CN110734616B - Preparation method of polyvinyl alcohol-based composite material - Google Patents
Preparation method of polyvinyl alcohol-based composite material Download PDFInfo
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- CN110734616B CN110734616B CN201910994116.4A CN201910994116A CN110734616B CN 110734616 B CN110734616 B CN 110734616B CN 201910994116 A CN201910994116 A CN 201910994116A CN 110734616 B CN110734616 B CN 110734616B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention discloses a preparation method of a polyvinyl alcohol-based composite material, which relates to the technical field of composite material processing and comprises the following steps: (1) swelling by microwave; (2) preparing shell powder; (3) surface modification; (4) extruding and granulating; the polyvinyl alcohol-based composite material is prepared by performing microwave swelling treatment on polyvinyl alcohol and surface modification treatment on shell powder, and can be applied to processing of various plastic products, such as films, hollow containers, injection-molded products and the like; the processed plastic product has excellent barrier property while ensuring good mechanical property.
Description
The technical field is as follows:
the invention relates to the technical field of composite material processing, in particular to a preparation method of a polyvinyl alcohol-based composite material.
Background art:
polyvinyl alcohol is a polymer with excellent performance and wide application, and a hollow container prepared from the polyvinyl alcohol has the advantages of good mechanical property, excellent oxygen and oil resistance, no dust absorption, transparency and the like, has water solubility and biodegradability under certain conditions, and plays an important role in packaging materials such as non-polar solvents and the like.
The polyvinyl alcohol belongs to a crystalline polymer, the molecule contains a large amount of hydroxyl groups, and a large amount of intramolecular and intermolecular hydrogen bonds can be formed, so that the melting point of the polyvinyl alcohol reaches 220-240 ℃, but the decomposition temperature is low, dehydration and etherification begin at 160 ℃, decomposition begins at 200 ℃, decomposition occurs in the melting process, a thermoplastic processing window is not provided, and the preparation of a hollow container is difficult.
Patent CN201510392452.3 discloses a polyvinyl alcohol/shell powder biomass composite material and a preparation method thereof, the composite material is prepared by melt blending of polyvinyl alcohol, shell powder and a plasticizer, the plasticizer is polyhydric alcohol, aliphatic amide, aliphatic alcohol amine and low molecular weight polyethylene glycol, although the composite material prepared by the embodiment has a tensile strength of 80MPa and an elongation at break of 300%, the composite material cannot have high tensile strength and elongation at break at the same time, the barrier property of the composite material to a nonpolar solvent is not tested, meanwhile, the shell powder adopted by the composite material is directly washed by water, and the shell is not treated at all to improve the service performance of the shell.
The invention content is as follows:
the invention aims to solve the technical problem of providing a preparation method of a polyvinyl alcohol-based composite material, wherein the polyvinyl alcohol-based composite material is prepared by performing microwave swelling treatment on polyvinyl alcohol and surface modification treatment on shell powder, the composite material can be applied to processing of various plastic products, and the processed plastic products have excellent barrier property while ensuring good mechanical property.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a preparation method of a polyvinyl alcohol-based composite material comprises the following steps:
(1) microwave swelling: adding polyvinyl alcohol into water, stirring and performing microwave reflux treatment by using a microwave reactor, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing the shell with water to remove impurities, drying to constant weight, and then performing coarse crushing and fine crushing to prepare 100-mesh and 200-mesh powder to obtain shell powder;
(3) surface modification: heating triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding shell powder, continuing to preserve heat and stir at the melting point temperature, and crushing the shell powder into powder of 200-mesh-300 meshes after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding the polyvinyl alcohol hydrogel and the modified shell powder into a high-speed mixer, uniformly mixing, feeding into a screw extruder, carrying out melt extrusion, and granulating to obtain the polyvinyl alcohol-based composite material.
The alcoholysis degree of the polyvinyl alcohol is 98-99%, and the viscosity is 55-65 mpa.s.
The mass ratio of the water to the polyvinyl alcohol is 1-10: 1.
The working conditions of the microwave reactor are microwave frequency of 2450MHz and microwave power of 500-.
The mass ratio of the triglycidyl isocyanurate to the shell powder is 0.1-0.5: 1.
The mass ratio of the polyvinyl alcohol hydrogel to the modified shell powder is 5-20: 1.
The extrusion temperature of the screw extruder is 190-220 ℃.
In order to further enhance the barrier property of the prepared composite material to a nonpolar solvent, the invention also adds the magnesium polydimethylacrylate as an auxiliary agent, and the specific technical scheme is as follows:
(1) microwave swelling: adding polyvinyl alcohol into water, stirring and performing microwave reflux treatment by using a microwave reactor, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing the shell with water to remove impurities, drying to constant weight, and then performing coarse crushing and fine crushing to prepare 100-mesh and 200-mesh powder to obtain shell powder;
(3) surface modification: heating triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding shell powder, continuing to preserve heat and stir at the melting point temperature, and crushing the shell powder into powder of 200-mesh-300 meshes after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding polyvinyl alcohol hydrogel, modified shell powder and magnesium polydimethylacrylate into a high-speed mixer, uniformly mixing, feeding into a screw extruder, carrying out melt extrusion, and granulating to obtain the polyvinyl alcohol-based composite material.
The mass ratio of the polyvinyl alcohol hydrogel to the modified shell powder to the magnesium dimethacrylate is 5-20:1: 0.05-0.5.
The magnesium dimethacrylate is prepared by in-situ polymerization of magnesium dimethacrylate, and the preparation method comprises the following steps: adding magnesium dimethacrylate and an initiator into 95% ethanol, introducing nitrogen for protection, adding a chain transfer agent, heating to a reflux state, keeping the temperature for reaction, centrifugally separating solid after the reaction is finished, and drying the obtained solid in an oven to obtain the magnesium dimethacrylate.
The mass ratio of the magnesium dimethacrylate, the initiator and the chain transfer agent is 20:0.02-0.1: 0.01-0.05.
The initiator is one of azobisisobutyronitrile or azobisisoheptonitrile.
The chain transfer agent is dodecyl mercaptan.
The processing principle of the invention is as follows:
(1) the microwave technology is utilized to swell the polyvinyl alcohol, and the flexibility of a polyvinyl alcohol molecular chain is improved while the hydrogel is prepared, so that the subsequent composite modification is facilitated.
(2) The shell mainly comprises calcium carbonate, the hardness and toughness of the shell are far higher than those of common calcium carbonate, the shell serving as an inorganic material can realize reasonable utilization of natural resources, and the mechanical property of the prepared polyvinyl alcohol-based composite material can be ensured.
(3) The corrosion resistance of the calcium carbonate is enhanced by taking triglycidyl isocyanurate as a modifier through surface modification of the calcium carbonate, and the surface modification principle adopts a coating modification mode, and particularly improves the barrier property of the finally prepared composite material to a non-polar solvent through the surface modification; meanwhile, the addition of the triglycidyl isocyanurate can also play a role of a plasticizer, so that the need of adding the plasticizer is avoided, and the triglycidyl isocyanurate is conventionally used as a resin curing agent or an adhesive, and the use of the triglycidyl isocyanurate as the plasticizer does not belong to the common knowledge in the field.
(4) The barrier property of the prepared composite material to a non-polar solvent is further enhanced by taking the magnesium polydimethylacrylate as an auxiliary agent, and the mechanical property of the prepared composite material is ensured.
The invention has the beneficial effects that: the polyvinyl alcohol-based composite material is prepared by performing microwave swelling treatment on polyvinyl alcohol and surface modification treatment on shell powder, and can be applied to processing of various plastic products, such as films, hollow containers, injection-molded products and the like; the processed and prepared plastic product has excellent barrier property while ensuring good mechanical property, the tensile strength reaches more than 55MPa, and the impact strength reaches 20KJ/m2Above, the permeabilities to benzene, toluene and xylene were lower than 0.5%, 0.35% and 0.15%, respectively.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The polyvinyl alcohols in the following examples and comparative examples were obtained from 2499, 98% alcoholysis, 61mpa.s viscosity, of Useradi Utility Co; the shell is from processing factory of mineral products of Zetong Lingshou county.
Example 1
Preparing a polyvinyl alcohol-based composite material:
(1) microwave swelling: adding 10kg of polyvinyl alcohol into 40kg of water, performing microwave reflux treatment for 10min by using a microwave reactor with microwave frequency of 2450MHz and microwave power of 600W while stirring, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing shell with water to remove impurities, drying at 80 deg.C to constant weight, coarse pulverizing, fine pulverizing to obtain 120 mesh powder;
(3) surface modification: heating 0.25kg of triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding 1kg of shell powder, continuing to preserve heat and stir at the melting point temperature for 2 hours, and crushing the shell powder into 200-mesh powder after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding 15kg of polyvinyl alcohol hydrogel and 1kg of modified shell powder into a high-speed mixer, mixing at a high speed of 800r/min for 10min, feeding into a screw extruder, carrying out melt extrusion at 210 ℃, and granulating to obtain the polyvinyl alcohol-based composite material.
Example 2
Preparing a polyvinyl alcohol-based composite material:
(1) microwave swelling: adding 10kg of polyvinyl alcohol into 40kg of water, performing microwave reflux treatment for 10min by using a microwave reactor with microwave frequency of 2450MHz and microwave power of 600W while stirring, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing shell with water to remove impurities, drying at 80 deg.C to constant weight, coarse pulverizing, fine pulverizing to obtain 120 mesh powder;
(3) surface modification: heating 0.2kg of triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding 1kg of shell powder, continuing to preserve heat and stir at the melting point temperature for 2 hours, and crushing the shell powder into 200-mesh powder after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding 20kg of polyvinyl alcohol hydrogel and 1kg of modified shell powder into a high-speed mixer, mixing at a high speed of 800r/min for 10min, feeding into a screw extruder, carrying out melt extrusion at 210 ℃, and granulating to obtain the polyvinyl alcohol-based composite material.
Example 3
The same procedure as in example 1 was repeated except that in example 3 in which an auxiliary was added was used as a control, the rest was the same as in example 1.
Preparing a polyvinyl alcohol-based composite material:
(1) microwave swelling: adding 10kg of polyvinyl alcohol into 40kg of water, performing microwave reflux treatment for 10min by using a microwave reactor with microwave frequency of 2450MHz and microwave power of 600W while stirring, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing shell with water to remove impurities, drying at 80 deg.C to constant weight, coarse pulverizing, fine pulverizing to obtain 120 mesh powder;
(3) surface modification: heating 0.25kg of triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding 1kg of shell powder, continuing to preserve heat and stir at the melting point temperature for 2 hours, and crushing the shell powder into 200-mesh powder after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding 15kg of polyvinyl alcohol hydrogel, 1kg of modified shell powder and 0.1kg of magnesium polydimethylacrylate into a high-speed mixer, mixing at a high speed of 800r/min for 10min, feeding into a screw extruder, carrying out melt extrusion at 210 ℃, and granulating to obtain the polyvinyl alcohol-based composite material.
Preparation of magnesium polydimethylacrylate: adding 20g of magnesium dimethacrylate and 0.1g of azobisisobutyronitrile into 100g of 95% ethanol, introducing nitrogen for protection, adding 0.05g of dodecanethiol, heating to a reflux state, keeping the temperature for reaction for 3 hours, centrifugally separating solid after the reaction is finished, and drying the obtained solid in an oven at 70 ℃ to obtain the magnesium polydimethylacrylate.
Comparative example 1
The comparative example 1 in which the polyvinyl alcohol was not swollen by the microwave was prepared as a control in example 1, and the rest was completely the same as example 1.
Preparing a polyvinyl alcohol-based composite material:
(1) swelling: adding 10kg of polyvinyl alcohol into 40kg of water, and stirring for 10min to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing shell with water to remove impurities, drying at 80 deg.C to constant weight, coarse pulverizing, fine pulverizing to obtain 120 mesh powder;
(3) surface modification: heating 0.25kg of triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding 1kg of shell powder, continuing to preserve heat and stir at the melting point temperature for 2 hours, and crushing the shell powder into 200-mesh powder after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding 15kg of polyvinyl alcohol hydrogel and 1kg of modified shell powder into a high-speed mixer, mixing at a high speed of 800r/min for 10min, feeding into a screw extruder, carrying out melt extrusion at 210 ℃, and granulating to obtain the polyvinyl alcohol-based composite material.
Comparative example 2
In comparison with example 1, comparative example 2 in which no surface modification was performed on the shell powder was prepared, and the rest was completely the same as example 1.
Preparing a polyvinyl alcohol-based composite material:
(1) microwave swelling: adding 10kg of polyvinyl alcohol into 40kg of water, performing microwave reflux treatment for 10min by using a microwave reactor with microwave frequency of 2450MHz and microwave power of 600W while stirring, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing shell with water to remove impurities, drying at 80 deg.C to constant weight, coarse pulverizing, fine pulverizing to obtain 200 mesh powder;
(3) and (3) extruding and granulating: adding 15kg of polyvinyl alcohol hydrogel and 1kg of shell powder into a high-speed mixer, mixing at a high speed of 800r/min for 10min, feeding into a screw extruder, carrying out melt extrusion at 210 ℃, and granulating to obtain the polyvinyl alcohol-based composite material.
Comparative example 3
The patent CN201510392452.3 example 1 made a polyvinyl alcohol/shell powder biomass composite material.
Examples 1 to 3 and comparative examples 1 to 3 were used to prepare polyvinyl alcohol-based composites, and 20kg of the prepared polyvinyl alcohol-based composites were melt-plasticized at 210 ℃ by an extruder to extrude preforms, and were subjected to axial stretching for 1.5, and then to blow molding at 150 ℃ by a mold to form hollow containers, and the use properties of the hollow containers were tested, and the results are shown in table 1.
The tensile strength test is according to the standard ASTM D638-2014, the impact strength test is according to the standard ASTM D256-2003, and the permeability test is according to the standard ASTM D2684-89.
TABLE 1
As can be seen from table 1, in the examples, the mechanical properties and the barrier properties to non-polar solvents of the prepared composite materials can be improved by performing microwave swelling treatment on polyvinyl alcohol, performing surface modification treatment on shell powder, and adding an auxiliary agent of magnesium polydimethylacrylate.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of a polyvinyl alcohol-based composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) microwave swelling: adding polyvinyl alcohol into water, stirring and performing microwave reflux treatment by using a microwave reactor, and naturally cooling to room temperature after the treatment is finished to obtain polyvinyl alcohol hydrogel;
(2) shell powder preparation: washing the shell with water to remove impurities, drying to constant weight, and then performing coarse crushing and fine crushing to prepare 100-mesh and 200-mesh powder to obtain shell powder;
(3) surface modification: heating triglycidyl isocyanurate to a melting point, preserving heat until the triglycidyl isocyanurate is completely molten, adding shell powder, continuing to preserve heat and stir at the melting point temperature, and crushing the shell powder into powder of 200-mesh-300 meshes after the modification is finished and the temperature is naturally reduced to be below 45 ℃ to obtain the modified shell powder;
(4) and (3) extruding and granulating: adding the polyvinyl alcohol hydrogel and the modified shell powder into a high-speed mixer, uniformly mixing, feeding into a screw extruder, carrying out melt extrusion, and granulating to obtain the polyvinyl alcohol-based composite material.
2. The method for preparing a polyvinyl alcohol-based composite material according to claim 1, characterized in that: the alcoholysis degree of the polyvinyl alcohol is 98-99%, and the viscosity is 55-65 mpa.s.
3. The method for preparing a polyvinyl alcohol-based composite material according to claim 1, characterized in that: the mass ratio of the water to the polyvinyl alcohol is 1-10: 1.
4. The method for preparing a polyvinyl alcohol-based composite material according to claim 1, characterized in that: the working conditions of the microwave reactor are microwave frequency of 2450MHz and microwave power of 500-.
5. The method for preparing a polyvinyl alcohol-based composite material according to claim 1, characterized in that: the mass ratio of the triglycidyl isocyanurate to the shell powder is 0.1-0.5: 1.
6. The method for preparing a polyvinyl alcohol-based composite material according to claim 1, characterized in that: the mass ratio of the polyvinyl alcohol hydrogel to the modified shell powder is 5-20: 1.
7. The method for preparing a polyvinyl alcohol-based composite material according to claim 1, characterized in that: the extrusion temperature of the screw extruder is 190-220 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864133A (en) * | 2010-06-30 | 2010-10-20 | 石家庄铁道大学 | Starch and polyvinyl alcohol composite material and preparation method thereof |
| CN105001569A (en) * | 2015-07-07 | 2015-10-28 | 四川大学 | Polyvinyl alcohol/shell powder biomass composite material and preparation method therefor |
| CN108298654A (en) * | 2018-01-25 | 2018-07-20 | 胡瑞滢 | The preparation method of sanitary sewage coagulation nano composite flocculant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864133A (en) * | 2010-06-30 | 2010-10-20 | 石家庄铁道大学 | Starch and polyvinyl alcohol composite material and preparation method thereof |
| CN105001569A (en) * | 2015-07-07 | 2015-10-28 | 四川大学 | Polyvinyl alcohol/shell powder biomass composite material and preparation method therefor |
| CN108298654A (en) * | 2018-01-25 | 2018-07-20 | 胡瑞滢 | The preparation method of sanitary sewage coagulation nano composite flocculant |
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