypiperidine (59.4 g, 378 mmol), stirred and heated to 110 ℃, titanium 2-ethyl-1-hexanoate (1.6 mmol, 0.90 g), titanium tetrakis (2-ethyl-1, 3-hexanediol) (1.0 mmol, 0.34 g) was added and the reaction mixture was heated to 145-. During this process, nitrogen was continuously introduced below the liquid surface at a rate of 0.5 liter/min to remove the produced methanol. After the reaction is finished, cooling to 100 ℃ under the protection of nitrogen, neutralizing with glacial acetic acid, washing twice with hot water of 80 ℃, and pouring the reaction mixture into a tray for crystallization. Gas chromatography analysis showed that the reaction mixture contained 99.5% bis (2, 2,6, 6-tetramethyl-4-piperidyl) adipate, no monomethyl mono (2, 2,6, 6-tetramethyl-4-piperidyl) adipate and no 2,2,6, 6-tetramethyl-4-hydroxypiperidine.

Example 7

The national standard GB/T16422.3-2014 plastic laboratory light source exposure experimental method part 3 fluorescent ultraviolet lamp is a standard for the operation implementation method of a light and water exposure instrument (fluorescent ultraviolet-condensation type) for exposing non-metal materials, and is a widely used national standard for the light source exposure experiment of the fluorescent ultraviolet lamp. The method is to simulate the damage caused by ultraviolet energy in rainwater or dew and sunlight by a manual method. The hindered amine light stabilizing compound synthesized by the invention is compared with the existing hindered amine light stabilizer Tinuvin-770 in an anti-ultraviolet aging test by using the standard.

1. Mixing of samples: (sample ratio is weight ratio)

Sample a, example 2 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 1.5, and the aging inhibitor was further compounded in an amount of 0.75% to polypropylene resin (brand: T30S)

Sample B, example 3 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 1.5, and the aging inhibitor was further compounded in an amount of 0.75% to polypropylene resin (brand: T30S)

Sample C, example 4 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 1.5, and the aging inhibitor was further compounded in an amount of 0.75% to polypropylene resin (brand: T30S)

Sample D, example 5 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 1.5, and the aging inhibitor was further compounded in an amount of 0.75% to polypropylene resin (brand: T30S)

Sample E, example 6 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 1.5, and the aging inhibitor was further compounded in an amount of 0.75% to polypropylene resin (brand: T30S)

Sample F, Tinuvin-770: antioxidant 1010: secondary antioxidant 168 is 5: 1: 1.5, and the aging inhibitor was further compounded in an amount of 0.75% to polypropylene resin (brand: T30S)

2. Preparing an ultraviolet aging resistant resin sample sheet:

(1) experimental equipment: CTE-20 twin screw extruder

(2) The preparation process conditions of the anti-aging master batch are as follows:

and pouring the mixed sample powder into a hopper of an extruder, and starting the double-screw extruder. At this time, the temperature of the compression section is 70-90 ℃, the temperature of the melting section is 160-180 ℃, the temperature of the homogenization section is 200-210 ℃, the rotating speed of the twin screw is 350 r/min, and the rotating speed of the feeding machine is 30 r/min. And melting the extruded material strips, cooling by water, and granulating to prepare the anti-aging master batch.

(3) The prepared anti-aging master batch is made into dumbbell test pieces with the sizes of 115mm multiplied by 25mm multiplied by 1mm by an injection molding machine.

3. And (3) testing the photo-aging resistance of the sample wafer:

testing an instrument: QUV ultraviolet aging tester, UTM-1422 electronic tensile tester

The test method comprises the following steps:

the dumbbell-shaped sample pieces were tested by UV-B fluorescent ultraviolet lamp (UV-313) with irradiation exposure at 70 deg.C for 8h and non-irradiation condensation exposure at 50 deg.C for 4h, and the test duration was 192hr,240hr, and 288hr, respectively. Tensile test data for the coupons at each test time are shown in the following table:

(Note: tensile force in units of N and elongation in units of mm)

And (3) analyzing experimental data: the experimental sample wafers A, B, C and D contain the composition, and the anti-aging effect of the experimental sample wafers is obviously better than that of the sample wafer F containing Tinuvin-770 after 288-hour ultraviolet aging experiments. Sample E, although containing the composition of the present invention, was significantly inferior to samples A, B, C, and D in anti-aging effect after washing with water, so the composition of the present invention did not require washing and refining to obtain good anti-aging effect.

Example 8

The plastic woven bag is made by using polypropylene (PP) and Polyethylene (PE) resin as main raw materials, extruding, stretching into flat filaments and weaving. The plastic woven bag is widely suitable for packing powdery or granular solid materials such as chemical fertilizers, synthetic materials, grain crops, salt, ore sand and the like. Because the plastic woven bag is frequently used outdoors, certain requirements are provided for the ultraviolet aging resistance of the plastic woven bag. The existing traditional light stabilizer Tinuvin-770 is still the mainstream product currently applied in the field. Now, through an aging experiment, the composite of the invention is compared with Tinuvin-770 in the ultraviolet aging resistant effect of the plastic woven bag.

1. Mixing of samples: (sample ratio is weight ratio)

Sample a: tinuvin-770: antioxidant 1010: auxiliary antioxidant 168: UV-326: calcium stearate 7: 0.5: 1: 0.5: 1, and mixing the antioxidant mixture with polypropylene resin (brand: T30S) at a ratio of 30%

Sample B: example 4 composition: antioxidant 1010: auxiliary antioxidant 168: UV-326: calcium stearate 7: 0.5: 1: 0.5: 1, and mixing the antioxidant mixture with polypropylene resin (brand: T30S) at a ratio of 30%

2. Preparing the ultraviolet aging resistant resin master batch:

(1) experimental equipment: CTE-20 twin screw extruder

(2) The preparation process conditions of the anti-aging master batch are as follows:

and pouring the mixed sample powder into a hopper of an extruder, and starting the double-screw extruder. At this time, the temperature of the compression section is 70-90 ℃, the temperature of the melting section is 160-180 ℃, the temperature of the homogenization section is 200-210 ℃, the rotating speed of the twin screw is 350 r/min, and the rotating speed of the feeding machine is 30 r/min. And melting the extruded material strips, cooling by water, and granulating to prepare the anti-aging master batch.

3, preparing a plastic woven fabric sample:

mixing the obtained anti-aging functional master batch with polypropylene (T30S) powder and calcium carbonate filling master batch 10% in a ratio of 4%, mixing, spinning, and weaving to obtain the polypropylene woven fabric. The woven fabric obtained was cut into a sample strip having a length of 300mm and a width of 60mm according to GB/T8946-1998 woven Plastic bags for experiments.

4. And (3) testing the photo-aging resistance of the sample wafer:

testing an instrument: QUV ultraviolet aging tester, UTM-1422 electronic tensile tester

The test method comprises the following steps:

the obtained test piece was tested with UV-B fluorescent ultraviolet lamp (UV-313) with irradiation exposure at 70 deg.C for 8h and non-irradiation condensation exposure at 50 deg.C for 4h, respectively, with test duration of 200hr and 272 hr. Tensile test data for the coupons at each test time are shown in the following table:

(Note: tensile force in units of N and elongation in units of mm)

200hr ageing data for weft sample of woven cloth

272hr aging data for weft sample of woven cloth

And (3) analyzing experimental data: sample B contains the anhydrous composition, and compared with sample A containing Tinuvin-770, the sample prepared by equivalently replacing Tinuvin-770 has basically equivalent anti-aging effect after 200hr ultraviolet light aging test. After 272hr of ultraviolet light aging test, the aging resistance of sample B is obviously better than that of sample A.

Example 9

The polyethylene resin can be processed by injection molding, extrusion molding, blow molding, or the like. Mainly used as agricultural films, industrial packaging films, medicine and food packaging films, mechanical parts and sun glassesArticles, building materials, wire, cable insulation, coatings andsynthetic paperAnd the like. As with polypropylene, is a very important plastic processing raw material. Compared with the traditional light stabilizer, the composition of the invention can obtain good light stability protection effect in polyethylene processing products through aging experiment tests.

1, mixing of samples: (sample ratio is weight ratio)

Sample a, example 2 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 2, and 0.7% of an antioxidant to be compounded into a polyethylene resin (brand: DFDA7042)

Sample B, example 3 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 2, and 0.7% of an antioxidant to be compounded into a polyethylene resin (brand: DFDA7042)

Sample C, example 4 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 2, and 0.7% of an antioxidant to be compounded into a polyethylene resin (brand: DFDA7042)

Sample D, example 5 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 2, and 0.7% of an antioxidant to be compounded into a polyethylene resin (brand: DFDA7042)

Sample E, example 6 composition: antioxidant 1010: secondary antioxidant 168 is 5: 1: 2, and 0.7% of an antioxidant to be compounded into a polyethylene resin (brand: DFDA7042)

Sample F, Tinuvin-770: antioxidant 1010: secondary antioxidant 168 is 5: 1: 2, and 0.7% of an antioxidant to be compounded into a polyethylene resin (brand: DFDA7042)

2, preparing an ultraviolet aging resistant resin sample sheet:

(1) experimental equipment: CTE-20 twin screw extruder

(2) The preparation process conditions of the anti-aging master batch are as follows:

and pouring the mixed sample powder into a hopper of an extruder, and starting the double-screw extruder. At this time, the temperature of the compression section is 70-90 ℃, the temperature of the melting section is 160-180 ℃, the temperature of the homogenization section is 200-210 ℃, the rotating speed of the twin screw is 350 r/min, and the rotating speed of the feeding machine is 30 r/min. And melting the extruded material strips, cooling by water, and granulating to prepare the anti-aging master batch.

(3) The prepared anti-aging master batch is made into dumbbell test pieces with the sizes of 115mm multiplied by 25mm multiplied by 1mm by an injection molding machine.

3, testing the anti-light aging performance of the sample wafer:

testing an instrument: QUV ultraviolet aging tester, UTM-1422 electronic tensile tester

The test method comprises the following steps:

testing the dumbbell-shaped sample sheet according to UV-B type fluorescent ultraviolet lamp (UV-313) with irradiation exposure at 70 deg.C for 8h and non-irradiation condensation exposure at 50 deg.C for 4h, wherein the test duration is 240hr,480hr and 720hr respectively. Tensile test data for the coupons at each test time are shown in the following table:

(Note: tensile force in units of N and elongation in units of mm)

And (3) analyzing experimental data: the experimental sample wafers A, B, C and D contain the composition, and the anti-aging effect of the composition is obviously better than that of the sample wafer F containing Tinuvin-770 after 720-hour ultraviolet aging experiment. Sample E, although containing the composition of the present invention, was significantly inferior to samples A, B, C, and D in anti-aging effect after washing with water, so the composition of the present invention did not require washing and refining to obtain good anti-aging effect.

Example 10

1. Mixing of samples: (sample ratio is weight ratio)

Sample a, example 4 composition: antioxidant 245: auxiliary antioxidant 626: 8: 1: 1, and the anti-aging agent is mixed with 1% of ABS resin (brand: POLYLAC D-120)

Sample B, example 6 composition: antioxidant 245: auxiliary antioxidant 626: 8: 1: 1, and the anti-aging agent is mixed with 1% of ABS resin (brand: POLYLAC D-120)

Sample C, Tinuvin-770: antioxidant 245: auxiliary antioxidant 626: 8: 1: 1, and the anti-aging agent is mixed with 1% of ABS resin (brand: POLYLAC D-120)

2. Preparing an ultraviolet aging resistant resin sample sheet:

(1) experimental equipment: CTE-20 twin screw extruder

(2) The preparation process conditions of the anti-aging master batch are as follows:

and pouring the mixed sample powder into a hopper of an extruder, and starting the double-screw extruder. At this time, the temperature of the compression section is 80-100 ℃, the temperature of the melting section is 200-. And melting the extruded material strips, cooling by water, and granulating to prepare the anti-aging master batch.

(3) The prepared anti-aging master batch is made into dumbbell test pieces with the sizes of 115mm multiplied by 25mm multiplied by 1mm by an injection molding machine.

3. And (3) testing the photo-aging resistance of the sample wafer:

testing an instrument: QUV ultraviolet aging tester, UTM-1422 electronic tensile tester, SC-80C whiteness tester;

the test method comprises the following steps:

testing the dumbbell-shaped sample sheet according to UV-B type fluorescent ultraviolet lamp (UV-313) with irradiation exposure at 70 deg.C for 8h and non-irradiation condensation exposure at 50 deg.C for 4h, wherein the test duration is 240hr,480hr and 720hr respectively. Tensile test data for the coupons at each test time are shown in the following table:

(Note: tensile force in units of N and elongation in units of mm)

And (3) analyzing experimental data: the anti-aging effect of experimental sample A and B containing the composition is better than that of sample C containing Tinuvin-770 after 480 and 720-hour ultraviolet aging experiments. For ABS resins, the experimental results also demonstrate that: compared with Tinuvin-770, the composition provided by the invention has a better anti-yellowing effect after a 720-hour ultraviolet aging experiment. Sample B, which also contained the composition of the present invention, was less resistant to aging and yellowing than sample a after washing with water. The results of this experiment thus again demonstrate: the composition of the invention can obtain good anti-aging effect without washing and refining treatment.