CN1434076A - Inorganic matter filled biodegrading material, preparation method and use thereof - Google Patents

Abstract

The invention is an inorganic-filled biodegradable polymer composite material, which consists of a matrix polymer of completely biodegradable aliphatic polyester with a weight average molecular weight of 200,000-400,000, 1500-3000 mesh inorganic mineral ultrafine powder, Composed of a coupling agent and a lubricant, the weight ratios of the aliphatic polyester, inorganic mineral ultrafine powder, coupling agent and lubricant are respectively 50-99.5: 0.5-50, 0-5 and 0-5 . It is a linear aliphatic polyester prepared by condensation polymerization or ring-opening polymerization, and can be a homopolymer or a copolymer. It is a polymer matrix that is different from the disintegrating filled degradable material, which is completely biodegradable, and the degradation products have no side effects on the environment. Moreover, the source of raw materials is wide, the price is low, the preparation process is simple, and the method is easy to implement. It can be used to prepare fully biodegradable products, such as masterbatches, films and products of various shapes.

Description

A kind of inorganic material filling biodegradable material, preparation method and application

technical field

The invention relates to a biodegradable material filled with inorganic matter blending and belongs to the field of polymer composite material preparation. The material is obtained by blending and modifying thermoplastic fully biodegradable aliphatic polyester or copolyester with inorganic matter. Because the polyester is completely biodegradable, and the inorganic matter for blending and filling comes from the natural environment, the material of the invention is a new environment-friendly polymer composite material.

technical background

As a multifunctional material that is developing rapidly, the application range of plastics continues to expand, but the accompanying large amount of plastic waste is causing increasingly serious environmental pollution. For this reason, the research on plastic degradation technology has been paid more and more attention. In the 1970s, British scientist G.J.L.Griffin first proposed to make filled polymers by adding starch to polymers, which triggered an upsurge in the research and development of filled degradable plastics. Since the 1980s, my country has also begun to study filled degradable plastics, and developed some products, and achieved many results.

A lot of research has also been carried out on filling-type degradable plastics in China. For example, Chinese patent CN00100127 relates to a basically biodegradable starch-containing resin composition and its preparation method and application. The composition contains high-content starch, metallocene Polyolefin, EAA, and additives and auxiliary agents can be used to manufacture blow molding products, extrusion molding products, injection molding products and foaming products. Chinese patent CN00105580 relates to a degradable composite material composition, which includes plant fiber, urea-formaldehyde resin, melamine and food coloring agent, and disposable tableware manufactured from the composite material. Chinese patent CN00106295 reports a composite degradable plastic masterbatch of inorganic base material, which is composed of 25-70% inorganic composite base material, 25-70% composite polyolefin and other additives, wherein the inorganic composite base material Contains 60-100% calcium carbonate and other inorganic substances. Chinese patent CN00110239 discloses a controllable environment degradable plastic masterbatch, which is composed of the following components in parts by weight: mineral powder 32-42%, compatibilizer 22-23%, low molecular weight polyethylene 3-4% %, 1-3% paraffin, 1.5-2.5% stearic acid, 4-6% n-butyl stearate (or epoxy soybean oil), 5-7% linear low-density polyethylene, 7-7% high-density polyethylene 19%, catalyst (ionic) 2%.

The characteristics of these patents are that degradable components, mainly starch or other natural plant-derived natural degradable substances are filled with environmentally non-degradable synthetic polymers to obtain filled degradable plastics. However, the above-mentioned filling-type degradable plastics should be said to be just a kind of "disintegrating-type degradable plastics" in terms of their essence. This type of plastic mainly refers to the mixing of biodegradable natural substances, such as starch, into general-purpose plastics, so that general-purpose plastics become small particles due to the degradation of biodegradable components under composting conditions. Because this kind of filled degradable plastic is under the action of microorganisms, only a small amount of biodegradable substances added are swallowed up, and most of the remaining general-purpose plastics are not rapidly biodegradable, so it can only solve the problem of tangible garbage or reduce the amount of garbage. That's all, but can't completely solve the problem of polluting the environment.

Recently, biodegradable synthetic polymers, such as polylactic acid (PLA), polyhydroxybutyric acid (PHA) (Japanese Patent Laid-Open No. 2001-507737 ), polycaprolactone (PCL), etc. It can be completely biodegradable, and is widely used in the fields of biomedical materials and environmentally friendly materials. Aliphatic polyester polyethylene succinate (PES), polybutylene succinate (PBS), polybutylene adipate (PBA) (US Patent 5310782; US Patent 5310782; Japan Fiber Society Journal, 52,320,1996; Polymer Degra.Stab., 59,209,1998) also obtained rapid development. In order to improve the singleness and processability of biodegradable polymer resins, a binary/multiple blend of biodegradable polymers has been developed on the basis of the above, such as PCL/PBS blends (Japanese Patent Laid-Open 2002 -060510), PHA/PLA blend (Japanese Patent Laid-Open No. 09-087499), aliphatic copolyester/starch blend (Japanese Patent Laid-Open 2002-294045), aliphatic copolyester/cellulose acetate co- mixture (Japanese Patent Laid-Open No. 2002-293986). The above-mentioned patents are mainly based on improving the processability of the biodegradable polymer resin itself, but there are certain disadvantages in terms of cost.

Contents of the invention

The purpose of the present invention is to solve the problem that ordinary inorganic filling materials do not have environmental friendliness, starch-filled degradable plastics only have disintegration and cannot be completely degraded, and environmentally friendly polymer materials that can be completely biodegraded are relatively expensive. In addition, due to the low modulus in the mechanical properties during processing, it is difficult to enter the practical fields such as plastics.

The purpose of the present invention is to provide a novel inorganic matter-filled biodegradable blended composite material with good mechanical properties and processing flow properties.

Another object of the present invention is to provide a method for preparing the above-mentioned inorganic matter-filled biodegradable blended composite material.

The object of the present invention is also to provide a use of the above-mentioned inorganic matter-filled biodegradable blended composite material.

The filler of the invention is inorganic mineral, and the polymer matrix is completely biodegradable aliphatic polyester or copolyester.

The main application of the inorganic-matter-filled biodegradable material provided by the invention is environment-friendly plastic.

The object of the present invention is to adopt following measure to realize.

A starting material formula of an inorganically filled biodegradable material is as follows by weight percentage:

Biodegradable aliphatic polyester: 50～99.5

Inorganic filler: 0.5～50

Coupling agent: 0～5

Lubricant: 0～5.

The biodegradable aliphatic polyester used in the present invention is characterized by high molecular weight and complete biodegradability, and has a weight average molecular weight of 200,000 to 400,000.

The biodegradable aliphatic polyester used in the present invention refers to the linear aliphatic polyester with the following chemical structural formula obtained by condensation polymerization or ring-opening polymerization, which can be a homopolymer or a copolymer:

The structural formula of a homopolymer:

The structural formula of the copolymer:

的均聚物，也可以是它们的共聚物。In the chemical structural formula of the above-mentioned biodegradable aliphatic polyester, R ₁ , R ₂ , R ₃ , and R ₄ are saturated straight-chain alkylene, unsaturated straight-chain alkylene, or alicyclic Group substituents, such as C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , C ₅ H ₁₀ , C ₆ H ₁₀ , CH ₂ -C ₆ H ₁₀ -CH ₂ etc. In the above chemical structural formula of the biodegradable aliphatic polyester, the mole percentage x is 0-100%, and y is 100-0%. In other words, the aliphatic polyester used in the present invention may be or

Homopolymers or their copolymers.

In the aliphatic polyester with the above general formula used in the present invention, R ₁ to R ₄ are preferably saturated linear alkylene groups with 2 to 8 carbon atoms, unsaturated linear alkylene groups, or alicyclic substituted The ideal number of carbon atoms is 2-6. The aliphatic polyester used in the present invention has: polyethylene succinate, polybutylene succinate, polybutylene adipate, polybutylene succinate adipate Polyester, Polybutylene Succinate Hexylene Glycol Copolyester.

The inorganic fillers used in the present invention refer to ultrafine powders of inorganic minerals, such as calcium carbonate, kaolin, montmorillonite, talcum powder, barium sulfate, etc., which are characterized by originating from the natural environment and having low environmental load. The ultrafine powder of the inorganic mineral is 1500-3000 mesh.

The coupling agent used in the present invention refers to a silane coupling agent or a titanate coupling agent, and its dosage is 0-5%, preferably 0-2%, more ideally 0-1%.

The general formula of the silane coupling agent used in the present invention is R-SiX ₃ , R is an organic group, such as a vinyl group, an epoxy group, an amino group, a methacrylic group, etc., and X is an alkane group with 1 to 3 carbon atoms. Oxygen, X can also be chlorine. The above-mentioned silane coupling agents generally include: vinyltriethoxysilane, vinyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropylpropyltriethoxysilane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane and the like.

The general formula of the titanate coupling agent used in the present invention is: or a ring structure:

Wherein R ₁ to R ₄ are alkoxy groups with 3 to 20 carbon atoms or phosphate groups and phosphite groups. The above-mentioned titanate coupling agents generally include: isopropyl-triisostearyl titanate, isopropyl-tri(lauric acid-tetradecyl) titanate, isopropyl-distearyl propylene Acyl titanate, Ethylenedioxy bis(dioctyl phosphate) titanate, Isopropyl-tris(dioctyl phosphate) titanate, Isopropyl-tris(dioctyl phosphate) pyrophosphate ester group) titanate, etc., tetraoctyloxytitanium-bis(dilauryl phosphite) titanate.

The lubricant used in the present invention can be hydrocarbons, fatty acids, fatty acid amides, esters, alcohols or metal soap lubricants, such as liquid paraffin, natural paraffin, microcrystalline paraffin, polyethylene wax, chlorinated paraffin , capric acid, stearic acid, peak flower acid, ricinoleic acid, stearamide, palmitamide, N, N'-methylene bis stearamide, N, N'-ethylene bis stearamide, stearic acid Butyl monostearate, ethylene glycol monostearate, glyceryl monostearate, decyl alcohol, lauryl alcohol, stearyl alcohol, peak wax alcohol, calcium stearate, sodium stearate, barium stearate, hard Magnesium stearate, cadmium stearate, zinc stearate, lead stearate, etc. Among them, it is ideal to use hydrocarbon or metal soap lubricants. Its dosage is 0-5%, preferably 0-2%, more ideally 0-1%

The coupling agent and lubricant used in the present invention are the reagents used in common plastic filling processing, which makes the present invention easy to popularize.

Weigh the above-mentioned biodegradable aliphatic polyester, inorganic filler, coupling agent, and lubricant separately, mix them evenly, add them to the screw extruder, and obtain an inorganic-filled biodegradable blend compound after melt mixing and granulation. pellets of material.

The screw extruder used in the preparation process of the present invention can be a single-screw extruder or a twin-screw extruder, the processing temperature is preferably 80-210°C, more ideally 110-190°C, and the screw speed is 5-100 rpm, preferably 10-50 rpm, ideally 20-30 rpm, aspect ratio 5-50, preferably 10-40, ideally 20-30 .

The inorganic-filled biodegradable material prepared by the present invention is white pellets. According to the variety of raw materials used and the proportion of the formula, products with a melting point of 80-130°C can be obtained. Since the filling substrate is internationally recognized and can Completely biodegradable aliphatic polyester, filled with inorganic minerals from nature, its composition can be completely degraded, with low environmental load.

The pellets can be further processed according to different processing requirements to obtain completely biodegradable finished products filled with inorganic matter.

Description of drawings

Fig. 1 is the degradation trend curve of the biodegradable blended composite material of the present invention in high temperature saturated steam.

In accompanying drawing 1, abscissa is material at 80 ℃, the degradation time (t) in saturated steam under 90% relative humidity, and ordinate is the weight-average molecular weight Mw (t) of residual polymer polyester in the material after degradation experiment t time Ratio to the initial weight average molecular weight of the material. Wherein the experimental data shown in icon ▲ is the result of embodiment 2, the experimental data shown in icon ■ is the result of embodiment 4, the experimental data shown in icon ● is the result of embodiment 10, and the experimental data shown in icon ★ is embodiment 12 the result of.

The aliphatic biodegradable polymer blend composite material and preparation method provided by the present invention can not only be used to prepare completely biodegradable products, such as masterbatches, films and products of various shapes, but also There are the following advantages:

1. According to the preparation method of the aliphatic biodegradable polymer composite material filled with inorganic matter provided by the present invention, the raw materials used are biodegradable polymers and natural minerals, and the polymer matrix has complete biodegradability, The degradation products have no side effects on the environment, so they are different from the disintegrating filled degradation materials.

2. According to the preparation method of the aliphatic biodegradable polymer composite material filled with inorganic matter provided by the present invention, because the inorganic mineral matter used has the characteristics of wide sources and low price, the cost of filling the degradable material can be greatly reduced, Easy to promote and use.

3. The aliphatic biodegradable polymer composite material filled with inorganic matter prepared according to the present invention has improved its cutting modulus due to the addition of inorganic minerals used in it, thereby improving its impact resistance, and due to adding Other additives with a total content of no more than 10% make it have good processability and can be further post-processed with general plastic processing equipment.

4. The whole preparation process is simple and easy to implement.

The specific implementation method and test analysis instrument adopted in the embodiment are specified as follows:

【Molecular Weight】

The molecular weight of the macromolecule used in the present invention is measured by gel permeation chromatography (GPC). Styrene with a series molecular weight of narrow molecular weight distribution is used as a calibration standard sample, and chloroform is used as an eluting phase. The measurement temperature is 40°C.

[Melting point temperature and melting enthalpy]

By differential scanning calorimetry (DSC), the melting point temperature and melting enthalpy can be measured. The scan rate was 20°C/min.

【Melt Index】

The melt index of the material is measured by a melt index meter, the test condition is a temperature of 190°C, and the test load is 2.16Kg.

【Mechanical Properties】

The material is made into a film with a thickness of 0.2 mm, and the mechanical properties of the tensile test are carried out on a universal tensile machine. The stretching speed is 20mm/min.

【Degradation performance】

The degradation performance was tested in a constant temperature and humidity chamber. The test temperature is 80°C, the relative humidity is 90%, and the degradation performance is judged by testing the molecular weight of the original sample and the sample after 240 hours of degradation.

The following examples will help to understand the present invention, but do not limit the content of the present invention.

Example 1

450 grams of polybutylene succinate with a weight average molecular weight of 300,000, 50 grams of calcium carbonate powder, and 0.20 grams of coupling agent isopropyl-triisostearyl titanate were weighed respectively, and after mixing evenly, add the A screw extruder with a fixed temperature of 150-190° C. is used to cool and granulate in a water tank to obtain inorganic calcium carbonate-filled pellets. The melting point temperature of the pellets is 111.6°C, the melting enthalpy is 51.1J/g, the melt index is 4.64g/10min, the tensile strength of the film is 25.9Mpa, the elongation at break is 168.5%, and the %1 secant modulus is 473.1.

Example 2

Weigh 400 grams of polybutylene succinate with a weight average molecular weight of 223,232, 100 grams of calcium carbonate powder, and 0.25 grams of vinyl triethoxysilane as a coupling agent. ℃ twin-screw extruder, and use a water tank to cool and pelletize to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 112.3°C, the melting enthalpy is 43.8J/g, the melt index is 4.36g/10min, the tensile strength of the film is 28.6Mpa, the elongation at break is 138.1%, the %1 secant modulus is 615.4, and the degradation takes 240 hours The final molecular weight was 51,390, which was 23% of the initial molecular weight.

The results of the degradation test of the material in this example at 80° C. and 90% relative humidity are shown in the icon ▲ in the accompanying drawing 1 .

Example 3

350 grams of polybutylene succinate with a weight average molecular weight of 300,000, 150 grams of calcium carbonate powder, 0.25 grams of coupling agent vinyltriethoxysilane, 0.1 grams of sodium stearate and polyethylene wax, weighed respectively After mixing evenly, add it to a twin-screw extruder with a set temperature of 150-190°C, and use a water tank to cool and granulate to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 112.3°C, the melting enthalpy is 39.6J/g, the melt index is 4.15g/10min, the tensile strength of the film is 22.5Mpa, the elongation at break is 125.9%, and the %1 secant modulus is 573.6.

Example 4

300 grams of polybutylene succinate with a weight average molecular weight of 244,893, 200 grams of calcium carbonate powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, sodium stearate, polyethylene wax 0.15 grams each, weighed separately, mixed evenly, added to a twin-screw extruder with a set temperature of 150-190° C., cooled in a water tank and granulated to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 112.9°C, the melting enthalpy is 32.9J/g, the melt index is 3.76g/10min, the tensile strength of the film is 19.2Mpa, the elongation at break is 66.2%, the %1 secant modulus is 635.8, and the degradation takes 240 hours The final molecular weight was 48,475, which was 19% of the initial molecular weight.

The degradation test results of the material in this example at 80°C and 90% relative humidity are shown in the icon ■ in the accompanying drawing 1 .

Example 5

275 grams of polybutylene succinate with a weight average molecular weight of 300,000, 225 grams of calcium carbonate powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, sodium stearate, polyethylene wax 0.2 grams each, weighed separately, mixed evenly, added to a twin-screw extruder with a set temperature of 150-190° C., cooled in a water tank and granulated to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 112.3°C, the melting enthalpy is 31.3J/g, the melt index is 3.62g/10min, the tensile strength of the film is 16.8Mpa, the elongation at break is 55.6%, and the %1 secant modulus is 695.5.

Example 6

325 grams of polybutylene succinate with a weight average molecular weight of 300,000, 175 grams of montmorillonite powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, sodium stearate, polyethylene 0.15 grams each of the waxes was weighed, mixed evenly, and added to a twin-screw extruder with a set temperature of 150-190° C., cooled in a water tank and granulated to obtain inorganic montmorillonite-filled biodegradable material pellets. The melting point temperature of the pellets is 113.1°C, the melting enthalpy is 36.1J/g, the melt index is 3.94g/10min, the tensile strength of the film is 22Mpa, the elongation at break is 67%, and the %1 secant modulus is 577.2.

Example 7

375 grams of polybutylene succinate with a weight average molecular weight of 300,000, 125 grams of kaolin powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, each of sodium stearate and polyethylene wax 0.15 g, weighed separately, mixed evenly, added to a twin-screw extruder with a set temperature of 150-190° C., cooled in a water tank and granulated to obtain inorganic kaolin-filled biodegradable material pellets. The melting point temperature of the pellets is 112.3°C, the melting enthalpy is 42.3J/g, the melt index is 4.22g/10min, the tensile strength of the film is 27.6Mpa, the elongation at break is 158.9%, and the %1 secant modulus is 642.4.

Comparative Example 1

Add 400 grams of polybutylene succinate with a weight-average molecular weight of 240,118 into a twin-screw extruder with a set temperature of 150-190° C., and use a water tank to cool and pelletize to obtain pure biodegradable material pellets. The melting point temperature of the pellets is 112.7°C, the melting enthalpy is 54.2J/g, the melt index is 4.98g/10min, the tensile strength of the film is 40.2Mpa, the elongation at break is 70.6%, the %1 secant modulus is 456.9, and it degrades for 240 hours The final molecular weight was 43,298, which was 18% of the initial molecular weight.

Example 8

The weight average molecular weight is 250,000 polybutylene succinate hexanediol ester copolymer 450 grams, calcium carbonate powder 50 grams, coupling agent isopropyl group-triisostearyl titanate 0.20 grams weigh respectively, mix After homogeneity, it is added to a twin-screw extruder with a set temperature of 110-170° C., cooled in a water tank and granulated to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 93.1°C, the melting enthalpy is 31.9J/g, the melt index is 5.83g/10min, the tensile strength of the film is 28.2Mpa, the elongation at break is 763.7%, and the %1 secant modulus is 205.3.

Example 9

Weigh 425 grams of polybutylene succinate hexanediol copolymer with a weight average molecular weight of 250,000, 75 grams of calcium carbonate powder, and 0.25 grams of vinyl triethoxysilane as a coupling agent, and add them after mixing evenly to set A twin-screw extruder with a temperature of 110-170° C. is used to cool and granulate in a water tank to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 90.5°C, the melting enthalpy is 33.1J/g, the melt index is 5.94g/10min, the tensile strength of the film is 27.7Mpa, the elongation at break is 695.3%, and the %1 secant modulus is 270.4.

Example 10

400 grams of polybutylene succinate hexylene glycol ester copolymer with a weight-average molecular weight of 263,537, 100 grams of calcium carbonate powder, and 0.25 grams of coupling agent isopropyl-triisostearyl titanate were weighed respectively, After mixing evenly, it is added to a twin-screw extruder with a set temperature of 110-170° C., cooled in a water tank and granulated to obtain inorganic calcium carbonate-filled biodegradable material pellets. The melting point temperature of the pellets is 88.1°C, the melting enthalpy is 28.2J/g, the melt index is 7.02g/10min, the tensile strength of the film is 23.9Mpa, the elongation at break is 567.3%, the %1 secant modulus is 308.3, and the degradation takes 240 hours The final molecular weight was 45,540, which was 17% of the initial molecular weight.

The degradation test results of the material in this example at 80° C. and 90% relative humidity are shown in the icon ● in the accompanying drawing 1 .

Example 11

The weight-average molecular weight is 250,000 polybutylene succinate hexanediol ester copolymer 375 grams, calcium carbonate powder 125 grams, coupling agent isopropyl-triisostearyl titanate 0.25 grams, sodium stearate 0.15 grams each of polyethylene wax, weighed separately, mixed evenly and added to a twin-screw extruder with a set temperature of 110-170 ° C, and cooled in a water tank and pelletized to obtain inorganic calcium carbonate-filled biodegradable material pellets . The melting point temperature of the pellets is 90.9°C, the melting enthalpy is 30.7J/g, the melt index is 5.28g/10min, the tensile strength of the film is 23.4Mpa, the elongation at break is 480.1%, and the %1 secant modulus is 359.1.

Example 12

300 grams of polybutylene succinate hexanediol copolymer with a weight average molecular weight of 276,814, 200 grams of calcium carbonate powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, stearic acid 0.15 grams each of sodium and polyethylene wax, weighed separately, mixed evenly, added to a twin-screw extruder with a set temperature of 110-170 ° C, and cooled in a water tank and granulated to obtain a biodegradable material filled with inorganic calcium carbonate pellets. The melting point temperature of the pellets is 93.5°C, the melting enthalpy is 21.2J/g, the melt index is 3.67g/10min, the tensile strength of the film is 15.7Mpa, the elongation at break is 172.7%, the %1 secant modulus is 428.8, and it degrades for 240 hours The final molecular weight was 41,437, which was 15% of the initial molecular weight.

The results of the degradation experiment of the materials in this example at 80°C and 90% relative humidity are shown in the icon ★ in Figure 1.

Example 13

350 grams of polybutylene succinate hexanediol copolymer with a weight average molecular weight of 251,864, 150 grams of kaolin powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, sodium stearate 0.15 grams each of polyethylene wax, respectively weighed, mixed evenly, added to a twin-screw extruder with a set temperature of 110-170 ° C, and cooled with a water tank and pelletized to obtain inorganic kaolin-filled biodegradable material pellets. The melting point temperature of the pellets is 91.5°C, the melting enthalpy is 27.1J/g, the melt index is 4.91g/10min, the tensile strength of the film is 17Mpa, the elongation at break is 254.1%, and the %1 secant modulus is 413.7, after 240 hours of degradation The molecular weight was 42,817, which was 17% of the initial molecular weight.

Example 14

325 grams of polybutylene succinate hexanediol ester copolymer with a weight average molecular weight of 261,574, 200 grams of montmorillonite powder, 0.25 grams of coupling agent isopropyl-triisostearyl titanate, stearin 0.15 grams each of sodium bicarbonate and polyethylene wax, respectively weighed, mixed evenly, and then added to a twin-screw extruder with a set temperature of 110-170 ° C, and cooled in a water tank and granulated to obtain inorganic montmorillonite-filled bio Degradable material pellets. The melting point temperature of the pellets is 91.1°C, the melting enthalpy is 24.3J/g, the melt index is 4.23g/10min, the tensile strength of the film is 15.5Mpa, the elongation at break is 224.9%, the %1 secant modulus is 430.5, and it degrades for 240 hours The final molecular weight was 44,468, which was 17% of the initial molecular weight.

Comparative Example 2

Add 400 grams of polybutylene succinate hexanediol copolymer with a weight average molecular weight of 249,785 to a twin-screw extruder with a set temperature of 110-170°C, and use a water tank to cool and granulate to obtain unfilled Biodegradable material pellets. The melting point temperature of the pellets is 81.6°C, the melting enthalpy is 34.7J/g, the melt index is 5.18g/10min, the tensile strength of the film is 37.8Mpa, the elongation at break is 806%, the %1 secant modulus is 214.4, and it degrades for 240 hours The final molecular weight was 36,417, which was 15% of the initial molecular weight.

Claims (10)

1. A biodegradable polymer composite material filled with inorganic substances, consisting of a matrix polymer of fully biodegradable aliphatic polyester with a weight average molecular weight of 200,000-400,000, 1500-3000 mesh inorganic mineral ultrafine powder, and even Composed of a coupling agent and a lubricant, the weight ratios of the aliphatic polyester, inorganic mineral ultrafine powder, coupling agent and lubricant are 50-99.5:0.5-50, 0-5 and 0-5 respectively. 2. The complete biodegradable polyester as claimed in claim 1, characterized in that it has the following chemical structural formula: Wherein, R ₁ and R ₂ are saturated linear alkylene groups, unsaturated linear alkylene groups, or alicyclic substituents having 2 to 12 carbon atoms. 3. The fully biodegradable copolyester as claimed in claim 1 is characterized in that it has the following chemical structural formula: Among them, R ₁ , R ₂ , R ₃ , and R ₄ are saturated straight-chain alkylene groups, unsaturated straight-chain alkylene groups, or alicyclic substituents with 2 to 12 carbon atoms, and the above-mentioned aliphatic copolyesters The mole percentage x in the chemical structural formula is 0-100%, and y is 100-0%. 4. A kind of inorganic material filled biodegradable material as claimed in claim 1, it is characterized in that described aliphatic polyester is polyethylene succinate, polybutylene succinate, poly Butylene adipate, polybutylene succinate adipate copolymer, and polybutylene succinate hexanediol copolymer. 5. The biodegradable material filled with inorganic matter according to claim 1, characterized in that said ultrafine powder of inorganic mineral is calcium carbonate, kaolin, montmorillonite or talcum powder. 6. coupling agent as claimed in claim 1 is characterized in that general formula is the silane coupling agent or the titanate coupling agent of R-SiX ₃ , and in the shown silane coupling agent, R is to comprise vinyl , epoxy group, amino group, organic group including methacrylic acid group, X is an alkoxy group with 1 to 3 carbon atoms, and X is a halogen; the general formula of the titanate coupling agent shown is as follows: or ring structure Wherein R ₁ -R ₄ are alkoxy groups with 3 to 20 carbon atoms or phosphate groups and phosphite groups. . 7. The lubricant according to claim 1, which is a lubricant of hydrocarbons, fatty acids, fatty acid amides, esters, alcohols or metal soaps. 8. A kind of preparation method of the biodegradable composite material filled with inorganic matter as claimed in claim 1, it is characterized in that above-mentioned biodegradable aliphatic polyester, inorganic filler, coupling agent, lubricant are mixed, in 80～230℃ and twin or single screw extruder, melt mixing, granulation, wherein the weight ratio of biodegradable aliphatic polyester, inorganic filler, coupling agent and lubricant is 50～99.5:0.5～50 respectively : 0~5: 0~5. 9. The fully biodegradable copolyester according to claim 2 or 3, characterized in that said R ₁ , R ₂ , R ₃ or R ₄ are C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , C ₅ H ₁₀ , C ₆ H ₁₀ or CH ₂ -C ₆ H ₁₀ -CH ₂ . 10. The use of an inorganic-filled biodegradable material as claimed in claim 1, characterized in that it is used to prepare fully biodegradable products including masterbatches, films and products of various shapes.