CN115725143A - Degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material and preparation method thereof - Google Patents
Degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material and preparation method thereof Download PDFInfo
- Publication number
- CN115725143A CN115725143A CN202211637854.1A CN202211637854A CN115725143A CN 115725143 A CN115725143 A CN 115725143A CN 202211637854 A CN202211637854 A CN 202211637854A CN 115725143 A CN115725143 A CN 115725143A
- Authority
- CN
- China
- Prior art keywords
- parts
- foam material
- wear
- degradable
- resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material and a preparation method thereof. The compound comprises the following components; 40 parts of polyvinyl chloride, 25 parts of PBAT, 20 parts of polylactic acid, 25 parts of thermoplastic starch, 1-5 parts of composite wear-resistant auxiliary agent, 6 parts of plasticizer, 3 parts of alkyl glycoside foaming agent, 6 parts of filler, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of lubricant, 0.15 part of paraffin, 0.2 part of ADR chain extender, 0.8 part of cross-linking agent and 0-3 parts of AC foaming agent. The preparation method comprises the following steps: the raw materials are subjected to banburying mixing and then are sent into a flat vulcanizing instrument for molding, so that the degradable high-strength wear-resistant PVC foam material can be obtained. The formula of the invention greatly increases the specific gravity of the degradable components while keeping the foaming function of the product, has scientific and reasonable formula, good compatibility of the degradable components and the foaming matrix, degradable capability and greatly improves the economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material and a preparation method thereof.
Background
Polylactic acid (PLA) has good solvent resistance and can be processed in a variety of ways, such as extrusion, spinning, biaxial stretching, injection blow molding. The product made of polylactic acid can be biodegraded, the degradation rate reaches 100%, and the product has good biocompatibility, glossiness, transparency, hand feeling and heat resistance. Because the strength and hardness of many degradable high polymer materials are low, polylactic acid is a few high-strength degradable high polymer materials, and can make up for the defects of the strength and hardness of common degradable high polymer materials such as starch.
PBAT belongs to thermoplastic biodegradable plastic, is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility, elongation at break and heat resistance; in addition, the biodegradable plastic has excellent biodegradability, the degradation rate is 100%, and the biodegradable plastic is one of the most popular degradable materials for the research and market application of biodegradable plastics. The PBAT is used as a novel biodegradable material and is mainly applied to the aspects of agricultural mulching films, food packaging and the like. However, PBAT has problems of poor crystallinity, low melt strength, low product strength hardness, and high price, etc., compared to common plastics, limiting its application in manufacturing.
Thermoplastic starch (TPS), modified from corn starch, is completely biodegradable. Since various starches are derived from foods in nature and are widely available and numerous, the price is very low. The melting temperature of the natural starch is as high as about 250 ℃, which is higher than the decomposition temperature of the natural starch, and the natural starch cannot be directly used for mechanical processing, so plasticizing modification is needed firstly, and the traditional method for plasticizing starch is to blend glycerol and starch in a high-speed mixer at high temperature and then melt and extrude the mixture. However, starch is a strong hydrophilic substance, glycerol makes the hydrophilicity of the starch stronger, and most degradable high polymer materials such as PBAT, PLA and the like belong to hydrophobic materials, so that the compatibility between the starch and the degradable materials is poor, the performance is influenced, and the application range of the starch is reduced. When the product is used for manufacturing various articles for daily use, such as garbage bags and tableware, the product quality is not enough due to insufficient strength, such as easy breakage, poor use experience of customers, such as short service life and the like. Therefore, it is important to plasticize starch to make it compatible with more degradable materials.
PVC is white powder with an amorphous structure, the branching degree is small, the glass transition temperature is 77 to 90 ℃, the decomposition starts at about 170 ℃, the stability to light and heat is poor, the PVC can be decomposed to generate hydrogen chloride at more than 100 ℃ or after being exposed to sunlight for a long time, the hydrogen chloride is further automatically catalyzed and decomposed to cause color change, the physical and mechanical properties are also rapidly reduced, and the stability to heat and light and the basic mechanical properties can be improved by adding a stabilizer and a cross-linking agent in practical application. PVC is a universal plastic with the largest yield in the world and has wide application. The product has wide application in building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like.
However, PVC belongs to petroleum-based materials, which are obtained by extraction from petroleum, which determines that PVC is a non-degradable material. Many PVC products in life such as plastic bag, disposal bag, plastic bottle, they are visible everywhere and need use and change constantly again, have resulted in a large amount of PVC products by abandonment, and PVC is nondegradable and abandonment handles improper can cause very big injury to the environment, and the non-recyclability of PVC has simultaneously led to the waste of a large amount of natural resources, causes the negative benefits of economy, environment. Therefore, it is very important to develop a degradable foaming material capable of partially replacing the non-degradable components in the traditional PVC foaming formula.
The invention adopts the degradable foaming agent alkyl glycoside (APG 0810) as the foaming agent in the formula, APG successfully replaces the use of the common non-degradable foaming agent, the foam holes are uniformly distributed in the material and are not large, and the influence on the mechanical property of the product is very small. The APG and the starch modified by maleic anhydride have good compatibility, and the anhydride group generated at high temperature can well graft PVC, APG, starch, PBAT and PLA together, thereby realizing the pairwise compatibilization among the polyvinyl chloride, the foaming agent and the degradable component. The formula of the invention greatly increases the specific gravity of the degradable components while keeping the foaming function of the product, has scientific and reasonable formula, good compatibility of the degradable components and the foaming matrix, degradable capability and greatly improves the economic and environmental benefits.
According to the invention, the graphene oxide and the nano-silicon dioxide are mutually compatible through the sodium dodecyl sulfate, so that the defect caused by directly mixing the graphene oxide and the nano-silicon dioxide with a single apparatus or only directly physically mixing the apparatus and a substrate in the traditional method is overcome, for example, the graphene oxide and the nano-silicon dioxide both have a large amount of hydroxyl groups, and the agglomeration is easily caused in the melting process, so that the wear resistance is rarely improved, and even the basic mechanical property is reduced. The sodium dodecyl sulfate respectively reacts with the graphene oxide and the nano silicon dioxide in a mode of occupying hydroxyl sites on molecules, so that the aggregation effect caused by the hydroxyl groups is reduced, the compatibility between the graphene oxide and the nano silicon dioxide is improved, the basic mechanical property and the wear resistance of the product are enhanced, the service life of the product is prolonged, and a huge economic effect is generated.
Disclosure of Invention
The invention aims to provide a degradable high-strength wear-resistant PVC foam material which has high mechanical property and is degradable and wear-resistant and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a degradable high-strength wear-resistant PVC (polyvinyl chloride) foaming material is prepared from the following raw materials in parts by weight: 40 parts of polyvinyl chloride (PVC), 25 parts of PBAT (butylene adipate and terephthalate), 20 parts of polylactic acid (PLA), 25 parts of thermoplastic starch (MTPS), 1-5 parts of composite wear-resistant additive (G-S-S), 6 parts of plasticizer, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of filler, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of lubricant, 0.15 part of paraffin, 0.2 part of ADR chain extender (Joncryl ADR 4300), 0.8 part of cross-linking agent and 0-3 parts of AC foaming agent;
further, the plasticizer is one or more of DBP (dibutyl phthalate) and DOP (dioctyl phthalate); the composite wear-resistant auxiliary agent is GO (graphene oxide) -SDS (sodium dodecyl sulfate) -nanoSiO 2 (nanosilica) composites.
Further, the preparation steps of the composite wear-resistant additive (G-S-S) are as follows;
(1) Dissolving 6g of nano silicon dioxide and 1.2g of SDS in 300ml of deionized water, and stirring for 1.5h at room temperature by using a 300rpm magnetic stirrer to obtain white slurry;
(2) Dissolving 2g of GO in 150ml of deionized water, and performing ultrasonic treatment for 1 hour to uniformly disperse the GO in the deionized water;
(3) Dissolving 0.4g of SDS in the solution in the step (2), and stirring the solution for 1.5h at room temperature by using a magnetic stirrer at 300rpm to obtain light brown slurry;
(4) Adding the solution obtained in the step (3) and the solution obtained in the step (1) into a three-neck flask together, and stirring for 1.5 hours at room temperature by using a 300rpm magnetic stirrer;
(5) And (5) moving the system in the step (4) into a stainless steel reaction kettle, reacting for 1 hour at 160 ℃, washing with a large amount of deionized water, centrifuging, and finally drying in an oven at 60 ℃ overnight to obtain a product marked as G-S-S for later use.
Further, the filler is; one or more of calcium carbonate and talcum powder; the cross-linking agent is: dicumyl peroxide (DCP); the lubricant agent is; one or more of lead stearate (PbST) and calcium stearate (CaST);
further, the preparation steps of the thermoplastic starch are as follows;
(1) Taking 300g of corn starch, drying at 70 ℃ for 2h, then putting the corn starch, 90g of glycerol and 30g of maleic anhydride into a high-speed mixer, stirring at 60 ℃ for 1h, and taking materials from a discharge port after the mixing is finished;
(2) Putting the blend obtained in the step (1) into a double-screw extruder, and circularly extruding for 2 times at 7 temperature regions from a hopper to a nozzle, wherein the temperature of the 7 temperature regions is respectively 80, 83, 86, 90, 94, 98 and 100 ℃;
(3) Granulating the product obtained in the step (2) by using a granulator, and recording the product as MTPS for later use;
further, the preparation method of the degradable high-strength wear-resistant PVC foam material comprises the following steps: 35 parts of polyvinyl chloride (PVC), 40 parts of PBAT (butylene adipate and terephthalate), 20 parts of polylactic acid (PLA), 25 parts of thermoplastic starch (MTPS), 1-5 parts of composite wear-resistant additive (G-S-S), 6 parts of plasticizer, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of filler, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of lubricant, 0.15 part of paraffin, 0.2 part of ADR chain extender (Joncryl ADR 4300), 0.8 part of cross-linking agent and 0-3 parts of AC foaming agent are put into an internal mixer for co-mixing, and then the blended product is subjected to cold-hot compression molding; the method specifically comprises the following steps:
(1) PBAT, PLA, joncryl ADR4300 and MTPS are put into a pre-heated internal mixer at 180 ℃ for blending for 10min, wherein the rotating speed of the internal mixer is 30rpm;
(2) Adding PVC, a composite wear-resistant auxiliary agent, a plasticizer, APG0810 (or an AC foaming agent), a filler, titanium dioxide, a calcium-zinc stabilizer, a lubricant, a cross-linking agent and paraffin into the blend obtained in the step (1), and continuously mixing in an internal mixer at 180 ℃ for 30min;
(3) And (3) cutting the blend in the step (2) by a chopper, transferring the cut blend into a flat vulcanizing machine for molding, wherein the temperature of an upper template and a lower template is 180 ℃, the pressure is 12MPa, the molding time is 150s, cooling for 360s, opening the mold and taking out the product.
Preferably, the plasticizer is DOP (dioctyl phthalate); the filler is calcium carbonate; the lubricant is calcium stearate (CaST).
The invention has the beneficial effects that:
(1) The alkyl glycoside serving as a degradable foaming agent (APG 0810) is used as the foaming agent in the formula, APG successfully replaces the common non-degradable foaming agent, and the mechanical property of the product is slightly influenced after the product is foamed.
(2) The APG and the starch modified by maleic anhydride have good compatibility, and the anhydride group generated at high temperature can well graft PVC, APG, starch, PBAT and PLA together, thereby realizing the compatibilization among the polyvinyl chloride, the foaming agent and the degradable component. The formula of the invention greatly increases the specific gravity of the degradable components while keeping the foaming function of the product, has scientific and reasonable formula, good compatibility of the degradable components and the foaming matrix, and degradable capability, and greatly improves the economic and environmental benefits.
(3) The graphene oxide and the nano-silica are mutually compatible through the sodium dodecyl sulfate, so that the defect caused by directly blending a single or only direct physical mixing instrument in the graphene oxide and the nano-silica with a matrix in the prior art is overcome, for example, the graphene oxide and the nano-silica both have a large amount of hydroxyl groups, and the aggregation is easily caused in the melting process, so that the wear resistance is rarely improved, and even the basic mechanical property is reduced. The sodium dodecyl sulfate respectively reacts with the graphene oxide and the nano silicon dioxide in a mode of occupying hydroxyl sites on molecules, so that the aggregation effect caused by the hydroxyl is reduced, the compatibility between the graphene oxide and the nano silicon dioxide is increased, the basic mechanical property and the wear resistance of the product are enhanced, the service life of the product is prolonged, and a huge economic effect is generated.
(4) From the whole product, the product obtained by the invention has excellent comprehensive mechanical property and excellent wear resistance, the service life is greatly prolonged, the degradable specific gravity is higher than that of similar PVC products, the high mechanical property is ensured, the product is environment-friendly and degradable, and the cost of waste treatment is reduced. Good economic benefit and wide market prospect, and conforms to the future development direction.
Drawings
FIG. 1 is a scanning electron microscope image of the composite wear-resistant additive (G-S-S) of example 1;
FIG. 2 is an infrared spectrum of Graphene Oxide (GO) from example 1;
FIG. 3 shows nanosilica (nano-SiO) in example 1 2 ) An infrared spectrogram;
FIG. 4 is an infrared spectrum of the composite abrasion resistance aid (G-S-S) of example 1.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The invention is further illustrated by the following examples.
Example 1
(1) Preparing thermoplastic starch; taking 300g of corn starch, drying at 70 ℃ for 2h, then putting the corn starch, 90g of glycerol and 30g of maleic anhydride into a high-speed mixer, stirring at 60 ℃ for 1h, and taking materials from a discharge port after mixing; then putting the mixed material into a double-screw extruder, circularly extruding for 2 times at 7 temperature zones from a hopper to a nozzle, wherein the temperature zones are respectively 80, 83, 86, 90, 94, 98 and 100 ℃, and chopping an internal mixing product, namely MTPS (methyl thiazolyl tetrazolium) for later use;
(2) Preparing a degradable polymer matrix: putting 25 parts of PBAT, 20 parts of PLA, 0.2 part of Joncryl ADR4300 and 25 parts of MTPS (namely the thermoplastic starch in the step 1) into a preheated internal mixer at the temperature of 180 ℃ and blending for 10min, wherein the rotating speed of the internal mixer is 30rpm;
(3) The preparation method of the composite wear-resistant additive (G-S-S) comprises the following steps:
(3-1) preparation of graphene oxide GO: 1 g of sodium nitrate was slowly added to 70 mL of concentrated sulfuric acid until completely dissolved. Then, 2.0 g of flake graphite was added and stirred at 0-4 ℃ for 30 minutes in an ice bath, and potassium permanganate (8.0 g) was added and stirred for 30 minutes. Then, the temperature was raised to 35-45 ℃ and stirred for 300 minutes. 240 ml of deionized water was added and stirred at 65-75 ℃ for 120 minutes. The mixture was heated to 95 ℃ and after 5 minutes, 25 mL (30%) of hydrogen peroxide solution was added and the solution was stirred for 30 minutes. Then, 40mL of a hydrochloric acid solution was added at a mass ratio of 5%, and the mixture was stirred for 30 minutes. After that, vacuum extraction and filtration were carried out while hot. The filter cake was then washed with deionized water and centrifuged until the pH of the GO solution became 5-6. Finally, the solution is dried in vacuum at 65 ℃ to obtain solid GO
(3-2) preparation of G-S-S: 1) Dissolving 6g of nano silicon dioxide and 1.2g of SDS in 300ml of deionized water, and stirring for 1.5h at room temperature by using a 300rpm magnetic stirrer to obtain white slurry; 2) Dissolving 2g of GO in 150ml of deionized water, and performing ultrasonic treatment for 1 hour to uniformly disperse the GO in the deionized water; 3) Dissolving 0.4g of SDS in the solution in the step 2), and stirring for 1.5h at room temperature by using a 300rpm magnetic stirrer to obtain light brown slurry; 4) Adding the solution obtained in the step 3) and the solution obtained in the step (1) into a three-neck flask, and stirring for 1.5 hours at room temperature by using a 300rpm magnetic stirrer; 5) Transferring the system in the step 4) into a stainless steel reaction kettle, reacting for 1h at 160 ℃, washing with a large amount of deionized water, centrifuging, and finally drying in an oven at 60 ℃ overnight to obtain a product marked as G-S-S for later use
(4) Preparing a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material:
(4-1) adding 40 parts of polyvinyl chloride (PVC), 1 part of composite wear-resistant additive (G-S-S), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP and 0.15 part of paraffin into an internal mixer, and continuously mixing the mixture and the molten blend in the step (2) in the internal mixer at 180 ℃ for 30min;
(4-2) cutting the blend obtained in the step (4-1) by a chopper, transferring the cut blend into a flat vulcanizing machine for molding, wherein the temperatures of an upper template and a lower template are both 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Example 2
(1) Preparing thermoplastic starch; same as example 1
(2) Preparing a degradable polymer matrix: same as example 1
(3) G-S-S was prepared as in example 1;
(4) Preparing a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material:
(4-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix in the step (2), 2 parts of composite wear-resistant additive (G-S-S), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP and 0.15 part of paraffin into an internal mixer, and continuously mixing the mixture and the molten blend in the step (2) in the internal mixer at 180 ℃ for 30min;
(4-2) transferring the mixture which is chopped by the chopper in the step (4-1) into a flat vulcanizing machine for molding, wherein the temperature of an upper template and a lower template is 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Example 3
(1) Preparing thermoplastic starch; same as example 1
(2) Preparing a degradable polymer matrix: same as example 1
(3) G-S-S was prepared as in example 1;
(4) Preparing a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material:
(4-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix in the step (2), 5 parts of composite wear-resistant additive (G-S-S), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP and 0.15 part of paraffin into an internal mixer, and continuously mixing the mixture and the molten blend in the step (2) in the internal mixer at 180 ℃ for 30min;
(4-2) cutting the blend in the step (4-1) by a chopper, transferring the cut blend into a flat vulcanizing machine for molding, wherein the temperature of an upper template and a lower template is 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
COMPARATIVE EXAMPLE 1 (G-free S-S enhancer)
(1) Preparing thermoplastic starch; same as example 1
(2) Preparing a degradable polymer matrix: same as example 1
(3) Preparing a degradable high-strength wear-resistant PVC foam material:
(3-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix in the step (2), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP and 0.15 part of paraffin into an internal mixer, and continuously mixing the mixture and the molten blend in the step (2) in the internal mixer at 180 ℃ for 30min;
(3-2) cutting the blend obtained in the step (3-1) by a chopper, transferring the cut blend into a flat vulcanizing machine for molding, wherein the temperatures of an upper template and a lower template are both 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Comparative example 2 (GO, nano-SiO) 2 And sodium dodecyl sulfate are added into the system independently without any composite treatment)
(1) Preparing thermoplastic starch; same as example 1
(2) Preparing a degradable polymer matrix: same as example 1
(3) Preparing a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material:
(3-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix in the step (2), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP, 0.15 part of paraffin, 1.2 parts of graphene oxide, 3.2 parts of nano-silica and 0.6 part of sodium dodecyl sulfate into an internal mixer, and continuously mixing the mixture and the molten blend in the step (2) in the internal mixer at 180 ℃ for 30min;
(3-2) chopping the blend obtained in the step (3-1) by a chopper, transferring the chopped blend into a flat vulcanizing machine for molding, wherein the temperatures of an upper template and a lower template are both 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Comparative example 3 (containing G-S-S reinforcing agent, but no maleic anhydride in thermoplastic starch)
(1) Preparing thermoplastic starch; taking 300g of corn starch, drying at 70 ℃ for 2h, then putting the corn starch and 90g of glycerol into a high-speed mixer, stirring at 60 ℃ for 1h, and taking materials from a discharge port after mixing; then putting the mixed material into a double-screw extruder, circularly extruding for 2 times at 7 temperature regions from a hopper to a nozzle, wherein the temperature of the 7 temperature regions is respectively 80, 83, 86, 90, 94, 98 and 100 ℃, and cutting an internal mixing product, namely TPS for later use;
(2) Preparing a degradable polymer matrix: the same as example 1;
(3) G-S-S was prepared as in example 1;
(4) Preparing a degradable high-strength wear-resistant PVC foam material:
(4-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix in the step (2), 5 parts of composite wear-resistant additive (G-S-S), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP, 0.15 part of paraffin, 1 part of graphene oxide, 3 parts of nano-silica and 0.6 part of sodium dodecyl sulfate into an internal mixer, and continuously mixing the mixture and the molten blend in the step (2) for 30min in the internal mixer at 180 ℃;
(4-2) chopping the blend obtained in the step (4-1) by a chopper, transferring the chopped blend into a flat vulcanizing machine for molding, wherein the temperatures of an upper template and a lower template are both 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Comparative example 4 (with G-S-S enhancer, without addition of thermoplastic starch)
(1) Preparing a degradable polymer matrix: putting 25 parts of PBAT, 20 parts of PLA and 0.2 part of Joncryl ADR4300 into a preheated internal mixer at 180 ℃ for blending for 10min, wherein the rotating speed of the internal mixer is 30rpm;
(2) Preparation of G-S-S, example 1;
(3) Preparing a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material:
(3-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix in the step (1), 5 parts of composite wear-resistant additive (G-S-S), 6 parts of DOP, 3 parts of alkyl glycoside foaming agent (APG 0810), 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP, 0.15 part of paraffin, 1 part of graphene oxide, 3 parts of nano-silica and 0.6 part of sodium dodecyl sulfate into an internal mixer, and continuously mixing the mixture and the molten blend in the step (1) in the internal mixer at 180 ℃ for 30min;
(3-2) chopping the blend obtained in the step (3-1) by a chopper, transferring the chopped blend into a flat vulcanizing machine for molding, wherein the temperatures of an upper template and a lower template are both 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Comparative example 5 (containing G-S-S reinforcing agent, but replacing APG0810 blowing agent in example 3 with AC blowing agent)
(1) Preparing thermoplastic starch; same as example 1
(2) Preparing a degradable polymer matrix: same as example 1
(3) G-S-S was prepared as in example 1;
(4) Preparing a degradable high-strength wear-resistant PVC (polyvinyl chloride) foam material:
(4-1) adding 40 parts of polyvinyl chloride (PVC), the degradable polymer matrix obtained in the step (2), 5 parts of composite wear-resistant additive (G-S-S), 6 parts of DOP, 3 parts of AC foaming agent, 6 parts of calcium carbonate, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of calcium stearate, 0.8 part of DCP and 0.15 part of paraffin into an internal mixer, and continuously mixing the mixture and the molten blend obtained in the step (2) in the internal mixer at 180 ℃ for 30min;
(4-2) cutting the blend in the step (4-1) by a chopper, transferring the cut blend into a flat vulcanizing machine for molding, wherein the temperature of an upper template and a lower template is 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the product.
Performance testing
From the test results in Table 1, the hardness, compression set, tensile strength, elongation at break, impact strength, abrasion resistance, resilience and tear strength of the composite wear-resistant additive are increased to different degrees from those of example 1 to example 3 with the increase of the content of G-S-S, compared with comparative example 1 without the composite wear-resistant additive (G-S-S), which shows that the composite functional wear-resistant additive of G-S-S is effective in modification and has good compatibility with the matrix. Observing the data of the comparative example 2, because the graphene oxide and the nano-silica belong to polyhydroxy substances and are added separately, and the graphene oxide and the nano-silica are directly added into the whole matrix without any chemical bonding treatment, the respective agglomeration of the graphene oxide and the nano-silica occurs during melting, the dispersibility in the matrix is poor, and the mechanical properties are not improved or reduced compared with those of the comparative example 1. Comparative example 5 the APG foaming agent of example 3 was replaced by a common AC foaming agent which is not well compatible with the degradable components in the matrix but has good compatibility with PVC; the APG foaming agent has good compatibility with the degradable matrix, and the compatibility of APG-PVC is comparable to that of AC foaming agent-PVC, so that the performance is slightly reduced compared with that of example 3, and although the influence on the practicability is not great, the performance is not optimal. The performance test data of comparative examples 3 and 4 and example 3 show that in the case of containing the G-S-S composite functional additive, if no maleic anhydride is contained in TPS, the thermoplastic starch has poor compatibility with PLA and PBAT, and the matrix structure becomes unstable, so that the performance (relative to example 3 and comparative example 4) is greatly reduced; example 3 thermoplastic starch modified with maleic anhydride not only retained the flexibility of starch and soft glycerol segments, but also made the starch grafted maleic anhydride react with PLA, PBAT at high temperature to produce graft, enhanced the compatibility of the matrix components and the stability of the matrix, which was higher than the performance of comparative example 4 without the addition of thermoplastic starch. In the embodiments 1-3, sodium Dodecyl Sulfate (SDS) is used as a mediator substance of graphene oxide and nano-silica, and the C-H bond on the SDS occupies sites on the hydrogen bond of the graphene oxide and the nano-silica, so that the graphene oxide and the nano-silica are chemically bonded, the agglomeration is reduced, the dispersibility is enhanced, and the wear resistance of the material is greatly improved under the condition that the basic mechanical property is not affected. The addition amount of the wear-resistant additive is small, and the comprehensive performance-price ratio is high.
Fig. 2, fig. 3 and fig. 4 are infrared spectrograms of graphene oxide, nano silicon dioxide and the composite functional wear-resistant additive (G-S), respectively. The small peaks at 2916 cm-1 and 2848 cm-1 in FIG. 4 represent-CH 2 Stretching vibration, but the peak was not found at the corresponding position in FIG. 2 and FIG. 3, which indicates-CH on Sodium Dodecyl Sulfate (SDS) 2 Successfully occupy-OH sites on the surfaces of the graphene oxide and the nano-silicon dioxide, namely the SDS is bonded with the surfaces of the nano-silicon dioxide and the graphene oxide, and the SDS serves as an intermediate bridge to successfully bridge the graphene oxide and the nano-silicon dioxide; 1463 cm −1 And 1375 cm −1 Small peak at represents-C-HBending vibration, which indicates the existence of graphene oxide in the product (G-S-S) (corresponding to the corresponding position in FIG. 2); 1042 cm −1 And 797 cm −1 The peak belongs to asymmetric Si-O-Si tensile vibration, which indicates that nano-silica (corresponding to the corresponding position in FIG. 3) exists in the product (G-S-S), and indicates that SDS is successfully grafted with the nano-silica and graphene oxide, and the nano-silica and graphene oxide exist in the product (G-S-S) and are not degenerated.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. The degradable high-strength wear-resistant PVC foam material is characterized in that: the composite material consists of the following raw materials in parts by weight: 40 parts of polyvinyl chloride, 25 parts of PBAT, 20 parts of polylactic acid, 25 parts of thermoplastic starch, 1-5 parts of a composite wear-resistant auxiliary agent, 6 parts of a plasticizer, 3 parts of an alkyl glycoside foaming agent, 6 parts of a filler, 3 parts of titanium dioxide, 4 parts of a calcium-zinc stabilizer, 0.4 part of a lubricant, 0.15 part of paraffin, 0.2 part of an ADR chain extender, 0.8 part of a cross-linking agent and 0-3 parts of an AC foaming agent.
2. The degradable high-strength wear-resistant PVC foam material according to claim 1, characterized in that: the plasticizer is one or a combination of dibutyl phthalate and dioctyl phthalate.
3. The degradable high-strength wear-resistant PVC foam material according to claim 1, characterized in that: the composite wear-resistant auxiliary agent is a graphene oxide-sodium dodecyl sulfate-nano silicon dioxide composite.
4. The degradable high-strength wear-resistant PVC foam material according to claim 3, characterized in that: the preparation steps of the composite wear-resistant additive are as follows;
(1) Dispersing nano silicon dioxide and sodium dodecyl sulfate in deionized water, and stirring for 1.5h at room temperature by using a 300rpm magnetic stirrer to obtain white slurry;
(2) Dispersing graphene oxide in deionized water, and performing ultrasonic treatment for 1 hour to uniformly disperse the graphene oxide;
(3) Dissolving sodium dodecyl sulfate in the solution obtained in the step (2), and stirring the solution for 1.5 hours at room temperature by using a magnetic stirrer with 300rpm to obtain light brown slurry;
(4) Mixing the light brown slurry obtained in the step (3) and the white slurry obtained in the step (1) and stirring the mixture for 1.5 hours at room temperature by using a 300rpm magnetic stirrer;
(5) And (3) reacting the solution obtained in the step (4) at 160 ℃ for 1h, cleaning, centrifuging, and finally drying in an oven at 60 ℃ overnight to obtain the composite wear-resistant additive.
5. The degradable high-strength wear-resistant PVC foam material according to claim 1, characterized in that: the filler is one or a combination of calcium carbonate and talcum powder.
6. The degradable high-strength wear-resistant PVC foam material according to claim 1, characterized in that: the cross-linking agent is dicumyl peroxide.
7. The degradable high-strength wear-resistant PVC foam material according to claim 1, characterized in that: the lubricant is one or a combination of lead stearate and calcium stearate.
8. The degradable high-strength wear-resistant PVC foam material according to claim 1, characterized in that: the preparation steps of the thermoplastic starch are as follows;
(1) Taking 300g of corn starch, drying at 70 ℃ for 2h, then putting the corn starch, 90g of glycerol and 30g of maleic anhydride into a high-speed mixer, stirring at 60 ℃ for 1h, and taking materials from a discharge port after the mixing is finished;
(2) Putting the blend obtained in the step (1) into a double-screw extruder, and circularly extruding for 2 times at 7 temperature regions from a hopper to a nozzle, wherein the temperature of the 7 temperature regions is respectively 80, 83, 86, 90, 94, 98 and 100 ℃;
(3) And (3) granulating the product obtained in the step (2) by using a granulator to obtain the thermoplastic starch.
9. The degradable high-strength wear-resistant PVC foam material according to any one of claims 1 to 8, wherein: 40 parts of polyvinyl chloride, 25 parts of PBAT, 20 parts of polylactic acid, 25 parts of thermoplastic starch, 1-5 parts of composite wear-resistant auxiliary agent, 6 parts of plasticizer, 3 parts of alkyl glycoside foaming agent, 6 parts of filler, 3 parts of titanium dioxide, 4 parts of calcium-zinc stabilizer, 0.4 part of lubricant, 0.15 part of paraffin, 0.2 part of ADR chain extender, 0.8 part of cross-linking agent and 0-3 parts of AC foaming agent are put into an internal mixer for blending, and then the blended product is subjected to cold-hot compression molding.
10. The preparation method of the degradable high-strength wear-resistant PVC foam material according to claim 9, characterized in that: the method comprises the following steps:
(1) PBAT, polylactic acid, ADR chain extender and thermoplastic starch are put into a pre-heated internal mixer at 180 ℃ to be mixed for 10min, and the rotating speed of the internal mixer is 30rpm;
(2) Adding polyvinyl chloride, a composite wear-resistant auxiliary agent, a plasticizer, an AC foaming agent, a filler, titanium dioxide, a calcium-zinc stabilizer, a lubricant, a cross-linking agent and paraffin into the blend obtained in the step (1), and continuously mixing in an internal mixer at 180 ℃ for 30min;
(3) And (3) cutting the blend obtained in the step (2) by using a cutting machine, then transferring the cut blend into a flat vulcanizing machine for molding, wherein the temperature of an upper template and a lower template is 180 ℃, the pressure is 12MPa, the molding time is 150s, and opening the mold after cooling for 360s to take out the degradable high-strength wear-resistant PVC foam material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211637854.1A CN115725143B (en) | 2022-12-20 | 2022-12-20 | Degradable high-strength wear-resistant PVC (polyvinyl chloride) foaming material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211637854.1A CN115725143B (en) | 2022-12-20 | 2022-12-20 | Degradable high-strength wear-resistant PVC (polyvinyl chloride) foaming material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115725143A true CN115725143A (en) | 2023-03-03 |
| CN115725143B CN115725143B (en) | 2023-09-29 |
Family
ID=85301598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211637854.1A Active CN115725143B (en) | 2022-12-20 | 2022-12-20 | Degradable high-strength wear-resistant PVC (polyvinyl chloride) foaming material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115725143B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205021A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic and PBAT blend and preparation method thereof |
| CN109486083A (en) * | 2018-12-20 | 2019-03-19 | 吉林中粮生化有限公司 | A kind of biodegradable blend film and preparation method thereof |
| CN110511442A (en) * | 2019-09-27 | 2019-11-29 | 福州绿帆包装材料有限公司 | A kind of Degradable environment-friendlyplastic plastic film formulation and its production technology |
| WO2020119158A1 (en) * | 2019-07-12 | 2020-06-18 | 上海昶法新材料有限公司 | Biodegradable product and preparation method therefor |
| CN111333950A (en) * | 2020-04-23 | 2020-06-26 | 福州大学 | High-mechanical-strength wear-resistant EVA composite foam material and preparation method thereof |
| CN112812515A (en) * | 2020-12-31 | 2021-05-18 | 浙江工业大学 | Degradable foaming material and preparation method thereof |
| CN112898753A (en) * | 2021-02-08 | 2021-06-04 | 沈阳工业大学 | Polylactic acid/PBAT/thermoplastic starch composite foaming flame-retardant material and preparation method thereof |
| CN112940474A (en) * | 2021-02-04 | 2021-06-11 | 杭州之西科技有限公司 | Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof |
| CN113861635A (en) * | 2021-10-19 | 2021-12-31 | 上海复命新材料科技有限公司 | Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof |
| CN114874637A (en) * | 2022-06-07 | 2022-08-09 | 临沂大学 | Environment-friendly degradable modified polyvinyl chloride composite material and preparation method and application thereof |
-
2022
- 2022-12-20 CN CN202211637854.1A patent/CN115725143B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205021A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic and PBAT blend and preparation method thereof |
| CN109486083A (en) * | 2018-12-20 | 2019-03-19 | 吉林中粮生化有限公司 | A kind of biodegradable blend film and preparation method thereof |
| WO2020119158A1 (en) * | 2019-07-12 | 2020-06-18 | 上海昶法新材料有限公司 | Biodegradable product and preparation method therefor |
| CN110511442A (en) * | 2019-09-27 | 2019-11-29 | 福州绿帆包装材料有限公司 | A kind of Degradable environment-friendlyplastic plastic film formulation and its production technology |
| CN111333950A (en) * | 2020-04-23 | 2020-06-26 | 福州大学 | High-mechanical-strength wear-resistant EVA composite foam material and preparation method thereof |
| CN112812515A (en) * | 2020-12-31 | 2021-05-18 | 浙江工业大学 | Degradable foaming material and preparation method thereof |
| CN112940474A (en) * | 2021-02-04 | 2021-06-11 | 杭州之西科技有限公司 | Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof |
| CN112898753A (en) * | 2021-02-08 | 2021-06-04 | 沈阳工业大学 | Polylactic acid/PBAT/thermoplastic starch composite foaming flame-retardant material and preparation method thereof |
| CN113861635A (en) * | 2021-10-19 | 2021-12-31 | 上海复命新材料科技有限公司 | Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof |
| CN114874637A (en) * | 2022-06-07 | 2022-08-09 | 临沂大学 | Environment-friendly degradable modified polyvinyl chloride composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115725143B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110655769A (en) | High-toughness fully-degradable composite material | |
| WO2022252266A1 (en) | Composite toughened and high-temperature-resistant polylactic acid modified material and preparation method therefor | |
| CN113956623B (en) | Full-biodegradable plastic composite modified material suitable for film bag and preparation method thereof | |
| CN113801350A (en) | Calcium carbonate filled PBAT/PLA biodegradable plastic film and preparation method thereof | |
| US11732058B2 (en) | Thermoplastic starch and starch-based biodegradable film | |
| CN112358708A (en) | Biodegradable film blowing modified material with high starch content and preparation method thereof | |
| CN106674923A (en) | Controllable-degradation PBAT/PLA (poly(butyleneadipate-co-terephthalate)/polylactic acid) composite film and preparation method thereof | |
| CN111763410B (en) | Biodegradable PBAT alloy with high starch content and preparation method thereof | |
| CN113861636A (en) | High-stiffness high-toughness fully-degradable PBAT/PLA resin composition and preparation method thereof | |
| CN109486138A (en) | PHA modified PLA/PBAT biodegradable resin and preparation method thereof | |
| CN115093721A (en) | Tea fiber/PHBV/PBAT ternary composite material and preparation method and application thereof | |
| CN102675841A (en) | Polylactic acid and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) nano modified composite | |
| CN114921069B (en) | Full-biodegradable film with high heat seal strength and preparation method and application thereof | |
| CN115725143B (en) | Degradable high-strength wear-resistant PVC (polyvinyl chloride) foaming material and preparation method thereof | |
| CN116218165A (en) | Nanoparticle-biodegradable polyester film and preparation method thereof | |
| CN114685961B (en) | Modified polylactic acid film material | |
| CN113896955A (en) | Starch-based sheet composition and preparation method thereof | |
| CN113956546A (en) | Preparation method of starch-based fully-degradable blown film composition | |
| CN111925563A (en) | High-impact-resistance injection molding grade biological starch plastic and preparation method thereof | |
| CN1135550A (en) | Degraded leather-imitation and production method and application thereof | |
| CN111423703A (en) | CaCO for high-filling PBAT biodegradable film3Surface treatment method and preparation of film | |
| CN112592576A (en) | Biodegradable functional master batch for film and preparation method thereof | |
| CN115819935B (en) | High-wear-resistance high-strength degradable high polymer material | |
| CN115536881B (en) | Preparation method of biodegradable PLA composite film | |
| CN115286904B (en) | Biodegradable breathable material, biodegradable breathable master batch, biodegradable breathable film and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |