阅读说明：本技术 纤维增韧的多层塑料型材及其制备方法、可降解食物餐盒 (Fiber-toughened multilayer plastic profile, preparation method thereof and degradable food lunch box ) 是由 徐建海 王美兰 于 2021-09-26 设计创作，主要内容包括：本申请公开了一种纤维增韧的多层塑料型材及其制备方法、可降解食物餐盒。本申请的多层塑料型材包括由混合填料和第一树脂料获得的填料树脂混合物,以及由玻璃纤维和第二树脂料获得的纤维树脂混合物。其中,填料树脂混合物的表面具有切割缝,纤维树脂混合物能够嵌入该切割缝中。由此,本申请的多层塑料型材具有交叉式的纤维增韧结构,其层间结合性能较优,机械性能和韧性均较好。(The application discloses a fiber toughened multilayer plastic profile, a preparation method thereof and a degradable food lunch box. The multilayer plastic profile of the present application comprises a filler resin mixture obtained by mixing a filler and a first resin material, and a fiber resin mixture obtained by glass fibers and a second resin material. Wherein the surface of the filler resin mixture has a cut seam into which the fiber resin mixture can be inserted. Therefore, the multilayer plastic profile has a crossed fiber toughening structure, and has better interlayer bonding performance, mechanical performance and toughness.)

1. A preparation method of a fiber toughened multilayer plastic profile is characterized by comprising the following steps:

s100, preparing a mixed filler, glass fibers, a first resin material and a second resin material respectively;

s200, mixing and extruding the mixed filler and the first resin material to obtain a filler resin mixture;

s300, spreading the filler resin mixture in a mold, carrying out first curing treatment, and cutting a plurality of cross cutting seams arranged in an array on the surface of the filler resin mixture subjected to the first curing treatment;

s400, guiding the glass fibers into the mold along a first direction, arranging the glass fibers on one side, provided with the plurality of cross cutting seams, of the filler resin mixture, and pouring the second resin material into the mold, so that the glass fibers are immersed in the second resin material;

s500, carrying out second curing treatment on the material in the die to obtain the multilayer plastic profile;

the length of the plurality of cross cutting seams is 6cm to 8cm, the width of the plurality of cross cutting seams is 0.8cm to 1.2cm, the depth of the plurality of cross cutting seams is 5 percent to 10 percent of the spreading thickness of the filler resin mixture, the included angle of any two cross cutting seams in the plurality of cross cutting seams is 80 degrees to 100 degrees, the included angle between the first direction and the angle bisector of any two cross cutting seams is-20 degrees to 20 degrees, the mixed filler comprises hydroxyapatite loaded with titanium oxide and silicon nitride, and the glass fiber is germanium bismuth borate glass fiber.

2. The method of making according to claim 1, wherein an angle between any two intersecting cutting seams of the plurality of intersecting cutting seams is from 85 ° to 95 °, and an angle between the first direction and a bisector of the angle of the any two intersecting cutting seams is from-10 ° to 10 °.

3. The method according to claim 1, wherein S200 specifically comprises:

s210, heating the first resin material to 55-65 ℃, adding the mixed filler accounting for 40wt% of the total adding amount into the first resin material, and mixing;

s220, after the first resin material is continuously heated to 75-85 ℃, adding the rest mixed filler accounting for 60wt% of the total addition amount into the first resin material and mixing;

and S230, heating the mixture of the mixed filler and the first resin material to 180-220 ℃ in a mixing roll, mixing for 1-2 h, and extruding through a screw extrusion device to obtain the filler resin mixture.

4. The production method according to claim 1,

the conditions of the first curing process in S300 include: the vacuum degree is 100Pa to 200Pa, the temperature is 120 ℃ to 130 ℃, and the time is 0.5h to 1 h;

the conditions of the second curing process in S500 include: the pressure is 20MPa to 30MPa, the temperature is 150 ℃ to 160 ℃, and the time is 2h to 3 h.

5. The method of any one of claims 1 to 4, wherein the hybrid filler comprises:

4 to 6 parts by mass of titanium oxide;

4 to 6 parts by mass of silicon nitride;

20 to 30 parts by mass of hydroxyapatite;

wherein at least a portion of the titanium oxide and at least a portion of the silicon nitride fill voids of the hydroxyapatite.

6. The method according to any one of claims 1 to 4, wherein the glass fiber is produced from the following raw materials:

4 to 6 parts by mass of zinc oxide;

10 to 12 parts by mass of silicon oxide;

10 to 12 parts by mass of germanium oxide;

20 to 30 parts by mass of boron oxide;

50 to 55 parts by mass of bismuth oxide.

7. The production method according to any one of claims 1 to 4, wherein the first resin material includes:

2 to 4 parts by mass of isophorone;

2 to 4 parts by mass of methyl paraben;

5 to 10 parts by mass of dioctyl phthalate;

15 to 20 parts by mass of polylactic acid;

15 to 20 parts by mass of polybutylene succinate;

20 to 25 parts by mass of a polyhydroxyalkanoate;

100 parts by mass of polyethylene.

8. The production method according to any one of claims 1 to 4, wherein the second resin material includes:

2 to 4 parts by mass of isophorone;

4 to 6 parts by mass of ethylene glycol;

4 to 6 parts by mass of isopentane;

8 to 10 parts by mass of sodium carboxymethylcellulose;

20 to 25 parts by mass of polyethylene terephthalate;

30 to 40 parts by mass of polybutylene terephthalate;

100 parts by mass of a copolymer of butylene adipate and butylene terephthalate.

9. A fiber-toughened multilayer plastic profile, characterized in that it is obtained with the production method according to any one of claims 1 to 8.

10. A degradable food lunch box prepared using the fiber-toughened multi-layer plastic profile of claim 9.

Technical Field

The application belongs to the technical field of plastic profile processing, particularly relates to the technical field of multilayer plastic profiles containing reinforcing materials and fillers, and particularly relates to a fiber-toughened multilayer plastic profile, a preparation method thereof and a degradable food lunch box.

Background

In recent years, plastic products containing a fiber reinforcement and/or an inorganic filler and a high molecular polymer have been increasingly widely used. For example, such plastic articles can be used in various fields such as daily necessities, catering processing, medical products, industrial packaging elements and the like.

Among them, the multilayer plastic products containing fiber reinforced material and/or inorganic filler have many advantages such as high mechanical strength, good toughness, excellent heat resistance, etc., and thus have a wide application prospect.

However, the following technical problems still remain to be solved in the materials: the materials of the layers in the multi-layer plastic product have different properties such as composition, surface energy and the like, so that the bonding property between the materials of the layers is not ideal.

In summary, it is a urgent task for those skilled in the art to improve the interlayer bonding performance of a multilayer plastic product containing a fiber reinforcement and/or an inorganic filler.

Disclosure of Invention

The application aims to provide a fiber toughened multilayer plastic profile, a preparation method thereof and a degradable food lunch box. In order to solve the above technical problem, the present application is implemented as follows.

The application provides a preparation method of a fiber toughened multilayer plastic profile, which comprises the following steps:

s100, preparing a mixed filler, glass fibers, a first resin material and a second resin material respectively;

s200, mixing and extruding the mixed filler and the first resin material to obtain a filler resin mixture;

s300, paving the filler resin mixture in a mold, carrying out first curing treatment, and cutting a plurality of cross cutting seams which are arranged in an array on the surface of the filler resin mixture subjected to the first curing treatment;

s400, introducing the glass fibers into a mold along a first direction, arranging the glass fibers on one side, provided with a plurality of cross cutting seams, of the filler resin mixture, and pouring a second resin material into the mold so that the glass fibers are immersed in the second resin material;

s500, carrying out second curing treatment on the material in the die to obtain a multilayer plastic profile;

the length of the plurality of cross cutting seams is 6cm to 8cm, the width of the plurality of cross cutting seams is 0.8cm to 1.2cm, the depth of the plurality of cross cutting seams is 5 percent to 10 percent of the spreading thickness of the filler resin mixture, the included angle of any two cross cutting seams in the plurality of cross cutting seams is 80 degrees to 100 degrees, the included angle between the first direction and the angle bisector of any two cross cutting seams is-20 degrees to 20 degrees, the mixed filler comprises hydroxyapatite loaded with titanium oxide and silicon nitride, and the glass fiber is germanium bismuth borate glass fiber.

In the technical scheme, the included angle of any two crossed cutting seams in the plurality of crossed cutting seams is 85-95 degrees, and the included angle between the first direction and the angle bisector of any two crossed cutting seams is-10 degrees.

In the above technical solution, S200 specifically includes:

s210, heating the first resin material to 55-65 ℃, adding mixed filler accounting for 40wt% of the total addition amount into the first resin material, and mixing;

s220, after the first resin material is continuously heated to 75-85 ℃, adding the residual mixed filler accounting for 60wt% of the total addition amount into the first resin material and mixing;

and S230, heating the mixture of the mixed filler and the first resin material to 180-220 ℃ in a mixing roll, mixing for 1-2 h, and extruding through a screw extrusion device to obtain the filler resin mixture.

In the above technical solution, the conditions of the first curing treatment in S300 include: the vacuum degree is 100Pa to 200Pa, the temperature is 120 ℃ to 130 ℃, and the time is 0.5h to 1 h; the conditions of the second curing process in S500 include: the pressure is 20MPa to 30MPa, the temperature is 150 ℃ to 160 ℃, and the time is 2h to 3 h.

In the above technical scheme, the mixed filler comprises: 4 to 6 parts by mass of titanium oxide; 4 to 6 parts by mass of silicon nitride; 20 to 30 parts by mass of hydroxyapatite; wherein at least part of the titanium oxide and at least part of the silicon nitride are filled in the gaps of the hydroxyapatite.

In the above technical scheme, the glass fiber adopts the following raw materials: 4 to 6 parts by mass of zinc oxide; 10 to 12 parts by mass of silicon oxide; 10 to 12 parts by mass of germanium oxide; 20 to 30 parts by mass of boron oxide; 50 to 55 parts by mass of bismuth oxide.

In the above technical solution, the first resin material includes: 2 to 4 parts by mass of isophorone; 2 to 4 parts by mass of methyl paraben; 5 to 10 parts by mass of dioctyl phthalate; 15 to 20 parts by mass of polylactic acid; 15 to 20 parts by mass of polybutylene succinate; 20 to 25 parts by mass of a polyhydroxyalkanoate; 100 parts by mass of polyethylene.

In the above technical solution, the second resin material includes: 2 to 4 parts by mass of isophorone; 4 to 6 parts by mass of ethylene glycol; 4 to 6 parts by mass of isopentane; 8 to 10 parts by mass of sodium carboxymethylcellulose; 20 to 25 parts by mass of polyethylene terephthalate; 30 to 40 parts by mass of polybutylene terephthalate; 100 parts by mass of a copolymer of butylene adipate and butylene terephthalate.

The application provides a fiber toughened multilayer plastic profile, which is obtained by adopting the preparation method of any one of the technical schemes.

The multilayer plastic profile is obtained by the preparation method according to any one of the above technical schemes, so that the multilayer plastic profile has all the beneficial effects of the preparation method according to any one of the above technical schemes, and details are not repeated herein.

The application provides a degradable food cutlery box, degradable food cutlery box adopts the preparation of the toughened multilayer plastic section bar of fibre as above-mentioned any one technical scheme.

The degradable food lunch box is prepared by adopting the multilayer plastic section bar in any technical scheme, so that the degradable food lunch box has all the beneficial effects of the multilayer plastic section bar in any technical scheme, and the degradable food lunch box is not repeated herein.

The beneficial effect of this application does: because the surface of the filler resin mixture is provided with a plurality of cutting seams, and the filler resin mixture is subjected to the first curing treatment in advance, but the fiber resin mixture is not subjected to the curing treatment, the fiber resin mixture in a flowing or powdery or semi-dry state can be filled and embedded into the plurality of cutting seams of the filler resin mixture, so that the filler resin mixture and the fiber resin mixture are fully connected and matched. The plurality of glass fibers are bent into the plurality of cutting seams by gravity or pressure from the second resinous material. Thereby, the glass fibers in the fiber resin mixture can form a corrugated structure alternating back and forth at the bonding position between the two layers of the filler resin mixture and the fiber resin mixture. Therefore, the interlayer bonding performance of the multilayer plastic product containing the fiber reinforced material and/or the inorganic filler can be improved, so that the aims of improving the mechanical strength, toughness and toughness of the multilayer plastic profile are fulfilled. In addition, the germanium bismuth borate glass fiber is selected to be mixed and impregnated with the second resin material, so that the germanium bismuth borate glass fiber can be ensured not to be broken or fractured when being bent and embedded into a plurality of cross cutting seams, and the connection strength between the fiber resin mixture and the filler resin mixture is further improved.

Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.

Drawings

FIG. 1 is a schematic view (top view) of an arrangement of a plurality of cross-cuts in a filler resin mixture according to an embodiment of the present disclosure;

FIG. 2 is a second schematic view (top view) of the arrangement of a plurality of cross-cuts in the filler resin mixture according to the embodiment of the present application;

fig. 3 is a third schematic view (side view) of the arrangement of a plurality of cross-cuts in the filler resin mixture according to the embodiment of the present application.

Fig. 4 is a schematic cross-sectional view of a multilayer plastic profile of an embodiment of the present application.

Detailed Description

Reference will now be made in detail to the embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The embodiment of the application provides a preparation method of a fiber toughened multilayer plastic profile, which comprises the following steps S100 to S500.

S100, preparing a mixed filler, glass fibers, a first resin material and a second resin material respectively.

In the above step, the mixed filler is specifically a filler obtained by mixing two or more inorganic substances. The function of the mixed filler is to improve the mechanical strength and hardness of the resin material and the corresponding resin layer. Therefore, particles or powders of metal or inorganic non-metal oxides are preferably used as the mixed filler. For example, the mixed filler includes at least two or more of the following: silicon oxide powder, aluminum oxide powder, magnesium oxide, silicon nitride powder, silicon carbide powder, glass powder and ceramic powder.

In the above steps, the glass fiber means a filament-like fiber material obtained by drawing a glass material. The glass fiber has the function of improving the mechanical strength and toughness of the resin material and the corresponding resin layer. Wherein binary, ternary, and multiple glass can be used to prepare the glass fiber. Illustratively, the glass fibers employed herein are silicate glass fibers or aluminosilicate glass fibers.

In the above step, the first resin material and the second resin material are respectively resin materials including one or more high molecular polymers and including appropriate additives. Wherein the additive comprises at least one of the following or a combination thereof: curing agent, molecular chain modifier, foaming agent, plasticizer, flame retardant, antioxidant, light stabilizer, brightener, lubricant, coupling agent and mold release agent. The first resin material and the second resin material can be at least one of the following materials or the combination thereof respectively: polyethylene resin, polypropylene resin, polyurethane resin, polyvinyl chloride resin, polystyrene resin.

And S200, mixing and extruding the mixed filler and the first resin material to obtain a filler resin mixture.

Exemplarily, S200 includes:

s210, heating the first resin material to 55-65 ℃, adding mixed filler accounting for 40wt% of the total adding amount into the first resin material, and mixing.

And S220, after the first resin material is continuously heated to 75-85 ℃, adding the residual mixed filler accounting for 60wt% of the total addition amount into the first resin material and mixing.

And S230, heating the mixture of the mixed filler and the first resin material to 180-220 ℃ in a mixing roll, mixing for 1-2 h, and extruding through a screw extrusion device to obtain the filler resin mixture.

In the above step, the mixed filler and the first resin material may be kneaded using an industrial apparatus such as a kneader, and extruded using an industrial apparatus such as a twin-screw extruder. Wherein, different mixing temperatures, mixing times, extrusion pressures and extrusion speeds can be adopted for the raw materials of different components. Illustratively, the mixing of the mixed filler with the first resin material may be performed for a time period of 1 to 4 hours at a temperature ranging from 160 to 240 ℃. In the case of a twin-screw extruder, the screw speed may be 220r/min to 300 r/min.

S300, paving the filler resin mixture in a mold, carrying out first curing treatment, and cutting a plurality of cross cutting seams arranged in an array on the surface of the filler resin mixture subjected to the first curing treatment.

It will be appreciated that the first curing treatment is a pre-curing treatment, the purpose of which is to cause the filler resin mixture to cure slightly, or not to cure completely, so as to effect a cutting treatment on the surface of the filler resin mixture. The curing temperature and time of the first curing process is lower than the normal curing temperature and time. Illustratively, the conditions of the first curing process in S300 include: the vacuum degree is 100Pa to 200Pa, the temperature is 120 ℃ to 130 ℃, and the time is 0.5h to 1 h.

A cutting slit may be cut in the surface of the filler resin mixture subjected to the first curing process using a cutter. As shown in fig. 1 and 2, the arrangement of the cutting seams is an array arrangement, and the array arrangement means that a plurality of cutting seams are arranged in parallel and form a matrix or a square matrix side by side. Wherein every two cutting seams are mutually crossed and converged at the same vertex. Thus, each two cutting lines jointly enclose a wedge-shaped structure.

S400, introducing the glass fibers into the mold along the first direction and arranging the glass fibers on one side, provided with a plurality of cross cutting seams, of the filler resin mixture, and pouring a second resin material into the mold so that the glass fibers are immersed in the second resin material.

Specifically, as shown in fig. 1 and 2, the method for implementing S400 may be: first, a plurality of glass fibers are introduced to the position of the mold by a draft device, and are laid over the filler resin mixture subjected to the first curing treatment. And then pouring a second resin material into the mould in a coating or injection mode. Thereby, the second resin charge immerses the glass fibers, forming a fiber resin mixture together with the glass fibers. The fiber resin mixture is laid on the surface of the filler resin mixture.

Wherein, because the surface of the filler resin mixture has a plurality of cutting seams, and the filler resin mixture has been subjected to a first curing treatment in advance, but the fiber resin mixture has not been subjected to a curing treatment, as shown in fig. 4, the fiber resin mixture in a flowing or powdery or semi-dry state can be filled and embedded in the plurality of cutting seams of the filler resin mixture to achieve sufficient connection and matching of the filler resin mixture and the fiber resin mixture. The plurality of glass fibers are bent into the plurality of cutting seams by gravity or pressure from the second resinous material. Thereby, the glass fibers in the fiber resin mixture can form a corrugated structure alternating back and forth at the bonding position between the two layers of the filler resin mixture and the fiber resin mixture.

S500, carrying out second curing treatment on the material in the die to obtain the multilayer plastic profile.

It will be appreciated that the second curing treatment is a normal curing treatment, the purpose of which is to fully cure the filler resin mixture with the fibre resin mixture. The curing temperature and time of the second curing process is higher than the curing temperature and time of the first curing process. Illustratively, the conditions of the second curing process in S500 include: the pressure is 20MPa to 30MPa, the temperature is 150 ℃ to 160 ℃, and the time is 2h to 3 h.

As shown in fig. 1 and 2, in the above technical solution, the length of the plurality of cross-cut seams is 6cm to 8cm, and the width of the plurality of cross-cut seams is 0.8cm to 1.2 cm. Too long a length of the plurality of cross cuts results in a decrease in strength at the surface location of the filler resin mixture. The length of the plurality of cross-cuts is too short, which results in insufficient tightness of the connection of the glass fibers with the filler resin mixture, and for this reason, the embodiment of the present application selects the above length range as the ideal length of the plurality of cross-cuts.

As shown in fig. 3, in the above technical solution, the depth of the plurality of cross-cuts is 5% to 10% of the spread thickness of the filler resin mixture. The depth of the plurality of cross cuts is too deep, resulting in a decrease in the strength of the surface location of the filler resin mixture. The depth of the plurality of cross-cuts is too shallow, which results in insufficient tightness of the connection between the glass fibers and the filler resin mixture, and for this reason, the above depth range is selected as the ideal depth of the plurality of cross-cuts in the embodiments of the present application.

As shown in fig. 1 and 2, any two intersecting cutting lines of the plurality of intersecting cutting lines have an included angle of 80 ° to 100 °. Preferably, any two intersecting cutting lines of the plurality of intersecting cutting lines have an included angle of 85 ° to 95 °. If the angle between any two intersecting cutting lines is too small, the strength of the surface of the filler resin mixture is reduced. Therefore, the included angle range is selected as an ideal included angle of the plurality of cross cutting seams.

As shown in fig. 1 and 2, the first direction forms an angle of-20 ° to 20 ° with respect to the bisector of any two intersecting cutting lines. Preferably, the angle between the first direction and the bisector of the angle of any two intersecting cutting lines is-10 ° to 10 °. The technical means aims to ensure that the arrangement direction of the glass fiber and the arrangement direction of any two crossed cutting seams form a specific included angle and a specific staggered relation. Specifically, the arrangement direction of the glass fibers and the arrangement direction of the cutting line are at an angle of about 40 ° to 50 °.

In the embodiment of the application, the mixed filler comprises hydroxyapatite loaded with titanium oxide and silicon nitride. Preferably, the particle diameters of titanium oxide and silicon nitride are 20nm to 100nm, respectively. The hardness of the silicon nitride is higher, and the mechanical strength and hardness of the filler resin mixture can be effectively improved. The titanium oxide has a narrow forbidden band width, and can effectively absorb and/or reflect ultraviolet rays so as to improve the ultraviolet resistance and the ageing resistance of the filler resin mixture. In addition, when titanium oxide is excited by ultraviolet wavelength light, electrons in the valence band are excited to pass through the forbidden band and enter the conduction band, and corresponding holes are generated in the valence band. The photo-generated electrons and photo-generated holes migrate to different positions on the surface of the titanium oxide and can react with oxygen and water which are in contact with the surface of the titanium oxide to generate peroxy radicals or hydroxyl radicals with high activity. These radicals decompose organic microorganisms such as bacteria or organic compounds such as formaldehyde, thereby playing roles in sterilization, self-cleaning, pollutant purification and the like. Thus, titanium oxide can kill bacteria and microorganisms, which can improve the antibacterial and bacteriostatic properties of the filler resin mixture. The hydroxyapatite not only serves as an inorganic toughening agent, but also serves as a carrier of titanium oxide and silicon nitride. Titanium oxide having a smaller particle size is more desirable in terms of antibacterial and ultraviolet resistance, but also has a higher surface energy. The hydroxyapatite is a material with a porous structure, and the powdery titanium oxide and silicon nitride can enter and occupy the gaps of the hydroxyapatite so as to effectively limit the agglomeration phenomenon of the titanium oxide and the silicon nitride with small particle size and high surface energy.

In the embodiment of the application, the glass fiber is preferably germanium bismuth borate glass fiber. Although the glass of the conventional composition such as aluminosilicate glass can also improve the mechanical strength of the fiber resin mixture, the glass of the conventional composition has high brittleness and unsatisfactory toughness. Therefore, when bending and embedding a plurality of cross-cut seams, the glass fiber with the conventional composition is easy to break and break, and the performance of the product is affected and reduced. Therefore, in order to ensure that the glass fiber can be smoothly bent and embedded into a plurality of cross cutting seams, the germanium bismuth borate glass fiber is selected in the embodiment of the application. The germanium bismuth borate glass is prepared from oxide raw materials including germanium oxide, bismuth oxide and boron oxide. The bismuthate glass has better toughness and bending degree. Germanium oxide and boron oxide can further improve the viscosity and toughness of the glass. Therefore, the germanium bismuth borate glass fiber is selected to be mixed and impregnated with the second resin material, so that the germanium bismuth borate glass fiber can be prevented from being broken or fractured when being bent and embedded into a plurality of cross cutting seams, and the connection strength between the fiber resin mixture and the filler resin mixture is further improved.

In some embodiments of the invention, the hybrid filler comprises: 4 to 6 parts by mass of titanium oxide; 4 to 6 parts by mass of silicon nitride; 20 to 30 parts by mass of hydroxyapatite; wherein at least part of the titanium oxide and at least part of the silicon nitride are filled in the gaps of the hydroxyapatite. Wherein, the vinyl triethoxysilane can be added as a silane coupling agent, and the polymethyl methacrylate can be added as an organic polymer modifier, which are used for reducing the surface energy of inorganic components in the mixed filler.

In some embodiments of the present invention, the glass fibers are made from raw materials comprising: 4 to 6 parts by mass of zinc oxide; 10 to 12 parts by mass of silicon oxide; 10 to 12 parts by mass of germanium oxide; 20 to 30 parts by mass of boron oxide; 50 to 55 parts by mass of bismuth oxide. Wherein, bismuth oxide is used as the main raw material of the glass, and germanium oxide and boron oxide are used as the auxiliary additive components of the glass. The bismuth oxide glass has higher toughness, and the addition of the germanium oxide and the boron oxide can further improve the viscosity and the toughness of the glass. Silicon oxide and zinc oxide can ensure the mechanical strength of the glass.

In some embodiments of the invention, the first resin material comprises: 2 to 4 parts by mass of isophorone; 2 to 4 parts by mass of methyl paraben; 5 to 10 parts by mass of dioctyl phthalate; 15 to 20 parts by mass of polylactic acid; 15 to 20 parts by mass of polybutylene succinate; 20 to 25 parts by mass of a polyhydroxyalkanoate; 100 parts by mass of polyethylene. Wherein, the polyethylene is used as the main material in the first resin material. Isophorone as curing agent, methylparaben as antibacterial agent, and dioctyl phthalate as plasticizer. Polylactic acid, poly butylene succinate and polyhydroxyalkanoate are polymer raw materials with relatively good degradation performance and biological-friendly performance. The first resin material adopting the raw materials and the components has good degradability and biosafety.

In some embodiments of the invention, the second resin material comprises: 2 to 4 parts by mass of isophorone; 4 to 6 parts by mass of ethylene glycol; 4 to 6 parts by mass of isopentane; 8 to 10 parts by mass of sodium carboxymethylcellulose; 20 to 25 parts by mass of polyethylene terephthalate; 30 to 40 parts by mass of polybutylene terephthalate; 100 parts by mass of a copolymer of butylene adipate and butylene terephthalate.

The isophorone is taken as a curing agent, the ethylene glycol and the sodium carboxymethylcellulose are taken as trace grinding aids, the isopentane is taken as a foaming agent, and the copolymer of the butanediol adipate and the butanediol terephthalate is a polymer main material with relatively good degradation performance and biological-friendly performance.

It should be noted that the surface energy of the inorganic filler is relatively high, and the surface energy of the high molecular polymer is relatively low. Therefore, it is difficult to uniformly disperse the inorganic filler in the high molecular weight polymer. In other words, the inorganic filler is liable to cause agglomeration in the high molecular weight polymer. The above problems lead to the unsatisfactory performance of the plastic products, especially the poor uniformity and stability, and the plastic products may fail, age and even separate layers after long-term use. For this reason, in order to avoid the above problems, in some embodiments of the present invention, the mixed filler of S100 is prepared by the following steps.

S111, preparing titanium oxide: silicon nitride: boron oxide: silicon oxide: water = (4-6): (4-6): (5-10): (5-10): weighing 100 parts by weight of the materials, mixing, and preparing a first mixed solution;

s112, as vinyltriethoxysilane: polypropylene glycol: sodium lauryl sulfate: vegetable oil = 2: 4: (6-8): (50-60) weighing and mixing the materials in parts by mass to prepare a second mixed solution;

s113, according to the first mixed solution: second mixed solution = 1: (0.8-1.2), mixing the first mixed solution and the second mixed solution, and performing ultrasonic emulsification uniformly to obtain a third mixed solution;

s114, according to the weight ratio of silicon nitride: hydroxyapatite = (4-6): (20-30) weighing hydroxyapatite according to the mass part ratio, adding the hydroxyapatite into the third mixed solution, and stirring to obtain a fourth mixed solution; wherein the stirring in S114 is under vacuum conditions of 100Pa to 200Pa and temperature conditions of 40 ℃ to 50 ℃;

s115, filtering the fourth mixed solution to obtain a solid-phase substance in the fourth mixed solution, and drying the solid-phase substance;

and S116, conveying the solid substance into a plasma torch by using an inert gas flow of 5slpm to 10slpm, and treating at the temperature of 1000 ℃ to 1100 ℃ and the system pressure of 50kPa to 60kPa to obtain the mixed filler.

In the above step, first, in S111, titanium oxide, silicon nitride, boron oxide, and silicon oxide are prepared as a first mixed liquid in a suspended state in water. Further, in step S112, vinyltriethoxysilane as a silane coupling agent, polypropylene alcohol and sodium lauryl sulfate as surfactants, and vegetable oil as a solvent are prepared as a second mixed liquid of an oil phase. Subsequently, the first mixed liquid and the second mixed liquid are ultrasonically emulsified by S113, and a third mixed liquid in an emulsion state can be obtained. Thus, through S111 through S113, an emulsion of inorganic toughening particles (i.e., titanium oxide, silicon nitride, boron oxide, and silicon oxide) that are homogeneously dispersed and have a reduced surface energy can be prepared. Further, by adding hydroxyapatite to the emulsion in S114, the inorganic toughening particles can be supported in and on the surface of the porous hydroxyapatite. Wherein, as the hydroxyapatite is in a loose porous structure, the inorganic toughening particles can be ensured to enter the pores of the hydroxyapatite by stirring under a vacuum condition, and further, the sufficient effective load is realized. Subsequently, the fourth mixed solution is filtered through S115, and a solid phase in which titanium oxide, silicon nitride, boron oxide, and silicon oxide and hydroxyapatite are blended can be obtained. Finally, the solid phase is sent to a plasma torch for treatment. The above-mentioned S111 to S113 are intended to mix and treat various fillers as inorganic substances in an emulsifier to reduce the surface energy thereof and ensure uniform mixing of the various fillers, particularly to ensure that titanium oxide, silicon nitride, boron oxide and silicon oxide can be filled in the pores of hydroxyapatite. Finally, the solid phase is sent to a plasma torch for processing. 1000 ℃ to 1100 ℃ is the critical temperature before the decomposition of the hydroxyapatite. Under the temperature condition, hydroxyapatite forms small spheres with uniform particle size under the conditions of air flow impact and high temperature, boron oxide and silicon oxide are melted to form a disordered glass phase, titanium oxide and silicon nitride are solidified in the glass phase, and the glass phase formed on the surface of the hydroxyapatite can close at least part of pores on the surface of the hydroxyapatite by melting. Therefore, the titanium oxide and the silicon nitride are better solidified and loaded in the inner pores of the hydroxyapatite. Therefore, with the mixed filler obtained by the above steps, it is difficult for the problem of agglomeration to recur during the mixing and extrusion with the first resin material.

It should be noted that glass fibers having smooth and filamentous surfaces, in addition to the inorganic filler, also have a problem of being difficult to bond to the resin. Therefore, the glass fiber impregnated in the resin is easily separated from the resin matrix. The related art approach to solve the above problems is generally to perform surface treatment, such as coating, on the glass fiber to apply a coupling agent. However, the above treatment method can only reduce the surface energy of the glass fiber to some extent, and the bonding strength between the glass fiber and the resin is still not satisfactory. For this reason, in order to improve the bonding strength of the glass fiber and the resin, in some embodiments of the present invention, the glass fiber of S100 is prepared by the following steps.

S121, adding zinc oxide: silicon oxide: germanium oxide: boron oxide: bismuth oxide = (4-6): (10-12): (10-12): (20-30): (50-55) weighing and mixing the materials in parts by mass to prepare a glass matrix;

s122, heating the glass substrate to 750-850 ℃ along with a furnace, preserving heat for 2-4 h to obtain molten glass, pouring the molten glass into a grinding tool to obtain a glass rod, and drawing the glass rod into glass fibers;

s123, immersing the glass fiber in 2-4 wt% hydrofluoric acid for treatment for 20-40 min, taking out, washing and drying;

and S124, putting the glass fiber treated in the S123 into a vacuum pyrolysis furnace, introducing tetraethoxysilane steam into the vacuum pyrolysis furnace, and performing chemical vapor deposition treatment for 12-15 h under the condition of deposition temperature of 260-280 ℃ and argon atmosphere to obtain the modified glass fiber.

In the steps, the hydrofluoric acid treatment causes the surface of the glass fiber to form defects, and the long-time chemical vapor deposition treatment of 12h to 15h causes silicon-based substances of the tetraethoxysilane to deposit and grow on the surfaces of the defects of the glass fiber, so that the roughness of the surface of the glass fiber is increased on the basis of reducing the surface energy of the glass fiber, and the bonding strength of the glass fiber and the resin is improved.

The features of the terms first and second in the description and in the claims of the present application may explicitly or implicitly include one or more of such features. In the description of the present application, "a plurality" means two or more unless otherwise specified. In addition, "and/or" in the specification and claims means at least one of connected objects, a character "/" generally means that a preceding and succeeding related objects are in an "or" relationship.

In the description herein, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

While embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the application, the scope of which is defined by the claims and their equivalents.