CN114957799B - Functional filler of degradable plastic with visual stable period and preparation method thereof - Google Patents

Functional filler of degradable plastic with visual stable period and preparation method thereof Download PDF

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CN114957799B
CN114957799B CN202210585266.1A CN202210585266A CN114957799B CN 114957799 B CN114957799 B CN 114957799B CN 202210585266 A CN202210585266 A CN 202210585266A CN 114957799 B CN114957799 B CN 114957799B
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cyclodextrin
plastic
cellulose
functional filler
sample
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CN114957799A (en
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陈超
郑传嵘
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East China Normal University
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Abstract

The invention discloses a functional filler of degradable plastic with a visual stable period and a preparation method thereof. The photocatalyst is wrapped by the photocatalyst stabilizing cage, the functions of the photocatalyst stabilizing cage structure and the color changing along with the illumination time are utilized, the functions of the function filler that the degradation activity of plastic is delayed to be opened and the color changes along with the degradation activity are realized, the function filler has a certain color at the initial stage of illumination, the function filler does not have the activity of photocatalytic degradation of plastic, and the color of the function filler changes after illumination for a certain time, so that the function filler has the activity of high-efficiency photocatalytic degradation of plastic. After the functional filler is mixed with plastic to form a composite material, the plastic can be added with a photodegradation function with adjustable stability period and visualization, the plastic is converted into degradable plastic, the obtained degradable plastic has good stability in the service period, has high-efficiency degradation rate in the waste period, and has different colors in the stability period and the degradation period.

Description

Functional filler of degradable plastic with visual stable period and preparation method thereof
Technical Field
The invention belongs to the field of degradable plastics, relates to a functional filler of degradable plastics with a visual stability period, a preparation method and application of the functional filler in preparation of degradable plastic products, and particularly relates to application of the functional filler in controlling the stability period, the degradation period and the degradation efficiency of plastics and indicating the beginning of the degradation period of plastics through color change.
Background
Because of the low cost, ease of molding, light weight, durability, sturdiness, etc., plastics are widely used in various fields, about 2 million tons of plastic waste are discharged into the environment each year, causing serious environmental problems. Common treatment methods for plastic waste include landfill and incineration. Landfill occupies a large amount of land resources and poses a potential risk to soil and groundwater due to migration and conversion of additives and contaminants in the plastic waste from the plastic waste. Particulate matter and a large amount of toxic and harmful volatile organic compounds are generated in the incineration process.
Degradable plastics are of great interest because of the increased degradation activity of plastics. Although the biodegradable plastic has good degradation activity, the proportion of the biodegradable plastic in the plastic market is less than 1%, and the biodegradable plastic has the problems of high production and use cost, poor mechanical property, poor gas barrier property, poor thermal stability and the like, and cannot solve the problem of plastic pollution under the condition of not affecting domestic life. The proportion of the traditional non-biodegradable plastics such as polyethylene, polypropylene, polystyrene and the like in the plastic market is more than 99%, so how to convert the traditional non-biodegradable plastics into the degradable plastics is a key for solving plastic pollution and sustainable development of assistance.
The degradability of the traditional non-biodegradable plastic is improved by using the functional filler capable of improving the plastic degradation activity, so that the plastic pollution problem is hopeful to be solved under the condition of not affecting the national life. The functional filler capable of improving the degradation activity of plastics mainly comprises a thermal degradation functional filler and a photodegradation functional filler. The photodegradation functional filler includes a photosensitizer and a photocatalyst. Wherein the photocatalyst has development potential due to high activity. However, since the photocatalyst exerts the photocatalytic activity under the condition of illumination, the degradability is brought to the plastic, and the performance of the corresponding degradable plastic is unstable in the use process, the photocatalyst needs to be treated so that the activity of the photocatalyst is delayed to be started; in addition, even if the photocatalyst can realize the delayed activation of the activity, the photocatalyst cannot indicate whether the photocatalytic activity is started or not through the color change, which results in that a consumer cannot distinguish whether the corresponding degradable plastic is in the stable phase or the degradation phase through the color, which hinders the application of the functional filler formed by the photocatalyst in the field of the degradable plastic.
Disclosure of Invention
Aiming at the technical defects of the existing photocatalytic functional filler in the field of degradable plastics, the invention provides a preparation method of the functional filler for constructing the degradable plastics with a visual stable period by utilizing a photocatalyst and a photocatalyst stabilizing cage and application of the functional filler in converting plastics into degradable plastics.
A first object of the present invention is to provide a functional filler which does not have a degradable plastic activity for a certain period of time under light and exhibits a certain color, which exhibits a degradable plastic activity after a certain period of time under light and exhibits another color, a color change occurring simultaneously with an activity change.
A second object of the present invention is to provide a process for the preparation of functional fillers capable of adding to plastics the degradability of the visible stability period.
The third object of the invention is to provide a degradable plastic product prepared by mixing functional filler and plastic master batch, wherein the degradable plastic has a controllable stable period under illumination, the degradable plastic shows one color in the stable period, the degradable plastic is in a degradation period after illumination for a certain time, the degradable plastic has high-efficiency degradation activity, and the degradable plastic shows another color in the degradation period. The color change of the degradable plastic occurs simultaneously with the transition between the stationary phase/the degradation phase.
The specific technical scheme for realizing the aim of the invention is as follows:
the functional filler of the degradable plastic with the visual stable period is characterized by comprising the following raw materials in parts by weight:
1) 1 part of a photocatalyst; the photocatalyst consists of one of the following photocatalysts:
ultraviolet light responsive TiO 2 、ZnO、SnO 2 、SrTiO 3 、KTaO 3 、K 4 Nb 6 O 17 Or BaTiO 3 ；
Cu of visible light response 2 O、CdS、WO 3 、g-C 3 N 4 、BiVO 4 Or Ag 3 PO 4 ；
2) 0.01-15 parts of photocatalyst stabilizing cage; the photocatalyst stabilizing cage consists of polyiodide ions, cyclodextrin and cellulose.
In the photocatalyst, the ultraviolet light responsive TiO 2 Including anatase, rutile or brookite; the ZnO responding to ultraviolet light comprises a hexagonal wurtzite structure, a cubic zincblende structure, a cubic rock salt structure or an amorphous form; the modified TiO of the visible light response 2 The modified ZnO comprises metal element modification, nonmetal element modification, noble metal modification, metal element/nonmetal element co-modification or dye sensitization modification method modification; the ultraviolet rayThe photocatalyst state of light response and visible light response includes powder, block, film or sol; the photocatalyst morphology of ultraviolet light response and visible light response comprises nanowires, nanotubes, nanospheres, nano polygonal blocks or nano irregular shapes.
In the photocatalyst stabilizing cage, the polyiodide is represented by I - And I 2 Composition, I - The material being derived from KI, naI, agI, znI 2 、NH 4 I、CoI 2 、C 6 H 8 IN、C 12 H 8 ClI、C 14 H 18 IN、C 16 H 36 I 3 N or C 16 H 36 Br 2 IN，I 2 And I - The molar ratio of (2) is in the range of 0.01 to 10. The cyclodextrin includes C 36 H 60 O 30 (alpha-cyclodextrin), C 42 H 70 O 35 (beta-cyclodextrin), C 48 H 80 O 40 (gamma-cyclodextrin), C 56 H 98 O 35 (dimethyl-beta-cyclodextrin), C 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin), C 63 H 112 O 35 (trimethyl-beta-cyclodextrin) or C 84 H 112 O 56 (triacetyl-beta-cyclodextrin), I 2 The molar ratio of cyclodextrin is in the range of 0.01-30. The cellulose comprises methyl cellulose, ethyl cellulose, cellulose triacetate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose or hydroxypropyl methyl cellulose, I 2 The molar ratio of the cellulose to the cellulose is in the range of 0.0001-10.I 2 The molar ratio of the catalyst to the photocatalyst is in the range of 0.01-90.
The preparation method of the functional filler adopts a layer-by-layer modification method, and comprises the following specific steps:
step 1: adding polyiodide ions into the solution, and stirring at 25-200deg.C for 30-120 min; wherein the polyiodide is represented by I - And I 2 The composition of the multi-iodine ion is that the concentration of multi-iodine ion is 0.1-25 g/L; i - KI, naI, agI, znI of a shape of KI, naI, agI, znI 2 、NH 4 I、CoI 2 、C 6 H 8 IN、C 12 H 8 ClI、C 14 H 18 IN、C 16 H 36 I 3 N or C 16 H 36 Br 2 IN; the solution is a mixed solution of water and cyclodextrin; in the mixed solution of water and cyclodextrin, the concentration of the cyclodextrin is 0.5-500 g/L; cyclodextrin is C 36 H 60 O 30 (alpha-cyclodextrin), C 42 H 70 O 35 (beta-cyclodextrin), C 48 H 80 O 40 (gamma-cyclodextrin), C 56 H 98 O 35 (dimethyl-beta-cyclodextrin), C 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin), C 63 H 112 O 35 (trimethyl-beta-cyclodextrin) or C 84 H 112 O 56 (triacetyl- β -cyclodextrin);
step 2: adding the photocatalyst into the mixed solution prepared in the step 1, stirring at 25-200 ℃ for 1-5 h, and filtering to obtain a filter cake; the photocatalyst is used for preparing the catalyst in step 1 2 The molar ratio of (2) is in the range of 0.01-100; the method comprises the steps of carrying out a first treatment on the surface of the The photocatalyst is TiO 2 、ZnO、SnO 2 、SrTiO 3 、KTaO 3 、K 4 Nb 6 O 17 、BaTiO 3 、Cu 2 O、CdS、WO 3 、g-C 3 N 4 、BiVO 4 Or Ag 3 PO 4 ；
Step 3: adding the filter cake obtained in the step 2 into a mixed solution of water and cellulose, stirring at 25-200 ℃ for 0.5-48 and h, filtering or centrifuging, and drying at 25-200 ℃ to obtain the functional filler; wherein, in the mixed solution of water and cellulose, the concentration of cellulose is 0.5-50 g/L; the cellulose is methyl cellulose, ethyl cellulose, cellulose triacetate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose or hydroxypropyl methyl cellulose.
The application of the functional filler in preparing degradable plastic products.
The application comprises the following specific steps:
step 1: dissolving plastic in water or one of the following organic solvents at 20-200 ℃: isopropanol, cyclohexane, acetone, ethanol, propanol, formic acid, xylene or tetrahydrofuran; the plastic comprises: polyethylene, polystyrene, polyvinyl chloride, polypropylene, polyamide, polylactic acid, polymethacrylate or polyethylene terephthalate; the concentration of the plastic is 1-20g/L;
step 2: adding the functional filler into the solution containing the plastic in the step 1, wherein the mass ratio of the functional filler to the plastic is 0.001-0.8;
step 3: stirring and mixing at 25-200deg.C for 0.1-5 h;
step 4: coating the mixture prepared in the step 3 on a substrate, and drying at 25-200 ℃ to obtain a degradable plastic product with a visual stability period, wherein the plastic product has one of the following colors: the weight reduction rate of the plastic is 0.01-1% in the sunlight illumination for 0.5-90 days, the plastic color is changed into bluish, light brown, light cyanosis, light brown, light coffee, light gray or white after the sunlight illumination for 0.5-90 days, and the weight reduction rate can be improved to 5-100% after the illumination for 0.5-90 days of the plastic product with the changed color; the plastic product is independently arranged on the surface of the substrate as a coating or peeled off from the substrate; when the plastic product is used as a coating, the substrate is selected from polyethylene, polystyrene, polypropylene, polyamide, glass or quartz; when the plastic article is independently present, the substrate is selected from glass, quartz, or a low surface energy polymer; wherein the low surface energy polymer comprises: polyvinylidene fluoride, polytetrafluoroethylene or ethylene-tetrafluoroethylene copolymers.
The application comprises the following specific steps:
step 1: mixing the functional filler with the plastic master batch, wherein the mass ratio of the functional filler to the plastic master batch is 0.001-0.8; wherein, the mixing mode of the functional filler and the plastic particles is as follows:
adding the functional filler and the plastic particle mixture into an extruder; or alternatively, the process may be performed,
the plastic particles are firstly added into the extruder, and the functional filler is added at the middle end of the extruder.
Step 2: using an extruder, extruding at a temperature of 50-280 ℃ to produce a degradable plastic article having a visual stability profile, said plastic article having one of the following colors: the weight reduction rate of the plastic is 0.01-1% in the sunlight illumination for 0.5-90 days, the plastic color is changed into light blue, light brown, light coffee, light gray or white after the sunlight illumination for 0.5-90 days, and the weight reduction rate is improved to 5-100% after the illumination for 0.5-90 days.
Compared with the prior art, the functional filler prepared by the invention has the advantages of adjustable stability period, degradation period time and color change time, simple and convenient operation, easy synthesis, little organic solvent used in the catalyst synthesis process, environment-friendly degradation products and the like, so that the activity opening time and the color change time of the functional filler are consistent, proper information is provided for a plastic product user, the bottleneck problem of inconsistent activity opening time and color change time of the functional filler is effectively solved, and the functional filler has a stronger market application prospect.
Drawings
FIG. 1 is an external view of samples 1 to 9 of the functional filler obtained in the example of the present invention;
FIG. 2 is a schematic illustration of controllable self-indicating photocatalytic degradation of a degradable polyethylene sample 14 having a visual stabilization period in accordance with the present invention;
fig. 3 is a schematic representation of the change in film color during photocatalytic degradation of a degradable polyethylene sample 14 having a visual stabilization period in accordance with the present invention.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
Will I 2 And C 16 H 36 Br 2 IN is added to 175.74 g/L C IN a molar ratio of 1:2 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin) solution, stirring for 120 min at 30deg.C in water bath, and stirring with magnetic force to obtain 1.325 g BiVO 4 Slowly adding the mixture into the solution, continuously stirring for 1 h after the addition is finished, centrifuging, adding the precipitate into 18 mL methyl cellulose solution (5 g/L) for stirring for 5 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 38 ℃ to obtain the functional filler sample 1.
Example 2
Will I 2 And NaI are added into 219.68 g/L C in turn in a molar ratio of 1:5 42 H 70 O 35 In the (. Beta. -cyclodextrin) solution, stirring was carried out for 90 min at 60℃in a water bath, and then 1.325 g of Fe was stirred magnetically 2 O 3 Slowly adding the mixture into the solution, continuously stirring for 2 h after the addition is finished, centrifuging, adding the precipitate into 18 mL ethyl cellulose solution (10 g/L) for stirring for 6 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 40 ℃ to obtain the functional filler sample 2.
Example 3
Will I 2 And AgI are added sequentially in a molar ratio of 1:7 to 292.9 g/L C 48 H 80 O 40 And (3) stirring the solution in gamma-cyclodextrin at the water bath of 90 ℃ for 60 min, slowly adding 1.325 g of ZnO into the solution under magnetic stirring, continuously stirring for 3 h after the addition, centrifuging, adding the precipitate into 18 mL cellulose triacetate solution (15 g/L) for 8 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 50 ℃ to prepare the functional filler sample 3.
Example 4
Will I 2 And ZnI 2 Sequentially adding the components into a mixture of 175.74 g/L C according to a molar ratio of 1:10 56 H 98 O 35 (dimethyl-beta-cyclodextrin) solution, stirred for 90 min at 90℃in a water bath, then 6.625 g of WO were stirred magnetically 3 Slowly adding into the above solution, stirring for 4 h, centrifuging, and adding the precipitate into 18 mL methyl hydroxyethyl fiberThe cellulose solution (20. 20 g/L) was stirred for 10. 10 h, after the reaction, centrifuged, and the precipitate was dried at 60℃in a constant temperature oven to prepare a functional filler sample 4 of the present invention.
Example 5
Will I 2 And KI are added sequentially in a molar ratio of 10:1 to 292.9. 292.9 g/L C 36 H 60 O 30 In the (. Alpha. -cyclodextrin) solution, stirring was carried out for 90 min at 90℃in a water bath, and 13.25 g of TiO was then stirred magnetically 2 Slowly adding the mixture into the solution, continuously stirring for 2 h after the addition is finished, centrifuging, adding the precipitate into 18 mL hydroxyethyl cellulose solution (50 g/L) for stirring for 24 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 60 ℃ to obtain the functional filler sample 5.
Example 6
Will I 2 And C 6 H 8 IN was added sequentially IN a molar ratio of 2:1 to 292.9 g/L C 63 H 112 O 35 In (trimethyl-beta-cyclodextrin) solution, stirring for 90 min at 90℃in a water bath, then stirring 6.625 g Cu under magnetic stirring 2 Slowly adding O into the solution, continuing stirring for 2 h after the addition is finished, centrifuging, adding the precipitate into 18 mL hydroxypropyl cellulose solution (30 g/L) for stirring for 16 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 70 ℃ to obtain the functional filler sample 6.
Example 7
Will I 2 And C 14 H 18 IN was added sequentially IN a molar ratio of 5:1 to 292.9. 292.9 g/L C 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin) solution, stirring for 90 min at 90deg.C in water bath, and stirring under magnetic force 6.625 g-C 3 N 4 Slowly adding the mixture into the solution, continuously stirring for 2 h after the addition is finished, centrifuging, adding the precipitate into a 9 mL hydroxyethyl cellulose solution (35 g/L) for stirring for 18 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 70 ℃ to obtain the functional filler sample 7.
Example 8
Will I 2 And C 16 H 36 I 3 N is added in turn to 292.9. 292.9 g/L C in a molar ratio of 7:1 84 H 112 O 56 (triacetyl-beta-cyclodextrin) solution, stirring for 90 min at the water bath of 90 ℃, then slowly adding 6.625 g of CdS into the solution under magnetic stirring, continuing stirring for 2 h after the addition is completed, centrifuging, adding the precipitate into 54mL of methyl hydroxyethyl cellulose solution (40 g/L) to stir for 20 h, centrifuging after the reaction is completed, and drying the precipitate in a constant temperature drying oven at 80 ℃ to obtain the functional filler sample 8.
Example 9
Will I 2 And NH 4 I is added into 219.68 g/L C in turn in a molar ratio of 1:1 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin) solution, stirring for 30 min at 90 ℃ in a water bath, and then stirring 6.625 g SnO under magnetic stirring 2 Slowly adding the mixture into the solution, continuously stirring for 5 h after the addition is finished, centrifuging, adding the precipitate into 18 mL hydroxypropyl methylcellulose solution (25 g/L) for stirring for 12 h, centrifuging after the reaction is finished, and drying the precipitate in a constant-temperature drying oven at 80 ℃ to obtain the functional filler sample 9. Referring to fig. 1, the appearance of samples 1-9 is shown.
Example 10
Polyethylene was dissolved in cyclohexane solution at 70℃to prepare a polyethylene solution of 5.5. 5.5 g/L, which was stirred for 2. 2 h. Subsequently, 10 mL absolute ethanol was added to the solution and stirred for 1 h, and sample 1 was added to the solution and stirred for a further 20 minutes with a mass ratio of sample 1 to polyethylene of 0.1:1. The resulting mixture was transferred to a glass petri dish and dried at room temperature for 1 d. The sample was then peeled from the petri dish to produce a degradable polyethylene sample 10 with visual stability. The prepared degradable polyethylene sample 10 with the visual stability period is put into a xenon lamp aging test box together with a pure polyethylene sample prepared under the same condition as a control sample at the temperature of 340 nm of 0.7w/m 2 And (3) carrying out a photocatalytic degradation experiment under the illumination condition, testing the weight loss rate of the sample, and recording the color change of the sample. The test results showed that the polyethylene sample 10 had a photocatalytic activity on time of 26 h and a color change time of 28 h.
Example 11
The same as in example 10, except that sample 2 was used instead of sample 1, a degradable polyethylene sample 11 with a visual stabilization period was produced. The test results showed that the photocatalytic activity on time of the degradable polyethylene sample 11 with the visual stabilization period was 0.5 h and the color change time was 2 h.
Example 12
The same as in example 10, except that sample 3 was used instead of sample 1, a degradable polyethylene sample 12 with a visual stabilization period was produced. The test results showed that the photocatalytic activity on time of the degradable polyethylene sample 12 with the visual stabilization period was 32 h and the color change time was 30 h.
Example 13
The same as in example 10, except that sample 4 was used instead of sample 1, a degradable polyethylene sample 13 with a visual stabilization period was produced. The test results show that the photocatalytic activity of the degradable polyethylene sample 13 with the visual stabilization period is started up for 90 h and the color change time is 86 h.
Example 14
The same as in example 10, except that sample 5 was used instead of sample 1, a degradable polyethylene sample 14 with a visual stabilization period was produced. Referring to fig. 2 and 3, the test results showed that the mass of the degradable polyethylene sample 14 with the visual stationary phase remained substantially unchanged in the pre-reaction 28, h, indicating that it was not significantly degraded, and the sample color appeared brown. The point a in fig. 2 is the active on time. 28 At h, sample 14 began to turn light brown in color, and the degradable polyethylene with the visually stable period began to degrade, and the weight loss rate of sample 14 reached 8.6% within 120 hours, at which time sample 14 was white. The degradable polyethylene sample 14 with visual stabilization period has a controllable self-indicating degradation function. I.e. the photocatalytic activity on time of the degradable polyethylene sample 14 with a visual stabilization period 28 h, the color change time 28 h.
Example 15
The same as in example 10, except that sample 6 was used instead of sample 1, a degradable polyethylene sample 15 with a visual stabilization period was produced. The test results showed that the photocatalytic activity on time of the degradable polyethylene sample 15 with the visual stabilization period was 16 h and the color change time was 20 h.
Example 16
The same as in example 10, except that sample 7 was used instead of sample 1, a degradable polyethylene sample 16 with a visual stabilization period was produced. The test results showed that the photocatalytic activity on time of the degradable polyethylene sample 16 with the visual stabilization period was 9 h and the color change time was 8 h.
Example 17
The same as in example 10, except that sample 8 was used instead of sample 1, a degradable polyethylene sample 17 with a visual stabilization period was produced. The test results showed that the photocatalytic activity of the degradable polyethylene sample 17 with the visual stabilization period was on-time 240 h and the color change time 232 h.
Example 18
The same as in example 10, except that sample 9 was used instead of sample 1, a degradable polyethylene sample 18 with a visual stabilization period was produced. The test results showed that the degradable polyethylene sample 18 with visual stabilization period was not stabilized, color change time 16 h.
Example 19
1 g polystyrene was added to 90 mL xylene and dissolved by heating. Subsequently, sample 1 was added to the solution and stirring was continued for 20 min with a mass ratio of sample 1 to polyethylene of 0.1:1. The resulting mixture was transferred to a glass petri dish and dried at room temperature for 1 d. The sample was then peeled from the petri dish to produce a degradable polystyrene sample 19 with visual stability.
Example 20
1 g polyvinyl chloride was added to 20 mL tetrahydrofuran and stirred until completely dissolved. Subsequently, sample 6 was added to the solution with continued stirring for 4 h, with a mass ratio of sample 6 to polyvinyl chloride of 0.001:1. The resulting mixture was transferred to a glass petri dish and dried at room temperature for 1 d. The sample is then peeled from the petri dish to produce a degradable polyvinyl chloride sample 20 with visual stability.
Example 21
1 g polypropylene was added to a 100 mL xylene solution and dissolved by heating. Subsequently, sample 3 was added to the solution and stirring was continued for 12 h. The mass ratio of sample 3 to polypropylene was 0.05:1. The resulting mixture was transferred to a glass petri dish and dried at room temperature for 1 d. The sample was then peeled from the petri dish to produce a degradable polypropylene sample 21 with visual stability.
Example 22
1 g polyamide was added to 100 mL formic acid solution and dissolved with stirring. Subsequently, sample 4 was added to the solution and stirring was continued 12 h. The mass ratio of sample 4 to polyamide was 0.01:1. The resulting mixture was transferred to a glass petri dish and dried at room temperature 2 d. The sample is then peeled from the petri dish to produce a degradable polyamide sample 22 with visual stability.
Example 23
3 g polylactic acid is added into 100 mL acetone solution, and stirred for dissolution. Subsequently, sample 9 was added to the solution and stirring was continued 12 h. The mass ratio of sample 9 to polylactic acid was 0.005:1. The resulting mixture was transferred to a glass petri dish and dried at room temperature 2 d. The sample was then peeled from the petri dish to produce a degradable polylactic acid sample 23 with visual stability.
Example 24
Polyethylene was mixed with sample 7, the mass ratio of sample 7 to polyethylene being 0.05:1. The mixture was fed into a twin screw extruder having L/d=40, d=16 mm, the extruder having 10 controllable temperature zones, wherein the 10 controllable temperature zones were fed into the extruder at 180 ℃ in the first and sixth stages, respectively, and the mixture of polyethylene and sample was extruded at 100 rpm in the screw rotation speed. A degradable polyethylene sample 24 with a visual stabilization period was produced.
Example 25
Polyethylene was fed to the first stage feed inlet of the extruder of example 24, extruded at 100 rpm at 180℃with the first to sixth temperature controlled zones at 180℃and sample 5 was fed to the sixth temperature controlled zone feed inlet with the seventh to tenth temperature controlled zones at 170 ℃. Sample 5 to polyethylene mass ratio was 0.05:1. A degradable polyethylene sample 25 with a visual stabilization period was produced.
Example 26
Polystyrene was mixed with sample 1, sample 1 to polystyrene mass ratio was 0.1:1. The mixture was fed into a twin screw extruder having L/d=25, d=16, mm, the extruder having 10 controllable temperature zones, wherein the 10 controllable temperature zones were fed into the extruder at 160 ℃ in the first and sixth stages, respectively, and the mixture of polystyrene and sample was extruded at 100 rpm in the screw rotation speed. A degradable polystyrene sample 26 with a visual stabilization period was produced.
Example 27
Polystyrene was fed to the first stage feed inlet of the extruder of example 26, extruded at 100 rpm at 160℃with the first to sixth temperature controlled zones at 160℃and sample 2 was fed to the sixth temperature controlled zone feed inlet with the seventh to tenth temperature controlled zones at 150 ℃. The mass ratio of sample 2 to polystyrene was 0.1:1. A degradable polystyrene sample 27 with a visual stabilization period was produced.
Example 28
Polyvinyl chloride was mixed with sample 5, the mass ratio of sample 5 to polyvinyl chloride being 0.01:1. The mixture was fed into a twin screw extruder having L/d=21, d=16, mm, the extruder having 10 controllable temperature zones, wherein in the extrusion direction, at the first and sixth stages, feed ports were provided, respectively, and the 10 controllable temperature zones were at 180 ℃, and the mixture of polyvinyl chloride and the sample was fed into the extruder at the feed port of the first stage, and extruded at a screw rotation speed of 100 rpm. A degradable polyvinyl chloride sample 28 with a visual stabilization period was produced.
Example 29
Polyvinyl chloride was fed into the first stage feed inlet of the extruder of example 28, extruded at 100 rpm at 180℃and at 180℃in the first to sixth temperature controlled zones, sample 3 was fed into the sixth temperature controlled zone feed inlet and at 160℃in the seventh to tenth temperature controlled zones. The mass ratio of sample 3 to polyvinyl chloride was 0.01:1. A degradable polyvinyl chloride sample 29 with a visual stabilization period was produced.
Example 30
Polypropylene was mixed with sample 3, the mass ratio of sample 3 to polypropylene being 0.03:1. The mixture was fed into a twin screw extruder having L/d=23, d=16, mm, the extruder having 10 controllable temperature zones, wherein the 10 controllable temperature zones were fed into the extruder at 190 ℃ in the first and sixth stages, respectively, and the mixture of polypropylene and sample was extruded at 100 rpm in the screw rotation speed. A degradable polypropylene sample 30 with a visual stabilization period was produced.
Example 31
Polypropylene was fed to the first stage feed inlet of the extruder described in example 30, extruded at 100 rpm at 190℃with the first to sixth temperature controlled zones at 190℃and sample 6 was fed to the sixth temperature controlled zone feed inlet with the seventh to tenth temperature controlled zones at 170 ℃. Sample 6 to polypropylene mass ratio was 0.03:1. A degradable polypropylene sample 31 with a visual stabilization period was produced.
Example 32
The polyamide was mixed with sample 7, the mass ratio of sample 7 to polyamide being 0.07:1. The mixture was fed into a twin screw extruder having L/d=30, d=16, mm, the extruder having 10 controllable temperature zones, wherein the 10 controllable temperature zones were fed into the extruder at 180 ℃ in the first and sixth stages, respectively, and the mixture of polyamide and sample was extruded at 100 rpm in the screw rotation speed. A sample 32 of degradable polyamide with a visual stabilization period was produced.
Example 33
The polyamide was fed into the first stage feed inlet of the extruder described in example 32, extruded at 100 rpm at 180℃with the first to sixth temperature controlled zones at 180℃and sample 4 was fed into the sixth temperature controlled zone feed inlet with the seventh to tenth temperature controlled zones at 160 ℃. The mass ratio of sample 4 to polyamide was 0.07:1. A sample 33 of degradable polyamide with a visual stabilization period was produced.
Example 34
Polylactic acid was mixed with sample 7, the mass ratio of sample 7 to polylactic acid was 0.05:1. The mixture was fed into a twin screw extruder having L/d=40, d=16, mm, the extruder having 10 controllable temperature zones, wherein the 10 controllable temperature zones were fed into the extruder at 200 ℃ in the first and sixth stages, respectively, and the mixture of polylactic acid and sample was extruded at 100 rpm in the screw rotation speed. A sample 34 of degradable polylactic acid with a visual stabilization period was produced.
Example 35
Polylactic acid is added into a first section feed inlet of the extruder in the embodiment 24, and extruded at 100 rpm under the condition of 200 ℃, the temperature of a temperature control zone from the first section to the sixth section is 200 ℃, a sample 4 is added into the feed inlet of the temperature control zone from the sixth section, and the temperature of a temperature control zone from the seventh section to the tenth section is 180 ℃. The mass ratio of the sample 4 to the polylactic acid is 0.05:1. A degradable polylactic acid sample 35 with a visual stabilization period was produced.

Claims (7)

1. The functional filler of the degradable plastic with the visual stable period is characterized by comprising the following raw materials in parts by weight:
1) 1 part of a photocatalyst; the photocatalyst consists of one of the following photocatalysts:
ultraviolet light responsive TiO 2 、ZnO、SnO 2 、SrTiO 3 、KTaO 3 、K 4 Nb 6 O 17 Or BaTiO 3 ；
Modified TiO of visible light response 2 Modified ZnO, cu 2 O、CdS、WO 3 、g-C 3 N 4 、BiVO 4 Or Ag 3 PO 4 ；
2) 0.01-15 parts of photocatalyst stabilizing cage; the photocatalyst stabilizing cage consists of polyiodide ions, cyclodextrin and cellulose.
2. The functional filler of claim 1, wherein the uv-responsive TiO 2 Including anatase, rutile or brookite; the ZnO responding to ultraviolet light comprises a hexagonal wurtzite structure, a cubic zincblende structure, a cubic rock salt structure or an amorphous form; the modified TiO of the visible light response 2 The modified ZnO comprises metal element modification, nonmetal element modification, metal element/nonmetal element co-modification or dye sensitization modification method modification; the ultraviolet light response and visible light response photocatalyst comprises powder, block, film or sol, and also comprises nanowires, nanotubes, nanospheres, nano polygonal blocks or nano irregular shapes.
3. The functional filler of claim 1, wherein the polyiodide is represented by I - And I 2 Composition, I - The material being derived from KI, naI, agI, znI 2 、NH 4 I、CoI 2 、C 6 H 8 IN、C 12 H 8 ClI、C 14 H 18 IN、C 16 H 36 I 3 N or C 16 H 36 Br 2 IN，I 2 And I - The molar ratio of (2) is in the range of 0.01-10; the cyclodextrin is C 36 H 60 O 30 (alpha-cyclodextrin), C 42 H 70 O 35 (beta-cyclodextrin), C 48 H 80 O 40 (gamma-cyclodextrin), C 56 H 98 O 35 (dimethyl-beta-cyclodextrin), C 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin), C 63 H 112 O 35 (trimethyl-beta-cyclodextrin) or C 84 H 112 O 56 (triacetyl- β -cyclodextrin); i 2 The molar ratio of the cyclodextrin to the cyclodextrin is in the range of 0.01-30; the cellulose is methyl cellulose, ethyl cellulose, cellulose triacetate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose or hydroxyPropyl methylcellulose, I 2 The molar ratio of the cellulose to the cellulose is in the range of 0.0001-10; i 2 The molar ratio of the catalyst to the photocatalyst is in the range of 0.01-90.
4. A method for preparing the functional filler according to claim 1, which is prepared by adopting a layer-by-layer modification method, and comprises the following specific steps:
step 1: adding polyiodide ions into the solution, and stirring at 25-200deg.C for 30-120 min; wherein the polyiodide is represented by I - And I 2 The composition of the multi-iodine ion is that the concentration of multi-iodine ion is 0.1-25 g/L; i - KI, naI, agI, znI of a shape of KI, naI, agI, znI 2 、NH 4 I、CoI 2 、C 6 H 8 IN、C 12 H 8 ClI、C 14 H 18 IN、C 16 H 36 I 3 N or C 16 H 36 Br 2 IN; the solution is a mixed solution of water and cyclodextrin; in the mixed solution of water and cyclodextrin, the concentration of the cyclodextrin is 0.5-500 g/L; cyclodextrin is C 36 H 60 O 30 (alpha-cyclodextrin), C 42 H 70 O 35 (beta-cyclodextrin), C 48 H 80 O 40 (gamma-cyclodextrin), C 56 H 98 O 35 (dimethyl-beta-cyclodextrin), C 56 H 98 O 42 (2-hydroxy-beta-cyclodextrin), C 63 H 112 O 35 (trimethyl-beta-cyclodextrin) or C 84 H 112 O 56 (triacetyl- β -cyclodextrin);
step 2: adding the photocatalyst into the mixed solution prepared in the step 1, stirring at 25-200 ℃ for 1-5 h, and filtering to obtain a filter cake; the photocatalyst is used for preparing the catalyst in step 1 2 The molar ratio of (2) is in the range of 0.01-100; the photocatalyst is TiO 2 、ZnO、SnO 2 、SrTiO 3 、KTaO 3 、K 4 Nb 6 O 17 、BaTiO 3 、Cu 2 O、CdS、WO 3 、g-C 3 N 4 、BiVO 4 Or Ag 3 PO 4 ；
Step 3: adding the filter cake obtained in the step 2 into a mixed solution of water and cellulose, stirring at 25-200 ℃ for 0.5-48 and h, filtering or centrifuging, and drying at 25-200 ℃ to obtain the functional filler; wherein, in the mixed solution of water and cellulose, the concentration of cellulose is 0.5-50 g/L; the cellulose is methyl cellulose, ethyl cellulose, cellulose triacetate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose or hydroxypropyl methyl cellulose.
5. Use of the functional filler of claim 1 for the preparation of degradable plastic articles.
6. The use according to claim 5, wherein the plastic article is produced by a cast film process comprising the following specific steps:
step 1: dissolving plastic in water or one of the following organic solvents at 20-200 ℃: isopropyl alcohol, cyclohexane and propyl alcohol
Ketones, ethanol, propanol, formic acid, xylene or tetrahydrofuran; the plastic comprises: polyethylene, polystyrene, polyvinyl chloride, polypropylene, polyamide, polylactic acid, polymethacrylate or polyethylene terephthalate; the concentration of the plastic is 1-20g/L;
step 2: adding the functional filler into the solution containing the plastic in the step 1, wherein the mass ratio of the functional filler to the plastic is 0.001-0.8;
step 3: stirring and mixing at 25-200deg.C for 0.1-5 h;
step 4: coating the mixture prepared in the step 3 on a substrate, and drying at 25-200 ℃ to obtain a degradable plastic product with a visual stability period, wherein the degradable plastic product has one of the following colors: black blue, brown, black, brown, coffee or gray, wherein the weight reduction rate is 0.01-1% within 0.5-90 days of sunlight illumination, the color is changed into light blue, light brown, light black, light brown, light coffee, light gray or white after 0.5-90 days of sunlight illumination, and the weight reduction rate is improved to 5-100% after the illumination is continued for 0.5-90 days; the degradable plastic product is independently arranged on the surface of the substrate as a coating or peeled off from the substrate; when the degradable plastic product is used as a coating, the substrate is selected from polyethylene, polystyrene, polypropylene, polyamide, glass or quartz; when the degradable plastic article is independently present, the substrate is selected from glass, quartz, or a low surface energy polymer; wherein the low surface energy polymer is: polyvinylidene fluoride, polytetrafluoroethylene or ethylene-tetrafluoroethylene copolymers.
7. The use according to claim 5, wherein the plastic article is produced by an extrusion film forming process comprising the specific steps of:
step 1: mixing the functional filler with the plastic master batch, wherein the mass ratio of the functional filler to the plastic master batch is 0.001-0.8; wherein, the mixing mode of the functional filler and the plastic master batch:
adding the functional filler and the plastic master batch mixture into an extruder; or alternatively, the process may be performed,
firstly, adding plastic master batches into an extruder, and adding functional fillers at the middle end of the extruder;
step 2: using an extruder, extruding at a temperature of 50-280 ℃ to prepare a degradable plastic product with a visual stability period, wherein the degradable plastic product has one of the following colors: the weight reduction rate of black blue, brown, cyanosis, brown, coffee or gray is 0.01-1% within 0.5-90 days of sunlight illumination, the color is changed into light blue, light brown, light cyanosis, light brown, light coffee, light gray or white after 0.5-90 days of sunlight illumination, the weight reduction rate is improved to 5-100% after the illumination is continued for 0.5-90 days.
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