CN110294910B - High-temperature water-soluble polyvinyl alcohol master batch and preparation method thereof - Google Patents
High-temperature water-soluble polyvinyl alcohol master batch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature water-soluble polyvinyl alcohol master batch and a preparation method thereof, wherein the high-temperature water-soluble polyvinyl alcohol master batch comprises the following components in parts by weight: 80-100 parts of completely alcoholyzed polyvinyl alcohol, 25-40 parts of composite plasticizer, 05-3 parts of composite antioxidant, 1-2 parts of heat stabilizer and 2-3 parts of composite lubricant. The melting processing temperature range of the polyvinyl alcohol master batch is increased from 20 ℃ of polyvinyl alcohol to 50-60 ℃, namely the melting temperature is 190 ℃ and the decomposition temperature is 250 ℃. The melt index of the polyvinyl alcohol master batch is improved, so that the processing difficulty of the polyvinyl alcohol master batch is reduced, the water-soluble resistance temperature of the polyvinyl alcohol master batch reaches over 75 ℃ through a scientific formula and a reasonable preparation process, and a film with the thickness of 5 mu m and the water-soluble resistance temperature of over 65 ℃ is processed and prepared by using the polyvinyl alcohol master batch.
Description
Technical Field
The invention relates to the technical field of polyvinyl alcohol processing, in particular to a high-temperature water-soluble polyvinyl alcohol master batch and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) was first discovered by german chemists w.o.hermann and by w.w.hachnel, doctor, 1924, and achieved a large-scale industrial shift between 1926 and 1950. PVA is white powder in appearance, is a water-soluble high molecular polymer obtained by polymerizing and alcoholyzing vinyl acetate, and has a molecular formula of [ C2H4O]n. PVA has different alcoholysis degrees, the alcoholysis degree of the PVA indicates the degree of hydroxyl group substituting acetate in the macromolecule of the PVA, the higher the alcoholysis degree of the PVA is, the lower the solubility of the PVA in cold water and hot water is, and the lower the alcoholysis degree of the PVA is, the higher the solubility of the PVA in both the cold water and the hot water is correspondingly.
The polyvinyl alcohol material and the product are functional polymer film materials, and are widely applied to the industries and fields of packaging of mechanical electronics, chemical engineering, petroleum exploitation, building materials, medicines, foods, precision instruments and the like, wherein the high-temperature water-soluble polyvinyl alcohol master batch with the water-soluble temperature of over 65 ℃ and the product have wider application range and field, and are formed by thermoplastic processing to produce various products such as injection molding parts, high-temperature water-soluble granules, high-barrier containers, high-temperature water-soluble films, high-temperature packaging films and the like which are urgently needed by the market.
Polyvinyl alcohol (PVA) is the only biodegradable and water-degradable environment-friendly material known in nature, the material and products have excellent degradability, antistatic property, chemical corrosion resistance, gas barrier property, mechanical physical property, high light transmittance and the like, and only CO is generated after degradation2And water, the environment is protected, and the market prospect is unlimited. However, since the temperature range between the melting point and the decomposition point of the material is only 20 ℃, thermoplastic processing is substantially impossible. At present, most of applications in the market are only processing into films by adopting a tape casting method, and injection molding and blow molding products with more complex processing difficulty cannot be produced, so that the exertion of excellent performance of the injection molding and blow molding products is limited. Although the modification technology is adopted at home and abroad in recent years, the polyvinyl alcohol normal-temperature water-soluble material has certain thermoplastic processing performance, but the technical quality is still unstable. In the aspect of development and application of high-temperature water-soluble polyvinyl alcohol master batches urgently needed by the market, at present, no qualified product is put into application at home, and most of the few similar products which are researched and developed have the problems of low water-soluble resistance temperature (below 50 ℃), unstable water-resistant temperature (the master batches are rapidly reduced by the water-resistant temperature after being placed for a short time), poor processability (the master batches are difficult to carry out hot plastic processing such as injection molding and blow molding), and cannot be applied at all. At present, the high-temperature water-soluble polyvinyl alcohol master batch and products with mature technology are difficult to trace.
Disclosure of Invention
The invention aims to provide a high-temperature water-soluble polyvinyl alcohol master batch. The temperature range of the fusion processing of the polyvinyl alcohol master batch is increased from 20 ℃ to 50-60 ℃, namely the melting temperature is 190 ℃ and the decomposition temperature is 250 ℃. The melt index (220 ℃, 21.6kg, melt index 59.39) of the polyvinyl alcohol master batch is improved, so that the processing difficulty of the polyvinyl alcohol master batch is reduced, the water-soluble resistance temperature of the polyvinyl alcohol master batch reaches over 75 ℃ through a scientific formula and a reasonable preparation process, and a film with the thickness of 5 mu m processed and prepared by the polyvinyl alcohol master batch has the water-soluble resistance temperature of over 65 ℃.
The invention also aims to perfect the preparation method of the high-temperature water-soluble polyvinyl alcohol master batch.
The high-temperature water-soluble polyvinyl alcohol master batch comprises the following components in parts by weight: 80-100 parts of completely alcoholyzed polyvinyl alcohol, 25-40 parts of composite plasticizer, 0.5-3 parts of composite antioxidant, 1-2 parts of heat stabilizer and 2-3 parts of composite lubricant.
Preferably, the degree of alcoholysis of the fully alcoholyzed polyvinyl alcohol is between 98 and 100%.
Preferably, the compound plasticizer comprises at least two components of glycerol, tri-n-butyl citrate and polyethylene glycol.
Preferably, the weight ratio of the glycerol to the tri-n-butyl citrate to the polyethylene glycol in the composite plasticizer is 10:3: 1.
Preferably, the composite antioxidant comprises 1010 antioxidant, TNP antioxidant and 168 antioxidant, and the weight ratio of the 1010 antioxidant to the TNP antioxidant is 5:2: 3.
Preferably, the stabilizer is a calcium zinc stabilizer.
Preferably, the composite lubricant comprises talcum powder, oleamide and polyethylene wax, and the weight ratio of the talcum powder to the oleamide to the polyethylene wax is 1:1: 1.
The preparation method of the high-temperature water-soluble polyvinyl alcohol master batch comprises the following steps:
putting the completely alcoholyzed polyvinyl alcohol into a mixer for premixing;
then adding a composite plasticizer, a composite antioxidant, a heat stabilizer and a composite lubricant in proportion, heating to 100 ℃ and 150 ℃, and performing heat preservation treatment for 10-30min for preplasticizing to obtain preplasticized polyvinyl alcohol;
adding pre-plasticized polyvinyl alcohol into a bin of a screw extruder, heating the temperature of each heating interval of the screw extruder to 100-250 ℃, then starting the screw extruder, adding the pre-plasticized polyvinyl alcohol in the bin into the extruder for melting and plasticizing, and extruding;
cooling the extruded plasticized product to 40-50 ℃, granulating the plasticized product by using a granulator, bagging and packaging to obtain the high-temperature water-soluble polyvinyl alcohol master batch.
Preferably, the heating temperature in the preplasticizing step is 110 ℃.
Preferably, the time for melt plasticizing the preplasticized polyvinyl alcohol in the extruder is 5-10 min.
Compared with the prior art, the invention has the following beneficial effects: the temperature range of the melt processing of the polyvinyl alcohol master batch is increased from 20 ℃ to 50-60 ℃, namely the melting temperature is 190 ℃ and the decomposition temperature is 250 ℃. The melt index (220 ℃, 21.6kg, melt index 59.39) of the polyvinyl alcohol master batch is improved, so that the processing difficulty of the polyvinyl alcohol master batch is reduced, the water-soluble resistance temperature of the polyvinyl alcohol master batch reaches over 75 ℃ through a scientific formula and a reasonable preparation process, the thickness of a film processed and prepared by the polyvinyl alcohol master batch is 5 mu m, and the water-soluble resistance temperature reaches over 65 ℃;
meanwhile, the preparation method of the high-temperature water-soluble polyvinyl alcohol master batch is simple, the processing can be realized without adopting large complex equipment, and the production cost is low.
Detailed Description
The invention is further illustrated with reference to specific examples. The used raw materials are chemical raw materials commonly used in the market, and the used raw materials are purchased in the market.
Example 1
The high-temperature water-soluble polyvinyl alcohol master batch comprises the following components in parts by weight:
100 parts of complete alcoholysis type polyvinyl alcohol, 40 parts of composite plasticizer, 2 parts of composite antioxidant, 1 part of heat stabilizer and 2 parts of composite lubricant. The degree of alcoholysis of the fully alcoholyzed polyvinyl alcohol is greater than 99%. The composite plasticizer is prepared by mixing glycerol, tri-n-butyl citrate and polyethylene glycol in a weight ratio of 10:3: 1. The composite antioxidant is prepared by mixing 1010 antioxidant, TNP antioxidant and 168 antioxidant in a weight ratio of 5:2: 3. The heat stabilizer is a calcium zinc stabilizer. The composite lubricant is prepared by mixing talcum powder, oleamide and polyethylene wax in a weight ratio of 1:1: 1.
The preparation method of the high-temperature water-soluble polyvinyl alcohol master batch comprises the following steps:
putting the completely alcoholyzed polyvinyl alcohol into a mixer for premixing;
then adding a composite plasticizer, a composite antioxidant, a heat stabilizer and a composite lubricant in proportion, heating to 110 ℃, and carrying out heat preservation treatment for 30min for preplasticizing to obtain preplasticized polyvinyl alcohol;
adding pre-plasticized polyvinyl alcohol into a bin of a screw extruder, heating the temperature of each heating interval of the screw extruder to 100-250 ℃, then starting the screw extruder, adding the pre-plasticized polyvinyl alcohol in the bin into the extruder for melting and plasticizing, and extruding;
cooling the extruded plasticized product to 40-50 ℃, granulating the plasticized product by using a granulator, bagging and packaging to prepare the high-temperature water-soluble polyvinyl alcohol master batch with the water-soluble resistance temperature of 75 ℃.
Example 2
The high-temperature water-soluble polyvinyl alcohol master batch comprises the following components in parts by weight:
90 parts of complete alcoholysis type polyvinyl alcohol, 30 parts of composite plasticizer, 1.5 parts of composite antioxidant, 2 parts of heat stabilizer and 2 parts of composite lubricant. The degree of alcoholysis of the fully alcoholyzed polyvinyl alcohol is greater than 99%. The composite plasticizer is prepared by mixing glycerol, tri-n-butyl citrate and polyethylene glycol in a weight ratio of 10:3: 1. The composite antioxidant is prepared by mixing 1010 antioxidant, TNP antioxidant and 168 antioxidant in a weight ratio of 5:2: 3. The heat stabilizer is a calcium zinc stabilizer. The composite lubricant is prepared by mixing talcum powder, oleamide and polyethylene wax in a weight ratio of 1:1: 1.
The preparation method of the high-temperature water-soluble polyvinyl alcohol master batch comprises the following steps:
putting the completely alcoholyzed polyvinyl alcohol into a mixer for premixing;
then adding a composite plasticizer, a composite antioxidant, a heat stabilizer and a composite lubricant in proportion, heating to 110 ℃, and carrying out heat preservation treatment for 15min for preplasticizing to obtain preplasticized polyvinyl alcohol;
adding pre-plasticized polyvinyl alcohol into a bin of a screw extruder, heating the temperature of each heating interval of the screw extruder to 100-250 ℃, then starting the screw extruder, adding the pre-plasticized polyvinyl alcohol in the bin into the extruder for melting and plasticizing, and extruding;
cooling the extruded plasticized product to 40-50 ℃, granulating the plasticized product by using a granulator, bagging and packaging to prepare the high-temperature water-soluble polyvinyl alcohol master batch with the water-soluble resistance temperature of 78 ℃.
Example 3
The high-temperature water-soluble polyvinyl alcohol master batch comprises the following components in parts by weight:
80 parts of completely alcoholyzed polyvinyl alcohol, 25 parts of composite plasticizer, 1 part of composite antioxidant, 2 parts of heat stabilizer and 3 parts of composite lubricant. The degree of alcoholysis of the fully alcoholyzed polyvinyl alcohol is greater than 99%. The composite plasticizer is prepared by mixing glycerol, tri-n-butyl citrate and polyethylene glycol in a weight ratio of 10:3: 1. The composite antioxidant is prepared by mixing 1010 antioxidant, TNP antioxidant and 168 antioxidant in a weight ratio of 5:2: 3. The heat stabilizer is a calcium zinc stabilizer. The composite lubricant is prepared by mixing talcum powder, oleamide and polyethylene wax in a weight ratio of 1:1: 1.
The preparation method of the high-temperature water-soluble polyvinyl alcohol master batch comprises the following steps:
putting the completely alcoholyzed polyvinyl alcohol into a mixer for premixing;
then adding a composite plasticizer, a composite antioxidant, a heat stabilizer and a composite lubricant in proportion, heating to 110 ℃, and carrying out heat preservation treatment for 10min for preplasticizing to obtain preplasticized polyvinyl alcohol;
adding pre-plasticized polyvinyl alcohol into a bin of a screw extruder, heating the temperature of each heating interval of the screw extruder to 100-250 ℃, then starting the screw extruder, adding the pre-plasticized polyvinyl alcohol in the bin into the extruder for melting and plasticizing, and extruding;
cooling the extruded plasticized product to 40-50 ℃, granulating the plasticized product by using a granulator, bagging and packaging to prepare the high-temperature water-soluble polyvinyl alcohol master batch with the water-soluble resistance temperature of 80 ℃.
The high-temperature water-soluble polyvinyl alcohol master batch prepared in the embodiment 1-3 of the invention is processed into a film product with the thickness of 5 mu m by adopting thermoplastic processing, and the water-soluble temperature of the product can reach more than 65 ℃. Meanwhile, the production and processing difficulty is reduced, and the performance of the membrane prepared by using the same is excellent.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (1)
1. The high-temperature water-soluble polyvinyl alcohol master batch is characterized by comprising the following components in parts by weight:
80 parts of polyvinyl alcohol which is completely alcoholyzed,
25 parts of a composite plasticizer, namely 25 parts of,
1 part of a compound antioxidant, namely 1 part,
2 parts of a heat stabilizer,
3 parts of a composite lubricant;
the alcoholysis degree of the completely alcoholyzed polyvinyl alcohol is more than 99 percent;
the composite plasticizer is prepared by mixing glycerol, tri-n-butyl citrate and polyethylene glycol in a weight ratio of 10:3: 1;
the composite antioxidant is prepared by mixing an antioxidant 1010, an antioxidant TNP and an antioxidant 168, wherein the weight ratio of the antioxidant 1010 to the antioxidant TNP to the antioxidant 168 is 5:2: 3;
the heat stabilizer is a calcium-zinc stabilizer;
the composite lubricant is prepared by mixing talcum powder, oleamide and polyethylene wax, and the weight ratio of the talcum powder to the oleamide to the polyethylene wax is 1:1: 1;
the preparation method of the high-temperature water-soluble polyvinyl alcohol master batch comprises the following steps:
putting the completely alcoholyzed polyvinyl alcohol into a mixer for premixing;
then adding a composite plasticizer, a composite antioxidant, a heat stabilizer and a composite lubricant in proportion, heating to 110 ℃, and carrying out heat preservation treatment for 10min for preplasticizing to obtain preplasticized polyvinyl alcohol;
adding pre-plasticized polyvinyl alcohol into a bin of a screw extruder, heating the temperature of each heating interval of the screw extruder to 100 ℃ and 250 ℃, then starting the screw extruder, adding the pre-plasticized polyvinyl alcohol in the bin into the extruder for melting and plasticizing, and extruding;
cooling the extruded plasticized product to 40-50 ℃, granulating the plasticized product by using a granulator, bagging and packaging to obtain the high-temperature water-soluble polyvinyl alcohol master batch.
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| CN103304851A (en) * | 2013-07-07 | 2013-09-18 | 华东理工大学 | High-starch-content waterproof totally-decomposed composite material and preparation method thereof |
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| CN105524384B (en) * | 2014-09-29 | 2019-03-26 | 中国石油化工集团公司 | A kind of melt-processable polyvinyl alcohol master batch and preparation method thereof |
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| CN101864132A (en) * | 2010-05-26 | 2010-10-20 | 四川大学 | Fusion preparation method of polyvinyl alcohol film |
| CN103724899A (en) * | 2013-12-30 | 2014-04-16 | 浙江七色鹿色母粒有限公司 | Thermal plasticizing polyvinyl alcohol modified material |
| CN105524385A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工集团公司 | Melt-processible polyvinyl alcohol master batch and preparation method thereof |
| CN104448641A (en) * | 2014-12-12 | 2015-03-25 | 广东银禧科技股份有限公司 | Polyvinyl alcohol wire for fused deposition molding and processing method of polyvinyl alcohol wire |
| CN106189010A (en) * | 2015-05-08 | 2016-12-07 | 中国石油化工集团公司 | A kind of polyvinyl alcohol film of blow molding and preparation method thereof |
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