CN113372587B - Preparation method of organic-inorganic nano-doped polymer material processing aid master batch - Google Patents
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Abstract
The invention relates to the field of material processing, and the organic-inorganic nano-doped polymer material processing aid master batch prepared by the invention comprises the following steps: preparing a modified inorganic composite powder material and preparing a high polymer material processing aid master batch; the invention can effectively improve the processing rheological property of the resin material, reduce the melt viscosity, reduce the screw torque, reduce the internal pressure of the machine barrel, reduce the processing temperature and reduce the processing difficulty. The modified inorganic composite powder material of the invention participates in polymerization reaction, and the polymer material processing aid master batch prepared by adopting an organic-inorganic doping copolymerization mode achieves the purpose of better improving processing of common PPA master batch, effectively eliminates the phenomenon of melt fracture caused by blow molding processing, and improves the processing stability.
Description
Technical Field
The invention relates to the field of material processing, in particular to a preparation method of an organic-inorganic nano-doped polymer material processing aid master batch.
Background
The fluorine compound in the fluorine-containing processing aid master batch has extremely low surface energy, so that the internal friction among resin molecules can be reduced in plastic processing, the melting rate and the deformability of a melt are increased, and the apparent viscosity of the melt is reduced, so that the overall plasticizing effect can be improved. Meanwhile, the fluorine-containing processing aid master batch seeps out of the melt from the inside of the melt to the surface of the melt in the processing process to form an isolation layer on the surface of metal, so that the adhesive force between the melt and the surfaces of a machine body and a die orifice metal is reduced, the friction between the melt and a wall of the machine body in the movement process is reduced, and the uneven movement state of the melt in the processing process is improved.
CN111087582A discloses a preparation method of a fluorine-containing polymer processing aid, which comprises the following steps: simultaneously putting epsilon-caprolactone and the fluoropolymer elastomer into a reactor, and heating to dissolve; and after the fluoropolymer elastomer is completely dissolved, cooling, adding polyol, uniformly mixing, adding an organic tin catalyst for polymerization reaction, cooling after the reaction is finished, and crushing or spray granulating to obtain the fluoropolymer processing aid. The processing aid prepared by the method can reduce the extrusion pressure of the polymer during extrusion, improve the processing efficiency, improve the phenomena of melt fracture and shark skin of the polymer extrusion and effectively improve the surface quality of products. Compared with the prior art, the processing aid has the characteristics of uniform dispersed particle size when the polymer is processed, difficult coking when being applied to a long-time die head of polymer extrusion processing, and the like.
CN106947113B relates to a fluorine-containing polymer processing aid and a preparation method thereof. The micro-particle comprises a core part and a shell part, wherein the core part is made of fluorocarbon polymer, and the shell part is made of organosilicon modified nano-silicon. The nano silicon refers to organosilicon modified nano silicon containing hydrogen bonds and hydroxyl groups. The invention aims to provide a fluorine-containing polymer processing aid which can obviously improve the extrusion speed and improve the surface smoothness when used for extruding and processing silane cross-linked polyolefin. The temperature resistance level of the nano silicon is very high, and the application range is wider; the invention also provides a preparation method of the composition.
CN1352668a provides a polymer processing aid composition, a melt processable polymer composition using the polymer processing aid, and a method of improving the melt processability of thermoplastic polymers. The polymer processing aid composition comprises a multimodal fluoropolymer, preferably comprising interpolymerized units derived from an ethylenically unsaturated fluoromonomer, tetrafluoroethylene, and at least one ethylenically copolymerizable alpha-olefin monomer.
The performance of the fluoropolymer processing aid prepared by the method and the prior art needs to be improved, and the use effects of various types of products in the market are different.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an organic-inorganic nano-doped high polymer material processing aid master batch.
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing a modified inorganic composite powder material: adding 32-60 parts of nano calcium carbonate, 1.5-4.5 parts of nano silicon dioxide and 1.8-4.4 parts of calcium hydroxy phosphate into 20-60 parts of ethanol according to the mass parts, uniformly stirring and dispersing, adding 0.5-1.8 parts of flow promoter, controlling the temperature to be 45-65 ℃, stirring and reacting for 10-30min, filtering, washing and drying after completion to obtain a modified inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 50-75 parts by mass of vinylidene fluoride-hexafluoropropylene copolymer, 0.3-0.9 part by mass of emulsifier and 60-120 parts by mass of water into a reaction kettle, stirring for 30-60min to fully emulsify a system, adding 0.1-0.6 part by mass of buffer into the reaction kettle, and uniformly stirring; adding 35-54 parts of methyl methacrylate, 5-20 parts of styrene and 1-10 parts of acrylonitrile into a reaction kettle, stirring for 5-20min, adding 5.2-12.6 parts of modified inorganic composite powder material, stirring for 5-20min, controlling the temperature to 55-75 ℃, slowly adding 5-12 parts of aqueous solution dissolved with 0.8-1.3 parts of initiator into the reaction kettle within 60-90min under the protection of nitrogen, controlling the temperature to 60-80 ℃ after the completion, stirring for polymerization reaction for 120-180min, cooling to room temperature after the completion, salting out to obtain a polymer, washing, drying and granulating the polymer to obtain the organic-inorganic nano-doped polymer material processing aid master batch.
Further: the preparation method of the flow promoter comprises the following steps:
adding 5-12 parts of tetramethyltetravinylcyclotetrasiloxane into 40-60 parts of dimethylbenzene for dispersion and stirring, then adding 3-8 parts of hexafluorobutyl acrylate, 0.5-1.2 parts of butenediol and 0.1-1 part of decenal, heating to 60-75 ℃, adding 0.001-0.01 part of benzoyl peroxide and 0.001-0.005 part of dodecyl mercaptan, reacting for 4-8h under the protection of nitrogen, and then distilling under reduced pressure at 140 ℃ for 0.5-2h to obtain the flow promoter.
The flow promoter is prepared by copolymerizing unsaturated double bonds in tetramethyl tetravinylcyclotetrasiloxane and fluorine-containing functional monomers and other functional monomers through free radicals, has a multi-end branched structure, and has a main reaction equation as shown in the specification:
the hexafluoropropylene content in the vinylidene fluoride-hexafluoropropylene copolymer is 30-45 w%.
The initiator is potassium persulfate or ammonium persulfate.
The buffer is sodium bicarbonate or disodium hydrogen phosphate.
The organic-inorganic nano-doped polymer material processing aid master batch prepared by the invention can effectively improve the processing rheological property of resin materials, reduce the melt viscosity, reduce the screw torque, reduce the internal pressure of a machine barrel, reduce the processing temperature and reduce the processing difficulty. The flow promoter for the uniformly mixed inorganic composite powder material is prepared by copolymerizing unsaturated double bonds in tetramethyl tetravinylcyclotetrasiloxane, fluorine-containing functional monomers and other functional monomers through free radicals, has a multi-end branching structure, and is grafted to the surface of powder to prepare the modified inorganic composite powder material; the modified inorganic composite powder material of the invention participates in polymerization reaction, and the polymer material processing aid master batch prepared by adopting an organic-inorganic doping copolymerization mode achieves the purpose of better improving processing of common PPA master batch, effectively eliminates the phenomenon of melt fracture caused by blow molding processing, and improves the processing stability.
Drawings
FIG. 1 is a Fourier infrared spectrum of the organic-inorganic nano-doped polymer material processing aid masterbatch prepared in example 2.
The stretching absorption peak of the carbon-hydrogen bond exists near 2496cm-1, the absorption peak of the ester carbonyl exists near 1732cm-1, and the methyl methacrylate participates in the reaction; an absorption peak of a fluorocarbon bond exists near 1039cm < -1 >, which indicates that the vinylidene fluoride-hexafluoropropylene copolymer participates in the reaction; a telescopic absorption peak of a benzene ring skeleton exists near 1500/1456/1377cm < -1 >, which indicates that styrene participates in the reaction; the presence of an absorption peak near 2224cm-1 for the nitrile group indicates that acrylonitrile is involved in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
the invention selects a hard PVC pipe extrusion formula as a test basic formula: 100g of PVC granules, 5.2g of composite lead salt stabilizer, 8g of calcium carbonate, 6g of titanium dioxide, 3g of processing aid and 8g of chlorinated polyethylene granules; the raw materials are uniformly mixed by a high-speed mixer, 62.5g of the mixture is weighed each time, a torque rheometer is used for testing (the temperature of the mixer is 170 ℃), the processability (plasticizing time and melting temperature) of the PVC material is measured by the torque rheometer, and the melting factor is calculated.
Example 1
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing a modified inorganic composite powder material: adding 32kg of nano calcium carbonate, 1.5kg of nano silicon dioxide and 1.8kg of calcium hydroxy phosphate into 20kg of ethanol, uniformly stirring and dispersing, adding 0.5kg of flow promoter, controlling the temperature at 45 ℃, stirring and reacting for 10min, filtering, washing and drying after completion to obtain a modified inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 50kg of vinylidene fluoride-hexafluoropropylene copolymer, 0.3kg of emulsifier and 60kg of water into a reaction kettle, stirring for 30min to fully emulsify the system, adding 0.1kg of buffer into the reaction kettle after completion, and uniformly stirring; adding 35kg of methyl methacrylate, 5kg of styrene and 1kg of acrylonitrile into a reaction kettle, stirring for 5min, adding 5.2kg of modified inorganic composite powder material, stirring for 5min, controlling the temperature to 55 ℃, then slowly adding 5kg of aqueous solution dissolved with 0.8kg of initiator into the reaction kettle within 60min under the protection of nitrogen, controlling the temperature to 60 ℃ after the completion of the reaction, stirring for polymerization for 120min, cooling to room temperature after the completion of the reaction, salting out to obtain a polymer, washing, drying and granulating to obtain the organic-inorganic nano-doped high polymer material processing aid master batch.
Further: the preparation method of the flow promoter comprises the following steps:
adding 5kg of tetramethyltetravinylcyclotetrasiloxane into 40kg of dimethylbenzene, dispersing and stirring, then adding 3kg of hexafluorobutyl acrylate, 0.5kg of butenediol and 0.1kg of decenal, heating to 60 ℃, adding 0.001kg of benzoyl peroxide and 0.001kg of dodecyl mercaptan, reacting for 4 hours under the protection of nitrogen, and then distilling under reduced pressure at 140 ℃ for 0.5 hour to obtain the flow promoter.
The hexafluoropropylene content in the vinylidene fluoride-hexafluoropropylene copolymer is 30%.
The initiator is potassium persulfate.
The buffer is sodium bicarbonate.
Example 2
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing a modified inorganic composite powder material: adding 46kg of nano calcium carbonate, 3kg of nano silicon dioxide and 3.1kg of calcium hydroxy phosphate into 40kg of ethanol, stirring and dispersing uniformly, adding 1.2kg of flow promoter, controlling the temperature to be 55 ℃, stirring and reacting for 20min, filtering, washing and drying after completion to obtain a modified inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 65kg of vinylidene fluoride-hexafluoropropylene copolymer, 0.6kg of emulsifier and 90kg of water into a reaction kettle, stirring for 45min to fully emulsify the system, adding 0.3kg of buffering agent into the reaction kettle after completion, and uniformly stirring; then adding 45kg of methyl methacrylate, 12kg of styrene and 5kg of acrylonitrile into a reaction kettle, stirring for 10min, adding 8.6kg of modified inorganic composite powder material, stirring for 15min, controlling the temperature to 65 ℃, then slowly adding 9kg of aqueous solution dissolved with 1.2kg of initiator into the reaction kettle within 80min under the protection of nitrogen, controlling the temperature to 70 ℃ after the completion of the reaction, stirring for polymerization for 150min, cooling to room temperature after the completion of the reaction, salting out to obtain a polymer, washing, drying and granulating to obtain the organic-inorganic nano-doped high polymer material processing aid master batch.
Further: the preparation method of the flow promoter comprises the following steps:
adding 8kg of tetramethyltetravinylcyclotetrasiloxane into 50kg of dimethylbenzene, dispersing and stirring, then adding 6kg of hexafluorobutyl acrylate, 0.9kg of butenediol and 0.6kg of decenal, heating to 68 ℃, adding 0.006kg of benzoyl peroxide and 0.003kg of dodecyl mercaptan, reacting for 6 hours under the protection of nitrogen, and then distilling at 140 ℃ under reduced pressure for 1.3 hours to obtain the flow promoter.
The hexafluoropropylene content in the vinylidene fluoride-hexafluoropropylene copolymer is 35w%.
The initiator is ammonium persulfate.
The buffer is disodium hydrogen phosphate.
Example 3
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing a modified inorganic composite powder material: adding 60kg of nano calcium carbonate, 4.5kg of nano silicon dioxide and 4.4kg of calcium hydroxy phosphate into 60kg of ethanol, stirring and dispersing uniformly, adding 1.8kg of flow promoter, controlling the temperature to 65 ℃, stirring and reacting for 30min, filtering, washing and drying after completion to obtain a modified inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 75kg of vinylidene fluoride-hexafluoropropylene copolymer, 0.9kg of emulsifier and 120kg of water into a reaction kettle, stirring for 60min to fully emulsify the system, adding 0.6kg of buffering agent into the reaction kettle after completion, and uniformly stirring; and then adding 54kg of methyl methacrylate, 20kg of styrene and 10kg of acrylonitrile into a reaction kettle, stirring for 20min, adding 12.6kg of modified inorganic composite powder material, stirring for 20min, controlling the temperature to 75 ℃, then slowly adding 12kg of aqueous solution dissolved with 1.3kg of initiator into the reaction kettle within 90min under the protection of nitrogen, controlling the temperature to 80 ℃ after the completion of the reaction, stirring for polymerization for 180min, cooling to room temperature after the completion of the reaction, salting out to obtain a polymer, washing, drying and granulating to obtain the organic-inorganic nano-doped high polymer material processing aid master batch.
And further: the preparation method of the flow promoter comprises the following steps:
adding 12kg of tetramethyltetravinylcyclotetrasiloxane into 60kg of dimethylbenzene, dispersing and stirring, then adding 8kg of hexafluorobutyl acrylate, 1.2kg of butenediol and 1kg of decenal, heating to 75 ℃, adding 0.01kg of benzoyl peroxide and 0.005kg of dodecyl mercaptan, reacting for 8 hours under the protection of nitrogen, and then distilling under reduced pressure at 140 ℃ for 2 hours to obtain the flow promoter.
The content of hexafluoropropylene in the vinylidene fluoride-hexafluoropropylene copolymer is 45w%.
The initiator is ammonium persulfate.
The buffer is disodium hydrogen phosphate.
The processing performance test results of the PVC material using the polymer material processing aid masterbatch prepared in the above example are shown in the following table:
| plastification time s | Melting temperature of | Melting factor N m/s | |
| Example 1 | 114 | 186.8 | 0.72 |
| Example 2 | 112 | 186.2 | 0.75 |
| Example 3 | 109 | 185.4 | 0.76 |
Comparative example 1
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing an inorganic composite powder material: adding 3.2kg of nano calcium carbonate, 1.5kg of nano silicon dioxide and 1.8kg of calcium hydroxy phosphate into 20kg of ethanol, stirring and dispersing uniformly, filtering, and drying to obtain an inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 50kg of vinylidene fluoride-hexafluoropropylene copolymer, 0.3kg of emulsifier and 60kg of water into a reaction kettle, stirring for 30min to fully emulsify the system, adding 0.1kg of buffer into the reaction kettle after completion, and uniformly stirring; and then adding 35kg of methyl methacrylate, 5kg of styrene and 1kg of acrylonitrile into a reaction kettle, stirring for 5min, adding 5.2kg of inorganic composite powder material, stirring for 5min, controlling the temperature to 55 ℃, then slowly adding 5kg of aqueous solution in which 0.8kg of initiator is dissolved into the reaction kettle under the protection of nitrogen within 60min, controlling the temperature to 60 ℃ after the completion, stirring for polymerization for 120min, cooling to room temperature after the completion, salting out to obtain a polymer, washing, drying and granulating the polymer to obtain the organic-inorganic nano-doped high polymer material processing aid master batch.
The content of hexafluoropropylene in the vinylidene fluoride-hexafluoropropylene copolymer is 30%.
The initiator is potassium persulfate.
The buffer is sodium bicarbonate.
Comparative example 2
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
preparing the polymer material processing aid master batch: adding 50kg of vinylidene fluoride-hexafluoropropylene copolymer, 0.3kg of emulsifier and 60kg of water into a reaction kettle, stirring for 30min to fully emulsify the system, adding 0.1kg of buffer into the reaction kettle after completion, and uniformly stirring; and then adding 35kg of methyl methacrylate, 5kg of styrene and 1kg of acrylonitrile into a reaction kettle, stirring for 5min, controlling the temperature to 55 ℃, then slowly adding 5kg of aqueous solution dissolved with 0.8kg of initiator into the reaction kettle within 60min under the protection of nitrogen, controlling the temperature to 60 ℃ after the completion of the reaction, stirring for polymerization for 120min, cooling to room temperature after the completion of the reaction, salting out to obtain a polymer, washing, drying and granulating the polymer to obtain the organic-inorganic nano-doped high polymer material processing aid master batch.
The content of hexafluoropropylene in the vinylidene fluoride-hexafluoropropylene copolymer is 30%.
The initiator is potassium persulfate.
The buffer is sodium bicarbonate.
Comparative example 3
A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing a modified inorganic composite powder material: adding 32-60kg of nano calcium carbonate, 1.5-4.5kg of nano silicon dioxide and 1.8-4.4kg of calcium hydroxy phosphate into 20-60kg of ethanol according to the mass kg, uniformly stirring and dispersing, adding 0.5-1.8kg of flow promoter, controlling the temperature to be 45-65 ℃, stirring and reacting for 10-30min, filtering, washing and drying after completion to obtain the modified inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 50kg of vinylidene fluoride-hexafluoropropylene copolymer, 0.3kg of emulsifier and 60kg of water into a reaction kettle, stirring for 30min to fully emulsify the system, adding 0.1kg of buffer into the reaction kettle after completion, and uniformly stirring; adding 35kg of methyl methacrylate, 5kg of styrene and 1kg of acrylonitrile into a reaction kettle, stirring for 5min, adding 5.2kg of modified inorganic composite powder material, stirring for 5min, controlling the temperature to 55 ℃, then slowly adding 5kg of aqueous solution dissolved with 0.8kg of initiator into the reaction kettle within 60min under the protection of nitrogen, controlling the temperature to 60 ℃ after the completion of the reaction, stirring for polymerization for 120min, cooling to room temperature after the completion of the reaction, salting out to obtain a polymer, washing, drying and granulating to obtain the organic-inorganic nano-doped high polymer material processing aid master batch.
And further: the preparation method of the flow promoter comprises the following steps:
adding 5kg of tetramethyltetravinylcyclotetrasiloxane into 40kg of dimethylbenzene, dispersing and stirring, then adding 0.5kg of butenediol and 0.1kg of decenal, heating to 60 ℃, adding 0.001kg of benzoyl peroxide and 0.001kg of dodecyl mercaptan, reacting for 4 hours under the protection of nitrogen, and then distilling at 140 ℃ under reduced pressure for 0.5 hour to obtain the flow promoter.
The mercapto modifier is gamma-mercaptopropyl trimethoxysilane.
The hexafluoropropylene content in the vinylidene fluoride-hexafluoropropylene copolymer is 30%.
The initiator is potassium persulfate.
The buffer is sodium bicarbonate.
The processing performance test results of the PVC material using the polymer material processing aid masterbatch prepared in the above comparative example are shown in the following table:
| plastification time s | Melting temperature of | Melting factor N m/s | |
| Comparative example 1 | 118 | 187.5 | 0.67 |
| Comparative example 2 | 123 | 187.8 | 0.65 |
| Comparative example 3 | 118 | 187.1 | 0.69 |
Claims (4)
1. A preparation method of organic-inorganic nano-doped polymer material processing aid master batch comprises the following steps:
step one, preparing a modified inorganic composite powder material: adding 32-60 parts of nano calcium carbonate, 1.5-4.5 parts of nano silicon dioxide and 1.8-4.4 parts of calcium hydroxy phosphate into 20-60 parts of ethanol according to the mass parts, uniformly stirring and dispersing, adding 0.5-1.8 parts of flow promoter, controlling the temperature to be 45-65 ℃, stirring and reacting for 10-30min, filtering, washing and drying after completion to obtain a modified inorganic composite powder material;
step two, preparing the polymer material processing aid master batch: adding 50-75 parts by mass of vinylidene fluoride-hexafluoropropylene copolymer, 0.3-0.9 part by mass of emulsifier and 60-120 parts by mass of water into a reaction kettle, stirring for 30-60min to fully emulsify a system, adding 0.1-0.6 part by mass of buffer into the reaction kettle, and uniformly stirring; adding 35-54 parts of methyl methacrylate, 5-20 parts of styrene and 1-10 parts of acrylonitrile into a reaction kettle, stirring for 5-20min, adding 5.2-12.6 parts of modified inorganic composite powder material, stirring for 5-20min, controlling the temperature to 55-75 ℃, slowly adding 5-12 parts of aqueous solution in which 0.8-1.3 part of initiator is dissolved into the reaction kettle within 60-90min under the protection of nitrogen, controlling the temperature to 60-80 ℃ after the reaction is finished, stirring for polymerization for 120-180min, cooling to room temperature after the reaction is finished, salting out to obtain a polymer, washing, drying and granulating the polymer to obtain the organic-inorganic nano-doped polymer material processing aid master batch;
the flow promoter is prepared by copolymerizing unsaturated double bonds in tetramethyl tetravinylcyclotetrasiloxane, fluorine-containing functional monomers and other functional monomers through free radicals;
the preparation method of the flow promoter comprises the following steps: adding 5-12 parts of tetramethyltetravinylcyclotetrasiloxane into 40-60 parts of dimethylbenzene for dispersion and stirring, then adding 3-8 parts of hexafluorobutyl acrylate, 0.5-1.2 parts of butenediol and 0.1-1 part of decenal, heating to 60-75 ℃, adding 0.001-0.01 part of benzoyl peroxide and 0.001-0.005 part of dodecyl mercaptan, reacting for 4-8h under the protection of nitrogen, and then distilling under reduced pressure at 140 ℃ for 0.5-2h to obtain the flow promoter.
2. The preparation method of the organic-inorganic nano-doped polymer material processing aid master batch according to claim 1, which is characterized by comprising the following steps of: the hexafluoropropylene content in the vinylidene fluoride-hexafluoropropylene copolymer is 30-45 w%.
3. The preparation method of the organic-inorganic nano-doped polymer material processing aid master batch according to claim 1, which is characterized by comprising the following steps of: the initiator is potassium persulfate or ammonium persulfate.
4. The preparation method of the organic-inorganic nano-doped polymer material processing aid master batch according to claim 1, which is characterized by comprising the following steps of: the buffer is sodium bicarbonate or disodium hydrogen phosphate.
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