CN108034199A - High filled biodegradable radiation cross-linked foam material and preparation method thereof - Google Patents

Abstract

The highly filled biodegradable radiation cross-linked foam material and its preparation method belong to the technical field of polymers and their processing. The invention solves the problem of how to provide a foam material with excellent physical properties, good water resistance, good durability, high expansion ratio and adjustable mechanical properties in a wide range. The foam material of the present invention comprises 60-100 parts by weight of polybutylene adipate-terephthalate, 0-40 parts by weight of filler, 0.5-15 parts by weight of foaming agent, and 0.01-5 parts by weight of auxiliary foam Agent and 0.1‑10 parts by weight of crosslinking agent. Wherein, the crosslinking agent is one or more of vinyltrimethylsilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane. The foam material has the advantages of excellent physical properties, good water resistance, good durability, and high foaming ratio, and by adding corresponding fillers for foaming, the mechanical properties of the foaming material can be adjusted in a wide range .

Description

Highly filled biodegradable radiation crosslinked foam material and preparation method thereof

technical field

The invention belongs to the technical field of polymers and their processing, and in particular relates to a high-filling biodegradable radiation-crosslinked foam material and a preparation method thereof.

Background technique

Polymer foam is a special multiphase material. It is composed of solid polymer and gas phase. It is a polymer material with plastic as the basic component and contains a large number of bubbles. Therefore, it can also be regarded as a gas-filled material. composite plastic. Compared with pure plastic, it has many excellent properties, such as light weight, high specific strength, absorbable impact load, good heat insulation and sound insulation performance, etc. Therefore, it has been widely used in industry, agriculture, construction, transportation and other fields.

At present, foam materials are mainly polymer foams such as polyethylene (PE) foam, polypropylene (PP) foam, polystyrene (PS) foam, polyvinyl chloride (PVC) foam and polyurethane (PU). Large in size, difficult to recycle, and non-degradable in the natural environment, bringing serious environmental problems and exacerbating "white pollution". Therefore, due to environmental considerations, vigorously developing and promoting degradable foam materials to replace traditional polymer foam materials has attracted worldwide attention from academia and industry. Compared with general-purpose foam materials, the biodegradable foam materials currently on the market have poor mechanical properties, poor water resistance, and poor product durability.

Poly(butylene adipate-terephthalate) is obtained by polycondensation of adipic acid, terephthalic acid and butanediol. It can be finally degraded into carbon dioxide and water under the action of bacteria or enzymes. Environmentally friendly. Moreover, since the raw materials used in the synthesis are relatively easy to obtain, and the synthesis process is simpler than the microbial fermentation method, etc., there are obvious advantages in cost. It is hoped that it will replace general-purpose polyethylene or polypropylene and enter the field of general-purpose plastics to alleviate the pollution caused by traditional plastics to the environment. BASF of Germany has realized the industrialized production of polybutylene adipate-terephthalate, whose trade name is It is a truly biodegradable plastic produced by BASF, because it can decompose in only a few weeks in the soil or fertilizer, and it will not leave any residue. Therefore, after it is prepared into a foam material, the pollution problem caused by the traditional foam material can be effectively solved. BASF launched this product to the market in 1998. Due to its excellent quality, it has become a leading man-made biodegradable material in the world market. In China, many enterprises have realized the industrial production of polybutylene adipate-terephthalate.

Although poly(butylene adipate-terephthalate) has excellent degradability and has been widely used, but with the improvement of people's pursuit of product quality, the performance requirements of foam materials are not only Satisfied with its environmental protection, people hope that it can have excellent comprehensive properties, such as physical properties, water resistance, durability, etc., and in order to meet the needs of different applications, there is also a certain vision for the controllability of material properties.

Contents of the invention

The purpose of the present invention is to solve the problem of how to provide a high-filling material with excellent physical properties, good water resistance, good durability, high expansion ratio, and the ability to regulate the mechanical properties of foamed materials within a wide range. Biodegradable radiation crosslinked foam material and its preparation method.

The technical scheme that the present invention solves the problems of the technologies described above is as follows:

Highly filled biodegradable radiation crosslinked foam material and preparation method thereof, including:

The crosslinking agent is a mixture of one or more of vinyltrimethylsilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane in any proportion;

The filler is one of starch, cellulose, lignin, silicon dioxide, talcum powder, montmorillonite, and calcium carbonate.

Preferably, the composition and parts by weight are:

Preferably, the blowing agent is azodicarbonamide, barium azodicarboxylate, diisopropyl azodicarboxylate, N,N-dinitrosopentamethylenetetramine, 4,4' - One or more of the oxybisbenzenesulfonyl hydrazides are mixed in any proportion.

Preferably, the foaming aid is one or more of zinc oxide, zinc stearate, and calcium stearate mixed in any proportion.

The above-mentioned high-filling biodegradable radiation-crosslinked foam material and its preparation method, the steps are as follows:

Step 1. Weigh each raw material according to the composition and parts by weight, add it to the extruder for mixing and granulation, the mixing and granulation temperature is 80-170°C, and the obtained mixing and granulating material is extruded on the sheet extruder Sheet, the thickness of the sheet is 0.5-3.0mm, and the extrusion temperature is 100-170°C;

Step 2, performing radiation crosslinking on the blend sheet in air at room temperature, with an irradiation dose of 0.5-9KGy, to obtain a precrosslinked material;

Step 3, further cross-linking the pre-crosslinked material in a hot water bath at 50-80°C for 2-48 hours to obtain a cross-linked material;

Step 4: Foaming the cross-linked material at a temperature of 190-250° C. for 1-20 minutes to obtain a highly filled biodegradable radiation-cross-linked foam material.

Preferably, the mixing and granulation is completed in a twin-screw extruder, and the equipment for extruding the sheet is a single-screw sheet extruder.

Preferably, the source of ionizing radiation is a ⁶⁰ Co source or an electron accelerator.

Preferably, the cross-linked material is foamed in a vertical or horizontal foaming furnace.

Compared with prior art, the beneficial effect of the present invention is:

The high-filling, biodegradable radiation-crosslinked foam material of the present invention and its preparation method have the advantages of excellent physical properties, good water resistance, good durability, and high expansion ratio, and can be foamed by adding corresponding fillers, The mechanical properties of the foamed material can be regulated in a wide range, such as compressive strength, compressive modulus, etc., so that it can meet more application fields. After testing, the apparent density of the foamed material of the present invention is 50- 500Kg/m ³ , tensile strength 1.10-2.64MPa, elongation at break 370-560%, compressive strength 0.45-5.56MPa.

The high-filling biodegradable radiation-crosslinked foam material of the present invention and its preparation method use vinyl-containing silane as a crosslinking agent to realize terephthalic acid-butylene terephthalate under low radiation doses Esters and their blends are irradiated and cross-linked to reduce the cost of irradiated processing. At the same time, the biodegradation rate of these biodegradable foaming materials can be accelerated by introducing silicon-oxygen bonds between molecular chains;

The preparation method of the highly filled biodegradable radiation crosslinked foam material of the present invention adopts the combination of radiation crosslinking and hydrothermal crosslinking, which can ensure that the material meets the needs of foaming, and obtains excellent physical properties, good water resistance and good durability , Foam plastics with higher expansion ratio, and further reduce the radiation dose;

The preparation method of the high-filling biodegradable radiation crosslinking foam material of the present invention adopts radiation crosslinking at room temperature, and the operation is simple.

Detailed ways

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with specific embodiments, but it should be understood that these descriptions are only to further illustrate the characteristics and advantages of the present invention rather than limit the claims of the present invention.

The highly filled biodegradable radiation-crosslinked foam material of the present invention consists of 60-100 parts by weight of polybutylene adipate-terephthalate, 0-40 parts by weight of a filler, and 0.5-15 parts by weight of a foaming agent. , 0.01-5 parts by weight of foaming aid and 0.1-10 parts by weight of crosslinking agent.

Among them, the weight part of polybutylene adipate-terephthalate is preferably 70-90, more preferably 75-85. The filler is one of starch, cellulose, lignin, silicon dioxide, talcum powder, montmorillonite, and calcium carbonate, and the parts by weight are preferably 10-35, more preferably 15-25. The foaming agent is azodicarbonamide, barium azodicarboxylate, diisopropyl azodicarboxylate, N,N-dinitrosopentamethylenetetramine, 4,4'-oxobisbenzenesulfonate One or more of the hydrazides are mixed in any proportion, preferably 5-10 parts by weight, more preferably 6-9 parts, and especially preferably 8 parts by weight. Foaming aid is the mixture of one or more of zinc oxide, zinc stearate and calcium stearate in any proportion, and the parts by weight are preferably 3-5, more preferably 3.5-4. The crosslinking agent is one or more of vinyltrimethylsilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane mixed in any proportion, and the parts by weight are preferably 4-9, more preferably 5.5-8, especially preferably 6-7.

The preparation method of highly filled biodegradable radiation crosslinked foam material of the present invention, the steps are as follows:

Step 1. Weigh each raw material according to the composition and parts by weight, and add it to a twin-screw extruder for mixing and granulation. The mixing and granulation temperature is 80-170°C. Extrude the sheet on the machine, the thickness of the sheet is 0.5-3.0mm, preferably 1mm, and the extrusion temperature is 100-170°C;

Step 2, performing radiation crosslinking on the blend sheet in air at room temperature, with an irradiation dose of 0.5-9KGy, to obtain a precrosslinked material;

Step 3, further cross-linking the pre-crosslinked material in a hot water bath at 50-80°C for 2-48 hours to obtain a cross-linked material;

Step 4. Foam the cross-linked material in a vertical or horizontal foaming furnace at a temperature of 190-250°C for 1-20 minutes, preferably at 220-240°C for 4-10 minutes to obtain highly filled bio Degradation of radiation crosslinked foams.

The present invention will be further described in detail through examples below. However, the present invention is not limited to these examples.

Example 1

Highly filled biodegradable radiation crosslinked foam material: 100 parts by weight of polybutylene adipate-terephthalate, 5 parts by weight of azodicarbonamide, 1 part by weight of zinc oxide and vinyltrimethylsilane 0.5 parts by weight.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 1.0mm. Then, an electron accelerator was used to pre-irradiate the sheet in air at room temperature with a radiation dose of 9KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 80°C for 2 hours. Finally, foaming was carried out in a vertical foaming furnace, the foaming temperature was 220° C., and the foaming time was 4 minutes to obtain a foam material.

The foam material obtained in Example 1 was tested for performance, and the test results are shown in Table 1.

Example 2

Highly filled biodegradable radiation cross-linked foam material: 60 parts by weight of polybutylene adipate-terephthalate, 40 parts by weight of starch, 5 parts by weight of azodicarbonamide, 1 part by weight of zinc oxide and It consists of 0.5 parts by weight of vinyltriethoxysilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 1.0mm. Then, an electron accelerator was used to pre-irradiate the sheet in air at room temperature with a radiation dose of 9KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 60°C for 36 hours. Finally, foaming was carried out in a vertical foaming furnace, the foaming temperature was 230° C., and the foaming time was 4 minutes to obtain a foam material.

The foam material obtained in Example 2 was tested for performance, and the test results are shown in Table 1.

Example 3

Highly filled biodegradable radiation-crosslinked foam material: 90 parts by weight of polybutylene adipate-terephthalate, 10 parts by weight of starch, and 15 parts by weight of 4,4'-oxobisbenzenesulfonyl hydrazide , 2 parts by weight of calcium stearate and 0.1 part by weight of vinyl tris (β-methoxyethoxy) silane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 1.5mm. Using ⁶⁰ Co source, the sheet was pre-irradiated in air at room temperature with a radiation dose of 8KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 70°C for 30h. Finally, it is foamed in a vertical foaming furnace, the foaming temperature is 250° C., and the foaming time is 1 min to obtain a foam material.

The foam material obtained in Example 3 was tested for performance, and the test results are shown in Table 1.

Example 4

Highly filled biodegradable radiation cross-linked foam material: 80 parts by weight of polybutylene adipate-terephthalate, 20 parts by weight of cellulose, 10 parts by weight of azodicarbonamide, and 2 parts by weight of stearic acid and 2 parts by weight of vinyltriethoxysilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 2.0mm. Using an electron accelerator, the sheet was pre-irradiated in air at room temperature with a radiation dose of 7KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 80°C for 10 hours. Finally, foaming was carried out in a vertical foaming furnace, the foaming temperature was 220° C., and the foaming time was 4 minutes to obtain a foam material.

The performance of the foam material obtained in Example 4 was tested, and the test results are shown in Table 1.

Example 5

Highly filled biodegradable radiation crosslinked foam material: 70 parts by weight of polybutylene adipate-terephthalate, 30 parts by weight of cellulose, 12 parts by weight of barium azodicarboxylate, 5 parts by weight of zinc stearate parts by weight and 10 parts by weight of vinyltrimethylsilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet was pre-irradiated in air at room temperature with a radiation dose of 0.5KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 80°C for 2 hours. Finally, it is foamed in a vertical foaming furnace, the foaming temperature is 240° C., and the foaming time is 3 minutes to obtain a foam material.

The foam material obtained in Example 5 was tested for performance, and the test results are shown in Table 1.

Example 6

Highly filled biodegradable radiation crosslinked foam material: 75 parts by weight of polybutylene adipate-terephthalate, 25 parts by weight of lignin, N,N-dinitrosopentamethylenetetramine 10 parts by weight, 1 part by weight of zinc stearate and 8 parts by weight of vinyl tris(β-methoxyethoxy)silane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 1.5mm. Using ⁶⁰ Co source, the sheet was pre-irradiated in air at room temperature with a radiation dose of 9KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 70°C for 8h. Finally, it is foamed in a vertical foaming furnace, the foaming temperature is 210° C., and the foaming time is 10 minutes to obtain a foam material.

The foam material obtained in Example 6 was tested for performance, and the test results are shown in Table 1.

Example 7

Highly filled biodegradable radiation-crosslinked foam material: 95 parts by weight of polybutylene adipate-terephthalate, 5 parts by weight of lignin, 10 parts by weight of azodicarbonamide, and 1 part by weight of stearic acid and 0.05 parts by weight of vinyl tris(β-methoxyethoxy)silane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet was pre-irradiated in air at room temperature with a radiation dose of 6KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 80°C for 6h. Finally, foaming was carried out in a vertical foaming furnace, the foaming temperature was 220° C., and the foaming time was 4 minutes to obtain a foam material.

The performance of the foam material obtained in Example 7 was tested, and the test results are shown in Table 1.

Example 8

Highly filled biodegradable radiation cross-linked foam material: 60 parts by weight of polybutylene adipate-terephthalate, 40 parts by weight of silicon dioxide, 10 parts by weight of azodicarbonamide, and 5 parts by weight of zinc oxide and 2 parts by weight of vinyltriethoxysilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 1.0mm. Using an electron accelerator, the sheet was pre-irradiated in air at room temperature with a radiation dose of 8KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 60°C for 40h. Finally, it is foamed in a vertical foaming furnace, the foaming temperature is 240° C., and the foaming time is 2 minutes to obtain a foam material.

The performance of the foam material obtained in Example 8 was tested, and the test results are shown in Table 1.

Example 9

Highly filled biodegradable radiation cross-linked foam material: 85 parts by weight of polybutylene adipate-terephthalate, 15 parts by weight of silicon dioxide, 15 parts by weight of diisopropyl azodicarboxylate, hard It consists of 0.01 parts by weight of zinc fatty acid and 3 parts by weight of vinyl tris(β-methoxyethoxy)silane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 2.5mm. Using an electron accelerator, the sheet was pre-irradiated in air at room temperature with a radiation dose of 9KGy, and the pre-irradiated cross-linked sheet was further cross-linked in a hot water bath at 80°C for 4 hours. Finally, it is foamed in a vertical foaming furnace, the foaming temperature is 200° C., and the foaming time is 12 minutes to obtain a foam material.

The foam material obtained in Example 9 was tested for performance, and the test results are shown in Table 1.

Example 10

Highly filled biodegradable radiation crosslinked foam material: 65 parts by weight of polybutylene adipate-terephthalate, 35 parts by weight of talcum powder, 5 parts by weight of barium azodicarboxylate, 1 part by weight of zinc stearate It is composed of 8 parts by weight and vinyltrimethylsilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet is pre-irradiated in air at room temperature, and the irradiation dose is 2KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 70°C for 12 hours, and foamed horizontally Foaming was carried out in a furnace, the foaming temperature was 250° C., and the foaming time was 1 min to obtain a foam material.

The performance of the foam material obtained in Example 10 was tested, and the test results are shown in Table 1.

Example 11

Highly filled biodegradable radiation cross-linked foam material: 75 parts by weight of polybutylene adipate-terephthalate, 25 parts by weight of talcum powder, N,N-dinitrosopentamethylenetetramine 10 parts by weight, 3 parts by weight of stearic acid and 0.2 parts by weight of vinyltriethoxysilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 1mm. Use an electron accelerator to pre-irradiate the sheet in the air at room temperature, and the irradiation dose is 9KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 80°C for 2 hours, and foamed horizontally Foaming was carried out in a furnace, the foaming temperature was 190° C., and the foaming time was 20 minutes to obtain a foam material.

The performance of the foam material obtained in Example 11 was tested, and the test results are shown in Table 1.

Example 12

Highly filled biodegradable radiation cross-linked foam material: 90 parts by weight of polybutylene adipate-terephthalate, 10 parts by weight of montmorillonite, 15 parts by weight of diisopropyl azodicarboxylate, hard It consists of 5 parts by weight of calcium fatty acid and 10 parts by weight of vinyltriethoxysilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet is pre-irradiated in air at room temperature, and the irradiation dose is 0.5KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 70°C for 6 hours, Foaming in a foaming furnace, the foaming temperature is 220° C., and the foaming time is 1 min to obtain a foam material.

The foam material obtained in Example 12 was tested for performance, and the test results are shown in Table 1.

Example 13

Highly filled biodegradable radiation crosslinked foam material: 70 parts by weight of polybutylene adipate-terephthalate, 30 parts by weight of montmorillonite, 15 parts by weight of azodicarbonamide, 5 parts by weight of stearic acid It consists of 6 parts by weight of vinyl tris (β-methoxyethoxy) silane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Use an electron accelerator to pre-irradiate the sheet in the air at room temperature, and the irradiation dose is 5KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 60°C for 20 hours, and foamed horizontally Foaming was carried out in a furnace, the foaming temperature was 220° C., and the foaming time was 2 minutes to obtain a foam material.

The foam material obtained in Example 13 was tested for performance, and the test results are shown in Table 1.

Example 14

Highly filled biodegradable radiation cross-linked foam material: 85 parts by weight of polybutylene adipate-terephthalate, 15 parts by weight of calcium carbonate, N,N-dinitrosopentamethylenetetramine 15 parts by weight, 5 parts by weight of zinc oxide and 10 parts by weight of vinyl tris(β-methoxyethoxy)silane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Use an electron accelerator to pre-irradiate the sheet in the air at room temperature, and the irradiation dose is 9KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 70°C for 8 hours, and foamed horizontally Foaming was carried out in a furnace, the foaming temperature was 220° C., and the foaming time was 2 minutes to obtain a foam material.

The foam material obtained in Example 14 was tested for performance, and the test results are shown in Table 1.

Example 15

Highly filled biodegradable radiation crosslinked foam material: 75 parts by weight of polybutylene adipate-terephthalate, 25 parts by weight of calcium carbonate, 10 parts by weight of azodicarbonamide, and 5 parts by weight of zinc oxide It is composed of 10 parts by weight of vinyltriethylsilane.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet is pre-irradiated in air at room temperature, and the irradiation dose is 9KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 70°C for 10 hours, and foamed horizontally. Foaming was carried out in a furnace, the foaming temperature was 200° C., and the foaming time was 12 minutes to obtain a foam material.

The foam material obtained in Example 15 was tested for performance, and the test results are shown in Table 1.

Comparative example 1

Highly filled biodegradable radiation crosslinked foam material: 75 parts by weight of polybutylene adipate-terephthalate, 25 parts by weight of calcium carbonate, 10 parts by weight of azodicarbonamide, and 5 parts by weight of zinc oxide and 10 parts by weight of triallyl isocyanurate.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet is pre-irradiated in air at room temperature, and the irradiation dose is 9KGy. The pre-irradiated cross-linked sheet is further cross-linked in a hot water bath at 70°C for 10 hours, and foamed horizontally. Foaming was carried out in a furnace, the foaming temperature was 200° C., and the foaming time was 12 minutes to obtain a foam material.

Comparative example 2

Highly filled biodegradable radiation crosslinked foam material: 75 parts by weight of polybutylene adipate-terephthalate, 25 parts by weight of calcium carbonate, 10 parts by weight of azodicarbonamide, and 5 parts by weight of zinc oxide and 10 parts by weight of triallyl isocyanurate.

The preparation of the above-mentioned high-filling biodegradable radiation-crosslinked foam material: take each raw material according to the proportion, add it to a twin-screw extruder for mixing and granulation, the mixing and granulation temperature is 80-170 ° C, and the obtained pellets are obtained by single-screw extruder The extruder is extruded into a sheet, the extrusion temperature is 100-170°C, and the thickness of the sheet is 0.5mm. Using an electron accelerator, the sheet is pre-irradiated in air at room temperature, and the irradiation dose is 100KGy. Foaming in a horizontal foaming furnace, the foaming temperature is 200°C, and the foaming time is 12 minutes, the foam material cannot be prepared.

The apparent density, expansion ratio, tensile strength, elongation at break, compressive strength and durability of the biodegradable radiation-crosslinked foam materials of Examples 1-15 and Comparative Example 2 were detected. Among them, the apparent density is tested by GB-T-6343-2009; the tensile strength and elongation at break are tested by the method in GB/T6344-1996; the compressive strength is tested by the method in GB/T8813-2008; The method used for durability is tested. The test results are shown in Table 1.

The performance of the biodegradable radiation crosslinked foam material of table 1 embodiment 1-15 and comparative example 1-2

As can be seen from Table 1, only by using the crosslinking agent of the present invention, can two-step crosslinking prepare the foam material with excellent properties, and the crosslinking agent in the prior art cannot adopt low irradiation dose to carry out crosslinking (comparative example 1) , the high-filling biodegradable radiation-crosslinked foam material of the present invention has the advantages of excellent physical properties, good durability, and high expansion ratio, which is not lower than that of the foam material prepared by cross-linking with a large radiation dose in the prior art. technology (comparative example 2), and by blending and foaming with other biodegradable polymers, such as polylactic acid, carbon dioxide-propylene oxide copolymer, polybutylene succinate, etc., it can be used in a wide range Internal regulation of the mechanical properties of the foamed material.

The water resistance of the foam materials of Examples 1-15 was tested by immersing the highly filled biodegradable radiation-crosslinked foam materials in water at 80 degrees Celsius for 15 days. After testing, after soaking for 30 days, the appearance of the foam material of the present invention is good without obvious change, and the tensile strength has no obvious decrease. It shows that the foam material of the present invention has good water resistance.

Claims (8)

1. high filled biodegradable radiation cross-linked foam material, it is characterised in that including：

The crosslinking agent is vinyl trimethylsilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) One or more mixing in any proportion in silane；

The filler is one kind in starch, cellulose, lignin, silica, talcum powder, montmorillonite, calcium carbonate.

2. high filled biodegradable radiation cross-linked foam material according to claim 1, it is characterised in that composition and weight Part it is：

3. high filled biodegradable radiation cross-linked foam material, it is characterised in that the foaming agent is azodicarbonamide, idol Nitrogen dioctyl phthalate barium, diisopropyl azodiformate, N, in N- dinitrosopentamethlyene tetramines, 4,4 '-oxobenzenesulfonyl hydrazide One or more mixing in any proportion.

4. high filled biodegradable radiation cross-linked foam material, it is characterised in that the blowing promotor is zinc oxide, stearic acid One or more mixing in any proportion in zinc, calcium stearate.

5. the preparation method of the high filled biodegradable crosslinking with radiation described in claim 1-4 any one, it is characterised in that Step is as follows：

Step 1: weighing each raw material by composition and parts by weight, add in extruder and carry out mixing granulator, mixing granulator temperature is 80-170 DEG C, obtained mixing granulator material extrusion sheet on sheet extruder, sheet thickness 0.5-3.0mm, extrusion temperature For 100-170 DEG C；

Step 2: at room temperature in air, crosslinking with radiation is carried out to blend sheet, irradiation dose 0.5-9KGy, is pre-payed Join material；

Step 3: by precrosslink material, 2-48h is further crosslinked in 50-80 DEG C of hot bath, obtains crosslinking material；

Step 4: crosslinking material is foamed, temperature is 190-250 DEG C, time 1-20min, and obtaining high filling can biology Degraded radiation cross-linked foam material.

6. the preparation method of high filled biodegradable crosslinking with radiation according to claim 5, it is characterised in that mixing is made Grain is completed in double screw extruder, and the equipment of extrusion sheet is single screw rod sheet extruder.

7. the preparation method of high filled biodegradable crosslinking with radiation according to claim 5, it is characterised in that ionization spoke The source of penetrating is⁶⁰Co sources or electron accelerator.

8. the preparation method of high filled biodegradable crosslinking with radiation according to claim 5, it is characterised in that cross-linking agent Material foams in vertical or horizontal foaming furnace.