Full-degradable short fiber reinforced foam material and preparation method thereof

Abstract

The invention belongs to the technical field of foaming materials, and discloses a fully-degradable short fiber reinforced foaming material and a preparation method thereof. The foaming material is prepared from the following materials in parts by weight: 100 parts of poly (adipic acid) / butylene terephthalate, 8-45 parts of starch, 2-15 parts of glycerol, 3-10 parts of regenerated cellulose short fibers with the length of 1.0-8.0 mm and the diameter of 11-13 microns, 8-26 parts of water, 1-40 parts of talcum powder with the particle size of 1250-5000 meshes and 0.2-2.2 parts of a curing agent, wherein the ratio of the regenerated cellulose short fibers to the water is 1.0: (2.0-3.0). The biomass short fibers are introduced, the compression modulus of the foam material is increased by 20% under the same foaming ratio, continuous and stable production of foam wires can be achieved, the technology is simple, the production process is safe and environmentally friendly, and the obtained foam material can replace non-degradable foam to be used for cushion packaging materials such as disposable cushions.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of foamed materials, specifically to the technical field of disposable cushion packaging materials and shockproof filling materials, and more specifically to a fully degradable short fiber reinforced foamed material and a preparation method thereof. BACKGROUND

[0002] Foamed materials are widely used in people's production and life. With the tightening of environmental protection policies and the global attention to plastic pollution control, the use of non-degradable foamed materials such as polystyrene, polyethylene, and polyvinyl chloride is huge and difficult to recycle and process, causing serious environmental pollution. The problem of difficult degradation and long-term environmental pollution has become a pain point in the industry, and the application is also strictly limited.

[0003] Using fully biodegradable materials to make foamed materials can reduce the pollution of foamed materials to the environment and reduce the difficulty of recycling and processing. Existing degradable foamed materials are mostly based on polybutylene adipate terephthalate (PBAT) and starch, but there are obvious defects. Using fully biodegradable materials to make foamed materials requires solving the problems of material selection and processing technology. The existing degradable foamed materials have poor performance, resulting in poor foam strength and resilience, and the control of foaming ratio and cell density requires high processing technology.

[0004] Therefore, it is a key requirement to develop a foamed material with excellent mechanical strength, full biodegradability, and stable production process to solve the bottleneck of existing technology. SUMMARY

[0005] The present application aims to solve the problems of insufficient mechanical strength, poor production stability, and limited degradation performance of existing degradable foamed materials, and provides a fully degradable short fiber reinforced foamed material and a preparation method thereof, achieving the following objectives: 1. improving the compression resistance and structural stability of the foamed material; 2. ensuring that the material can be completely degraded in natural environment or conventional composting conditions; 3. simplifying the production process, realizing continuous and stable production, and reducing production cost.

[0006] To achieve the purpose of the present application, the fully degradable short fiber reinforced foamed material of the present application comprises polybutylene adipate terephthalate (PBAT), starch, glycerol, regenerated cellulose short fiber, water, talcum powder, and curing agent.

[0007] Further, in some embodiments of the present application, the fully degradable short fiber reinforced foamed material is made from the following raw materials by weight: polybutylene adipate terephthalate (PBAT) 100 parts, starch 8-45 parts, glycerol 2-15 parts, regenerated cellulose short fiber with a length of 1.0-8.0 mm and a diameter of 11-13 μm 3-10 parts, water 8-26 parts, talcum powder 1-40 parts, and curing agent 0.2-2.2 parts.

[0008] Further, in some embodiments of the present application, the fully degradable short fiber reinforced foamed material is made of the following raw materials in parts by weight: polybutylene adipate-co-terephthalate (PBAT) 100 parts, starch 10-40 parts, glycerol 2-12 parts, regenerated cellulose short fiber 3-10 parts with length 1.5-7.5 mm and diameter 11-13 μm, water 8-25 parts, talc 5-30 parts, curing agent 0.3-2.0 parts.

[0009] Further, in some embodiments of the present application, the regenerated cellulose short fiber is regenerated cellulose short fiber with length 2.0-6.0 mm and diameter 11.5-12.5 μm.

[0010] Further, in some embodiments of the present application, the talc has particle size of 1250-5000 mesh.

[0011] Further, in some embodiments of the present application, the ratio of the regenerated cellulose short fiber to water is 1.0:2.0-3.0, and the water provides a carrier for the dispersion of the regenerated cellulose short fiber, which can improve the compatibility of the regenerated cellulose short fiber with the base material.

[0012] Further, in some embodiments of the present application, the curing agent is a high-temperature reaction type curing agent.

[0013] Further, in some embodiments of the present application, the curing agent is one or more of waterborne aromatic isocyanate, waterborne aliphatic isocyanate, and silane coupling agent, which can enhance the interfacial bonding force between the base material and the short fiber.

[0014] In another aspect, the present application also provides a preparation method of a fully degradable short fiber reinforced foamed material, which comprises: mixing starch, glycerol, regenerated cellulose short fiber, talc, and curing agent in a V-type mixer, mixing at high speed and adding water, then adding PBAT and mixing at low speed, and then adding the obtained mixture into an extruder for melt mixing to obtain the fully degradable short fiber reinforced foamed material.

[0015] Further, in some embodiments of the present application, the water is added in two times.

[0016] Further, in some embodiments of the present application, the V-type mixer is a high-speed mixer different from the conventional stirring paddle type, and the V-type mixer is selected to prevent the stratification of different packing states of the powder, liquid, fiber, and particle in the mixing system of the present application.

[0017] Further, in some embodiments of the present application, the high-speed mixing is mixing at 15-20 revolutions / min for 7-13 min.

[0018] Further, in some embodiments of the present application, the low-speed mixing is carried out at a low speed of 6-12 rpm for 3-7 min.

[0019] Further, in some embodiments of the present application, the temperature of the extruder is set at 130-160°C, and the screw rotation speed is 80-150 rpm, which can ensure sufficient melting of the raw materials and avoid excessive degradation.

[0020] Compared with the prior art, the advantages of the present application include but are not limited to: Significant improvement in compression resistance: By introducing regenerated cellulose short fibers of a specific size, the compression strength of the material is increased by more than 20% compared with traditional degraded foaming materials at the same foaming ratio, which can meet the mechanical requirements of cushion packaging.

[0021] Full biodegradability: The raw materials of the foaming material of the present application are all degradable components, and PBAT, starch, and regenerated cellulose short fibers can be completely degraded under natural environment or composting conditions without residual pollution, which meets the environmental protection requirements.

[0022] Excellent production stability: By optimizing the mixing sequence and process parameters, the present application solves the problem of poor compatibility between the base material and the additive, and can realize continuous and stable production of foaming filaments, with a production efficiency improved by more than 30%.

[0023] Wide raw material sources and controllable cost: Starch and regenerated cellulose short fibers are both biomass raw materials, which are abundant in source and low in price. Combined with the use of PBAT, the material cost is reduced while the performance is ensured. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a sample of the foaming material reinforced by the fully degradable short fibers of the present application; Figure 2 is a diagram showing the mixing effect of a V-shaped mixer (left) and the mixing effect of a high-speed mixer with a conventional stirring paddle (right) in the present application. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solutions and advantages of the present application more clear and explicit, the present application is further described in detail below in combination with the drawings and examples. Additional aspects and advantages of the present application will be partially given in the following description, partially will become apparent from the following description, or will be understood by practicing the present application. It should be understood that the following description is only used to explain the present application, and is not used to limit the present application.

[0026] When equivalent, concentration, or other value or parameter is expressed in a range, a preferred range, or a series of upper preferred values and lower preferred values, it is to be understood that all ranges formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, even if the range is not explicitly disclosed, are to be specifically disclosed. For example, if a range "1 to 5" is disclosed, then the description is to be interpreted to include ranges such as "1 to 4," "1 to 3," "1 to 2," "1 to 2 and 4 to 5," "1 to 3 and 5," etc. When numerical ranges are disclosed, unless otherwise stated, the range is intended to include both the upper and lower values and all intervening values of the range, even if the range is not explicitly disclosed.

[0027] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "Optional" or "any of" means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where the event occurs and instances where it does not.

[0028] Approximating language such as, for example, "approximately," "substantially," and "about" are terms concerning the relative tolerances, permits, and / or measurements of magnitude, such that a measurement of a first quantity is approximately equal to a measurement of a second quantity when the magnitude of the first quantity is within a threshold of the magnitude of the second quantity. In some examples, the approximating language can correspond to the precision with which instrument measures the quantity. In the description of the application and in the claims, ranges are described using the terms "between" and "from...to..." These terms are used in their inclusive sense and describe all the values and subranges falling within the indicated ranges. In some examples, the approximating language may

[0029] The indefinite articles "a" and "an," as used herein in the specification, unless clearly indicated to the contrary, should be understood to mean "at least one." The indefinite article "a" or "an" thus includes a plurality unless the context clearly dictates otherwise. Thus, for example, reference to "a component" is a reference to one or more components and thus also covers a plurality of components unless the context clearly dictates otherwise.

[0030] Furthermore, the description herein of any devices, embodiments, examples, or the like that can have claimed priority is intended to embrace both the specific embodiments and examples described and equivalents thereto. Accordingly, features indicated with the suffix "s" and words like "one or more" or "at least one" are intended to embrace both the features individually and in combination. Furthermore, the terms "a" or "an," as used herein in the specification, can mean one or more than one. Finally, the terms "plurality" or "a plurality" as used herein in the specification can mean two or more than two. The terms "first," "second," "third," "fourth," etc. as used herein are not intended to denote a physical order or priority but to denote different claimed subject matter.

[0031] Experimental materials: PBAT: Blue Stone River, TH801T Regenerated cellulose staple: Cordenka, Germany, Rayon Yarn 700 Talcum powder: Liaoning Jinghua New Material Co., Ltd., SK-96, NA-7800, SK-98 Starch: Food-grade corn starch, Jilin COFCO Biochemical Energy Sales Co., Ltd. Glycerol: Superol K, Malaysia Curing agent: Bayhydur® BL 5335, WANNATE® HT-100, Hafotex® HF-9061, KH-550. Example 1

[0032] Raw material composition (weight fraction): PBAT 100 parts, starch 20 parts, glycerol 5 parts, regenerated cellulose short fiber (length 2 mm, diameter 12 μm) 10 parts, water 25 parts (regenerated cellulose short fiber to water ratio 1:2.5), talcum powder (2000 mesh) 15 parts, curing agent BL5335 0.5 parts.

[0033] Preparation process: Add starch, glycerol, regenerated cellulose short fiber, talcum powder, and curing agent to a V-type mixer, first add 12.5 parts of water, mix at a speed of 20 revolutions / min for 5 min; then add the remaining 12.5 parts of water, continue to mix at a speed of 20 revolutions / min for 5 min; Add PBAT, mix at a speed of 10 revolutions / min for 5 min to obtain the mixed material. Add the mixed material to the extruder, set the barrel zone one at 130°C, zone two at 140°C, zone three at 145°C, and the die at 140°C, the screw speed at 100 revolutions / min, melt mix, then extrude and foam, wind ring cooling and granulation to obtain the fully degradable short fiber reinforced foam material. Example 2

[0034] Raw material composition (weight fraction): PBAT 100 parts, starch 40 parts, glycerol 10 parts, regenerated cellulose short fiber (length 6 mm, diameter 12 μm) 7 parts, water 21 parts (regenerated cellulose short fiber to water ratio 1:3), talcum powder (3000 mesh) 30 parts, curing agent HT-100 1.0 parts.

[0035] Preparation process: Add starch, glycerol, regenerated cellulose short fiber, talcum powder, and curing agent to a V-type mixer, first add 10.5 parts of water, mix at a speed of 15 revolutions / min for 5 min; then add the remaining 10.5 parts of water, continue to mix at a speed of 15 revolutions / min for 5 min.

[0036] Add PBAT, mix at a speed of 12 revolutions / min for 5 min to obtain the mixed material.

[0037] The mixture is added into the extruder, and the barrel zone 1, zone 2, zone 3 of the double screw are set to 140℃, 150℃, 155℃, the die is set to 150℃, the screw rotation speed is 120r / min, and the foamed material is obtained after melting and mixing. Example 3

[0038] The raw material composition (weight fraction) is: PBAT 100 parts, starch 10 parts, glycerol 3 parts, regenerated cellulose short fiber (length 3mm, diameter 12μm) 3 parts, water 8.4 parts (regenerated cellulose short fiber and water ratio 1:2.8), talc (1250 mesh) 5 parts, curing agent HF-9061 0.3 parts.

[0039] Preparation process: The starch, glycerol, regenerated cellulose short fiber, talc, and curing agent are added into the V-type mixer, 4.2 parts of water is added first, and high-speed mixing is carried out at 20r / min for 5min; then the remaining 4.2 parts of water is added, and high-speed mixing is continued at 20r / min for 5min.

[0040] PBAT is added, and low-speed mixing is carried out at 6r / min for 5min to obtain the mixture.

[0041] The mixture is added into the extruder, and the barrel zone 1, zone 2, zone 3 of the double screw are set to 120℃, 130℃, 135℃, the die is set to 130℃, the screw rotation speed is 80r / min, and the foamed material is obtained after melting and mixing. Example 4

[0042] The raw material composition (weight fraction) is: PBAT 100 parts, starch 30 parts, glycerol 8 parts, regenerated cellulose short fiber (length 3mm, diameter 12μm) 8 parts, water 20 parts (regenerated cellulose short fiber and water ratio 1:2.5), talc (5000 mesh) 30 parts, curing agent KH-550 2.0 parts.

[0043] Preparation process: The starch, glycerol, regenerated cellulose short fiber, talc, and curing agent are added into the V-type mixer, 10 parts of water is added first, and high-speed mixing is carried out at 18r / min for 5min; then the remaining 10 parts of water is added, and high-speed mixing is continued at 18r / min for 5min.

[0044] PBAT is added, and low-speed mixing is carried out at 10r / min for 5min to obtain the mixture.

[0045] The mixture is added into the extruder, and the barrel zone 1, zone 2, zone 3 of the double screw are set to 150℃, 160℃, 165℃, the die is set to 160℃, the screw rotation speed is 150r / min, and the foamed material is obtained after melting and mixing. Comparative Example 1

[0046] Comparative Example 1 was operated in the same way as Example 2, except that the amount of regenerated cellulose short fiber was 0, and the weight fractions of other materials were unchanged. Comparative Example 2

[0047] Comparative Example 2 was operated in the same way as Example 2, except that the amount of curing agent was 0, and the weight fractions of other materials were unchanged. Comparative Example 3

[0048] Comparative Example 3 was operated in the same way as Example 2, except that the regenerated cellulose short fiber was 12 mm in length and 12 μm in diameter, and the weight fractions of other materials were unchanged. Comparative Example 4

[0049] Comparative Example 1 was operated in the same way as Example 2, except that the amount of water was 28 parts by weight, and was added in two portions, 14 parts each, and the weight fractions of other materials were unchanged. Comparative Example 5

[0050] Comparative Example 1 was operated in the same way as Example 2, except that the mixing was performed in a conventional high-speed mixer, and the procedure was as follows The starch, glycerol, regenerated cellulose short fiber, talc, curing agent, and 10.5 parts of water were added to a high-speed mixer with conventional stirring paddles, and were mixed at 15 revolutions / min for 5 min. The remaining 10.5 parts of water was then added, and the mixing was continued at 15 revolutions / min for 5 min.

[0051] PBAT was added, and was mixed at 12 revolutions / min for 5 min, to obtain the mixed material.

[0052] At this point, the pre-mixed material was obviously layered, as shown in Figure 2 the right-hand drawing, in which the upper layer was mainly powder, fiber, and plasticizer absorbed by the powder, and the lower layer was PBAT granules.

[0053] The foamed materials obtained in each example and comparative example were tested for performance, and the test results are shown in Table 1.

[0054] Table 1 Composition, foaming ratio, and strength of foamed materials of each example and comparative example

[0055] Those skilled in the art will readily understand that the above description is only some examples of the present application, and is not intended to limit the present application, and any modification, equivalent replacement, and improvement, etc. made within the spirit and principles of the present application, should be included in the protection scope of the present application.

Claims

1. A fully degradable short fiber-reinforced foamed material, characterized by, The full-degradation short fiber reinforced foamed material comprises polybutylene adipate terephthalate, starch, glycerol, regenerated cellulose short fiber, water, talcum powder and curing agent.

2. Fully degradable short fiber reinforced foamed material according to claim 1, characterized in that, The full-degradation short fiber reinforced foamed material is made of the following raw materials by weight: 100 parts of polybutylene adipate terephthalate, 8-45 parts of starch, 2-15 parts of glycerol, 3-10 parts of regenerated cellulose short fiber with a length of 1.0-8.0 mm and a diameter of 11-13 μm, 8-26 parts of water, 1-40 parts of talcum powder and 0.2-2.2 parts of curing agent; preferably, the full-degradation short fiber reinforced foamed material is made of the following raw materials by weight: 100 parts of polybutylene adipate terephthalate, 10-40 parts of starch, 2-12 parts of glycerol, 3-10 parts of regenerated cellulose short fiber with a length of 1.5-7.5 mm and a diameter of 11-13 μm, 8-25 parts of water, 5-30 parts of talcum powder and 0.3-2.0 parts of curing agent.

3. Fully degradable short fiber-reinforced foamed material according to claim 1 or 2, characterized in that, The regenerated cellulose short fiber has a length of 2.0-6.0 mm and a diameter of 11.5-12.5 μm.

4. The fully degradable short fiber reinforced foamed material of claim 1, wherein, The talcum powder has a particle size of 1250-5000 mesh.

5. The fully degradable short fiber reinforced foamed material of claim 1, wherein, The regenerated cellulose short fiber is mixed with water at a ratio of 1.0:2.0-3.

0.

6. The fully degradable short fiber reinforced foamed material of claim 1, wherein, The curing agent is a high-temperature reaction type curing agent; preferably, the curing agent is one or more of water-based aromatic isocyanate, water-based aliphatic isocyanate and silane coupling agent.

7. The fully degradable short fiber reinforced foamed material of claim 1, wherein, The starch, glycerol, regenerated cellulose short fiber, talcum powder and curing agent are mixed in a V-type mixer during the preparation of the full-degradation short fiber reinforced foamed material.

8. Process for the production of fully degradable short fiber reinforced foamed materials according to any one of claims 1 to 7, characterized in that, The method comprises: mixing the starch, glycerol, regenerated cellulose short fiber, talcum powder and curing agent in a V-type mixer, mixing at high speed and adding water, then adding PBAT and mixing at low speed, and then adding the obtained mixture into an extruder for melt mixing to obtain the full-degradation short fiber reinforced foamed material.

9. The process for the production of fully degradable short fiber reinforced foamed materials according to claim 8, characterized in that, The water is added in two times.

10. The process for producing a fully degradable short fiber reinforced foam material according to claim 8, wherein, The high-speed mixing is mixing at 15-20 revolutions / min for 7-13 min; preferably, the low-speed mixing is mixing at 6-12 revolutions / min for 3-7 min; preferably, the temperature of the extruder is set at 130-160 °C and the screw rotation speed is 80-150 revolutions / min.

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