PP composition capable of being degraded by light and oxygen, preparation method of PP composition and degradable PP non-woven fabric
By using photooxygen-degradable PP compositions, including photodegradable masterbatches and oxygen-degradable masterbatches, the problem of slow decomposition speed of traditional polypropylene nonwovens is solved, and the good degradation and mechanical properties of polypropylene nonwovens are achieved, and it is suitable for the application of environmentally friendly materials.
Patent Information
- Application Number
- CN202411807602.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-10
- Publication Date
- 2025-04-15
AI Technical Summary
Traditional polypropylene non-woven fabrics have slow decomposition speed in the natural environment, resulting in environmental pollution. The existing degradable materials are expensive and have poor spinning performance. The existing technology still needs to be improved in terms of polypropylene degradation and mechanical properties.
Degradable PP nonwoven fabrics are prepared by mixing and melt extrusion processes using photooxygen degradable PP compositions, including polypropylene resins, photodegradable masterbatches and oxygen degradable masterbatches. Photodegradation masterbatches are prepared from benzophenone-grafted PP masterbatches, and oxygendegradation masterbatches are prepared from acetylacetonate-grafted PP masterbatches.
The good degradation and mechanical properties of polypropylene non-woven fabrics are achieved, which can be controlled degraded in a short time, and the preparation method is simple and does not require additional equipment.
Smart Images
Figure BDA0005179691660000081
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of degradable materials, and particularly relates to a photo-oxidatively degradable PP composition, a preparation method thereof and a degradable PP non-woven fabric. Background Art
[0002] Polypropylene non-woven fabrics are widely used in many fields such as medical care, packaging materials and agriculture due to their good physical properties and chemical stability. However, traditional polypropylene non-woven fabrics do not have easily degradable functional groups, and decompose very slowly in the natural environment after being discarded. It may take hundreds of years to completely degrade, thus causing serious pollution to the environment.
[0003] Existing biodegradable materials such as PLA (polylactic acid), PBAT (polybutylene adipate terephthalate), PBS (polybutylene succinate), PHA (polyhydroxyalkanoate) and other materials are not only expensive but also have poor spinning performance.
[0004] In order to solve the above problems, there are currently three most commonly used methods. The first is to add degradable masterbatch to polypropylene, such as PLA or PBAT and other materials. This method will affect the mechanical properties of polypropylene non-woven fabrics, and the degradation rate is slow; the second method is to add natural degradable materials, such as cellulose or starch and other materials, which are prone to problems such as poor compatibility and uneven dispersion, and will also affect the mechanical properties; the third method is to modify the polypropylene itself to improve the degradation performance of polypropylene. This method can make polypropylene easier to degrade and has almost no effect on the mechanical properties of its non-woven fabrics.
[0005] The existing technical solutions are as follows: Solution 1 discloses the use of polypropylene, degradation masterbatch, compatibilizer and additives to prepare degradable polypropylene materials, wherein the degradation masterbatch is composed of polypropylene, modified titanium dioxide and coupling agent. This polypropylene material has excellent degradation performance and can also improve its mechanical properties. This method mainly enhances the photodegradation performance of polypropylene. Solution 2 blends polypropylene, polycaprolactone, erucamide, maleic anhydride grafted polypropylene, first modified cellulose nanocrystals, second modified cellulose nanocrystals, stearic acid, and 3-aminopropyltrimethoxysilane to melt and prepare a degradable masterbatch. This method can improve the biodegradability of polypropylene non-woven fabrics, but it is prone to poor compatibility and uneven dispersion. The above-mentioned existing technologies still need to be further improved in terms of polypropylene degradation performance and mechanical properties.
[0006] Therefore, there is an urgent need to provide a new polypropylene nonwoven fabric, which has both good degradation performance and good mechanical properties. Summary of the invention
[0007] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a photo-oxidative degradable PP (polypropylene) composition, a preparation method thereof and a degradable PP non-woven fabric, wherein the PP non-woven fabric has both good degradation performance and good mechanical properties.
[0008] A first aspect of the present invention provides a photo-oxidatively degradable PP composition.
[0009] Specifically, a photo-oxidatively degradable PP composition includes a polypropylene resin, a photo-degradable masterbatch, and an oxidatively degradable masterbatch.
[0010] Preferably, the photodegradable masterbatch comprises benzophenone-grafted PP masterbatch.
[0011] Preferably, the oxygen-degradable masterbatch comprises PP masterbatch grafted with acetylacetone. PP masterbatch can also be called polypropylene.
[0012] Preferably, the PP composition, by weight, comprises 100 parts of polypropylene resin, 3-15 parts of photodegradable masterbatch, and 4-15 parts of oxygen-degradable masterbatch; further preferably, the PP composition, by weight, comprises 100 parts of polypropylene resin, 5-10 parts of photodegradable masterbatch, and 5-10 parts of oxygen-degradable masterbatch.
[0013] The second aspect of the present invention provides a method for preparing a photo-oxidatively degradable PP composition.
[0014] Specifically, a method for preparing a photo-oxidatively degradable PP composition comprises the following steps:
[0015] The polypropylene resin, the photodegradable masterbatch and the oxygen-degradable masterbatch are mixed and melt-extruded to obtain the PP composition.
[0016] Preferably, the preparation method comprises the following steps:
[0017] The polypropylene resin, the photodegradable masterbatch and the oxygen-degradable masterbatch are added into a mixer according to weight proportions and mixed, and then put into a twin-screw extruder for melt extrusion and granulation to obtain the PP composition.
[0018] Preferably, the melt extrusion temperature of the twin-screw extruder is 150-240° C., and the screw speed is 500-800 r / min. More preferably, the melt extrusion temperature of the twin-screw extruder is 170-230° C., and the screw speed is 500-800 r / min.
[0019] Preferably, the method for preparing the photodegradable masterbatch comprises the following steps:
[0020] The benzophenone is mixed with a solvent, and then the PP masterbatch is added, stirred, and irradiated under ultraviolet light to obtain a crude grafted product, which is then washed and dried to obtain the photodegradable masterbatch.
[0021] Preferably, the method for preparing the photodegradable masterbatch comprises the following steps:
[0022] (1) dissolving benzophenone in a solvent to form a uniform solution, fully soaking and dissolving the dried PP masterbatch in the solution, and stirring uniformly to obtain a mixed solution;
[0023] (2) placing the mixed solution obtained in step (1) under an ultraviolet light source to irradiate, thereby obtaining a crude grafted product;
[0024] (3) washing the crude grafted product with a solvent to remove unreacted monomers to obtain a PP grafted product, and then drying the grafted product to remove residual solvent to obtain the photodegradable masterbatch.
[0025] Preferably, the solvent is at least one of acetone, tetrahydrofuran, acetic anhydride, ethanol and toluene.
[0026] Preferably, in step (1), when benzophenone is added, a surfactant is also added, and the surfactant is at least one of sodium polyacrylate, sodium lauryl sulfate, and polyethylene glycol.
[0027] Preferably, in step (1), by weight, PP is 60-90 parts, benzophenone is 2-7 parts, and surfactant is 0.1-1 part.
[0028] Preferably, in step (1), the stirring speed is 30-100 rpm and the stirring time is 1-3 h.
[0029] Preferably, in step (2), the wavelength of the ultraviolet light source is 285-400nm, and the intensity of the ultraviolet light source is 200-1000w / cm 2 The irradiation time of the ultraviolet light source is 5-60min.
[0030] Preferably, in step (3), the washing is performed 2 to 3 times and the drying temperature is 60-100°C.
[0031] Preferably, in step (3), the washing is performed using at least one of ethanol, distilled water and acetone.
[0032] Preferably, the method for preparing the oxygen-degradable masterbatch comprises the following steps:
[0033] The PP masterbatch is mixed with a solvent, and then a catalyst and a surfactant are added, stirred, an initiator and acetylacetone are added, and heated and stirred under a protective gas atmosphere to obtain a crude grafted product, which is then washed and dried to obtain the oxygen-degradable masterbatch.
[0034] Preferably, the method for preparing the oxygen-degradable masterbatch comprises the following steps:
[0035] (1) dissolving the dried PP in a selected solvent to form a uniform solution; then adding a catalyst and a surfactant to the solution and stirring the solution to obtain a mixture;
[0036] (2) adding an initiator and acetylacetone to the mixture obtained in step (1), introducing a protective gas, heating and stirring, to obtain a crude grafted product;
[0037] (3) The crude graft obtained in step (2) is washed with distilled water to remove unreacted reagents and other impurities to obtain a PP graft, and then the PP graft is dried to obtain the oxygen-degradable masterbatch.
[0038] Preferably, in step (1), the solvent is at least one of xylene, toluene, ethanol, acetone, ether and chloroform.
[0039] Preferably, in step (1), the surfactant is at least one of benzophenone, sodium dodecyl sulfate and polyethylene glycol.
[0040] Preferably, in step (2), the catalyst is at least one of nickel acetylacetonate and molybdenum acetylacetonate.
[0041] Preferably, in step (2), the initiator is at least one of formyl peroxide, dibenzoyl peroxide, and azobisisobutyronitrile.
[0042] Preferably, by weight, the PP masterbatch is 70-90 parts, acetylacetone is 2-5 parts, the catalyst is 0.1-2 parts, the surfactant is 0.5-3 parts, and the initiator is 0.1-2 parts.
[0043] Preferably, in step (2), the temperature of heating and stirring is 165-190° C., and the time of heating and stirring is 3-6 h.
[0044] Preferably, in step (2), the stirring speed of the heating stirring is 100-200 rpm.
[0045] Preferably, the protective gas includes nitrogen or argon.
[0046] Preferably, in step (3), the number of washing times is not limited, preferably 2-3 times, and the drying temperature is 70-90°C.
[0047] The third aspect of the present invention provides an application of a photo-oxidatively degradable PP composition.
[0048] A degradable PP nonwoven fabric comprises the above PP composition.
[0049] The above-mentioned degradable PP non-woven fabric is prepared by using a PP composition through a conventional spunbonding process.
[0050] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0051] (1) The PP composition of the present invention contains specific photodegradable masterbatch and oxygen-degradable masterbatch, wherein the photodegradable masterbatch includes benzophenone-grafted PP masterbatch, and the oxygen-degradable masterbatch includes acetylacetone-grafted masterbatch, so that the PP composition of the present invention has both good degradation performance and good mechanical properties.
[0052] (2) The present invention uses photo-oxidative degradation masterbatch and polypropylene for blending, which has good compatibility, significant degradation effect, and can also ensure that the mechanical properties of the PP non-woven fabric are not affected.
[0053] (3) The present invention uses light-oxygen dual degradation technology to transform ordinary PP non-woven fabrics into degradable and environmentally friendly materials, and can controllably degrade PP non-woven fabrics in a relatively short period of time. At the same time, the preparation method is simple and does not require the addition of new equipment. DETAILED DESCRIPTION
[0054] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be noted that the following embodiments do not limit the protection scope of the present invention.
[0055] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.
[0056] Example 1: Preparation of PP composition and nonwoven fabric
[0057] A photo-oxidatively degradable PP composition comprises, by weight, 100 parts of polypropylene resin, 5 parts of photo-degradable masterbatch, and 5 parts of oxygen-degradable masterbatch.
[0058] The preparation process of photodegradable masterbatch is as follows:
[0059] (1) 2 parts of benzophenone and 0.1 parts of sodium polyacrylate were uniformly mixed with acetone, and then 60 parts of polypropylene were added, and the mixture was stirred at 30 rpm for 1 hour to form a uniform mixed solution;
[0060] (2) The uniform solution obtained in step (1) was irradiated under an ultraviolet light source for 5 min, wherein the wavelength of the ultraviolet light source was 285 nm and the intensity of the ultraviolet light source was 200 w / cm 2 , a crude grafted product is obtained;
[0061] (3) After step (2) is completed, the crude grafted product is washed twice with distilled water, and the residue is dried in an oven at 60° C. to obtain a photodegradable masterbatch (i.e., benzophenone-grafted polypropylene).
[0062] The preparation process of oxygen-degradable masterbatch is as follows:
[0063] (1) dissolving 70 parts of the dried PP in chloroform to form a uniform solution; then adding 0.1 parts of nickel acetylacetonate catalyst and 0.5 parts of polyethylene glycol surfactant to the solution, stirring uniformly to obtain a mixture;
[0064] (2) adding 0.1 parts of oxyformyl initiator and 2 parts of acetylacetone to the mixture obtained in step (1), introducing nitrogen, stirring at 100 rpm for 3 h at 165° C., and obtaining a crude grafted product;
[0065] (3) The crude grafted product was washed twice with distilled water, and the residue was dried in an oven at 70° C. to obtain oxygen-degradable masterbatch (i.e., acetylacetone-grafted polypropylene).
[0066] A method for preparing a photo-oxidatively degradable PP composition comprises the following steps:
[0067] Polypropylene resin, photodegradable masterbatch and oxygen-degradable masterbatch are added into a mixer according to weight proportions and mixed, and then put into a twin-screw extruder for melt extrusion and granulation to obtain a PP composition. The melt extrusion temperature of the twin-screw extruder is 170° C. and the screw speed is 500 r / min.
[0068] A photo-oxidation-degradable PP non-woven fabric comprises the above-mentioned PP composition. The non-woven fabric is prepared from the above-mentioned PP composition through a conventional spunbonding process.
[0069] Example 2
[0070] A photo-oxidatively degradable PP composition comprises, by weight, 100 parts of polypropylene resin, 10 parts of photo-degradable masterbatch, and 10 parts of oxygen-degradable masterbatch.
[0071] The preparation process of photodegradable masterbatch is as follows:
[0072] (1) 4 parts of benzophenone and 0.5 parts of sodium polyacrylate were uniformly mixed with acetone, and then 75 parts of polypropylene were added, and the mixture was stirred at 60 rpm for 2 h to form a uniform mixed solution;
[0073] (2) The uniform solution obtained in step (1) was irradiated under an ultraviolet light source for 30 min, wherein the wavelength of the ultraviolet light source was 350 nm and the intensity of the ultraviolet light source was 500 w / cm 2 , a crude grafted product is obtained;
[0074] (3) After step (2) is completed, the crude grafted product is washed twice with distilled water, and the residue is dried in an oven at 80° C. to obtain a photodegradable masterbatch (i.e., benzophenone-grafted polypropylene).
[0075] The preparation process of oxygen-degradable masterbatch is as follows:
[0076] (1) dissolving 80 parts of the dried PP in chloroform to form a uniform solution; then adding 1 part of nickel acetylacetonate catalyst and 1.5 parts of polyethylene glycol surfactant to the solution, stirring uniformly to obtain a mixture;
[0077] (2) adding 1 part of oxyformyl initiator and 3.5 parts of acetylacetone to the mixture obtained in step (1), introducing nitrogen, stirring at 150 rpm for 4 h at 180° C., and obtaining a crude grafted product;
[0078] (3) The crude grafted product was washed twice with distilled water, and the residue was dried in an oven at 80° C. to obtain oxygen-degradable masterbatch (i.e., acetylacetone-grafted polypropylene).
[0079] A method for preparing a photo-oxidatively degradable PP composition comprises the following steps:
[0080] The polypropylene resin, photodegradable masterbatch and oxygen-degradable masterbatch are added into a mixer according to weight proportions and mixed, and then put into a twin-screw extruder for melt extrusion and granulation to obtain a PP composition. The melt extrusion temperature of the twin-screw extruder is 190° C. and the screw speed is 650 r / min.
[0081] A photo-oxidation-degradable PP non-woven fabric comprises the above-mentioned PP composition. The non-woven fabric is prepared from the above-mentioned PP composition through a conventional spunbonding process.
[0082] Example 3
[0083] A photo-oxidatively degradable PP composition comprises, by weight, 100 parts of polypropylene resin, 15 parts of photo-degradable masterbatch, and 15 parts of oxygen-degradable masterbatch.
[0084] The preparation process of photodegradable masterbatch is as follows:
[0085] (1) 4 parts of benzophenone and 0.5 parts of sodium polyacrylate were uniformly mixed with acetone, and then 75 parts of polypropylene were added, and the mixture was stirred at 60 rpm for 2 h to form a uniform mixed solution;
[0086] (2) The uniform solution obtained in step (1) was irradiated under an ultraviolet light source for 30 min, wherein the wavelength of the ultraviolet light source was 350 nm and the intensity of the ultraviolet light source was 500 w / cm 2 , a crude grafted product is obtained;
[0087] (3) After step (2) is completed, the crude grafted product is washed twice with distilled water, and the residue is dried in an oven at 80° C. to obtain a photodegradable masterbatch (i.e., benzophenone-grafted polypropylene).
[0088] The preparation process of oxygen-degradable masterbatch is as follows:
[0089] (1) dissolving 80 parts of the dried PP in chloroform to form a uniform solution; then adding 1 part of nickel acetylacetonate catalyst and 1.5 parts of polyethylene glycol surfactant to the solution, stirring uniformly to obtain a mixture;
[0090] (2) adding 1 part of oxyformyl initiator and 3.5 parts of acetylacetone to the mixture obtained in step (1), introducing nitrogen, stirring at 150 rpm for 4 h at 180° C., and obtaining a crude grafted product;
[0091] (3) The crude grafted product was washed twice with distilled water, and the residue was dried in an oven at 80° C. to obtain oxygen-degradable masterbatch (i.e., acetylacetone-grafted polypropylene).
[0092] A method for preparing a photo-oxidatively degradable PP composition comprises the following steps:
[0093] The polypropylene resin, photodegradable masterbatch and oxygen-degradable masterbatch are added into a mixer according to weight proportions and mixed, and then put into a twin-screw extruder for melt extrusion and granulation to obtain a PP composition. The melt extrusion temperature of the twin-screw extruder is 190° C. and the screw speed is 650 r / min.
[0094] A photo-oxidation-degradable PP non-woven fabric comprises the above-mentioned PP composition. The non-woven fabric is prepared from the above-mentioned PP composition through a conventional spunbonding process.
[0095] Comparative Example 1
[0096] Compared with Example 2, the difference of Comparative Example 1 is that no photodegradable masterbatch is used in Comparative Example 1, and the rest of the process is the same as that of Example 2.
[0097] Comparative Example 2
[0098] Compared with Example 2, the difference of Comparative Example 2 is that no oxygen-degradable masterbatch is used in Comparative Example 2, and the rest of the process is the same as that of Example 2.
[0099] Comparative Example 3
[0100] Compared with Example 2, the difference of Comparative Example 3 is that no photodegradable masterbatch and oxygen-degradable masterbatch are used in Comparative Example 3, and the rest of the process is the same as that of Example 2.
[0101] Comparative Example 4
[0102] The difference between Comparative Example 4 and Example 1 is that an equal amount of methyl benzoylbenzoate is used instead of benzophenone to prepare the photodegradable masterbatch, and the rest of the process is the same as Example 1.
[0103] Comparative Example 5
[0104] The difference between Comparative Example 5 and Example 1 is that an equal amount of ethyl acetoacetate is used instead of acetylacetone to prepare the oxygen-degradable masterbatch, and the rest of the process is the same as Example 1.
[0105] Product effect testing
[0106] The PP nonwoven fabrics prepared in the above Examples 1-3 and Comparative Examples 1-5 were taken to test the mechanical properties of the PP nonwoven fabrics, and the test was performed with reference to GB / T24218.18-2014. The test results are shown in Table 1 (MD represents longitudinal direction, and CD represents transverse direction).
[0107] Table 1: Mechanical properties of examples and comparative examples
[0108] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Weight gsm 30.7 31.2 30.5 30.9 32.2 29.2 29.5 30.4 MD strength, N / 5cm 71.5 68.2 67.5 67.3 64.5 64.9 60.4 58.7 MD elongation, % 87.1 92.5 86.7 82.5 84.6 86.4 83.4 80.5 CD strength, N / 5cm 45.2 48.2 44.9 44.8 44.2 43.5 41.6 40.8 CD elongation, % 116.8 126.5 120.4 114.6 116.2 118.6 105.6 109.8
[0109] As can be seen from Table 1, the addition of visible light degradation masterbatch and oxygen degradation masterbatch has no significant effect on the mechanical properties of PP non-woven fabric. However, it can be seen from Example 1 and Comparative Examples 4-5 that changing the raw materials in the preparation process of light degradation masterbatch or oxygen degradation masterbatch will have a significant impact on the mechanical properties of the product.
[0110] 300 g of each PP non-woven fabric prepared in Examples 1-3 and Comparative Examples 1-5 were taken and placed in outdoor soil. After 6 months, the PP non-woven fabrics were taken out and weighed respectively, and then the weight loss rate of degradation was calculated (weight loss rate = (initial weight of PP non-woven fabric - weight of PP non-woven fabric after 6 months in outdoor soil) / initial weight of PP non-woven fabric * 100%). The results are shown in Table 2. The larger the weight loss rate, the better the degradation performance.
[0111] Table 2
[0112]
[0113] It can be seen from Table 2 that the degradation performance of the PP non-woven fabric prepared in the embodiment of the present invention is significantly better than that of the comparative example.
Claims
1. A PP composition, characterized in that: Including polypropylene resin, photodegradable masterbatch and oxygen-degradable masterbatch.
2. The PP composition according to claim 1, characterized in that The photodegradable masterbatch comprises benzophenone-grafted PP masterbatch.
3. The PP composition according to claim 1, characterized in that The oxygen-degradable masterbatch comprises PP masterbatch grafted with acetylacetone.
4. The PP composition according to any one of claims 1 to 3, characterized in that: The PP composition comprises, by weight, 100 parts of polypropylene resin, 3-15 parts of photodegradable masterbatch, and 4-15 parts of oxygen-degradable masterbatch.
5. The method for preparing the PP composition according to any one of claims 1 to 4, characterized in that: The following steps are involved: The polypropylene resin, the photodegradable masterbatch and the oxygen-degradable masterbatch are mixed and melt-extruded to obtain the PP composition.
6. The preparation method according to claim 5, characterized in that: The method for preparing the photodegradable masterbatch comprises the following steps: The benzophenone is mixed with a solvent, and then the PP masterbatch is added, stirred, and irradiated under ultraviolet light to obtain a crude grafted product, which is then washed and dried to obtain the photodegradable masterbatch.
7. The preparation method according to claim 6, characterized in that: The method for preparing the photodegradable masterbatch comprises the following steps: (1) dissolving benzophenone in a solvent to form a solution, soaking and dissolving the dried PP masterbatch in the solution, and stirring to obtain a mixed solution; (2) placing the mixed solution obtained in step (1) under an ultraviolet light source to irradiate, thereby obtaining a crude grafted product; (3) washing the crude grafted product with a solvent to remove unreacted monomers to obtain a PP grafted product, and then drying the PP grafted product to remove residual solvent to obtain the photodegradable masterbatch.
8. The preparation method according to claim 5, characterized in that: The preparation method of the oxygen-degradable masterbatch comprises the following steps: The PP masterbatch is mixed with a solvent, and then a catalyst and a surfactant are added, stirred, an initiator and acetylacetone are added, and heated and stirred under a protective gas atmosphere to obtain a crude grafted product, which is then washed and dried to obtain the oxygen-degradable masterbatch.
9. The preparation method according to claim 8, characterized in that: The preparation method of the oxygen-degradable masterbatch comprises the following steps: (1) dissolving the dried PP in a solvent to form a solution; then adding a catalyst and a surfactant to the solution and stirring to obtain a mixture; (2) adding an initiator and acetylacetone to the mixture obtained in step (1), introducing a protective gas, heating and stirring, to obtain a crude grafted product; (3) The crude graft obtained in step (2) is washed with distilled water to remove unreacted reagents and other impurities to obtain a PP graft, and then the PP graft is dried to obtain the oxygen-degradable masterbatch.
10. A degradable PP nonwoven fabric, characterized in that: The PP composition comprises the PP composition according to any one of claims 1 to 4.