CN111518352A - High-temperature water-soluble PVA master batch composition and high-temperature water-soluble PVA particles - Google Patents
High-temperature water-soluble PVA master batch composition and high-temperature water-soluble PVA particles Download PDFInfo
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Abstract
The invention relates to the field of biodegradable materials, and discloses a high-temperature water-soluble PVA master batch composition and high-temperature water-soluble PVA particles. The method comprises the following steps: 1) mixing PVA and a plasticizer to preplasticize the PVA; 2) continuously adding the heat stabilizer, the lubricant and the antioxidant, and mixing at high temperature; 3) extruding and granulating the mixed material obtained in the step 2). The method provided by the invention can effectively reduce the melting temperature of the PVA, broaden the processing window and realize continuous granulation of the high-temperature water-soluble PVA.
Description
Technical Field
The invention belongs to the field of biodegradable materials, and particularly relates to a high-temperature water-soluble PVA master batch composition and high-temperature water-soluble PVA particles.
Background
In recent years, the demand for plastic packaging products is increasing, and to a certain extent, the plastic packaging is used as an integral part of the packaging of food, fruits and vegetables, daily chemicals and the like, and the plastic packaging is more widely applied to daily life and food storage. Therefore, the requirement of people on environmental protection is increased day by day, and the plastic packaging product is required to have higher performance and multiple functions, and is further required to have no pollution and public nuisance to food, people and environment. Therefore, research has been focused on moving to new plastic packaging materials that do not degrade in a contaminating manner.
The PVA film is soluble in water, has high mechanical property, good transparency and high oil resistance and corrosion resistance, enters the visual field of people at the initial stage of the 20 th century, and is rapidly developed at home and abroad. In the production process of PVA film, the melting temperature is close to the decomposition temperature, so the melt extrusion method has high processing difficulty in industrial production, and the casting method is mostly used for film forming. In the modification production of PVA films, Japan is to develop a high temperature (80 ℃) resistant water-soluble PVA film in advance of other countries, and creates favorable conditions for the wide application of the PVA film. Although the research on the water and temperature resistance of the PVA film in China is advanced to a certain extent, the intermediate temperature PVA film which has the advantages of low water and temperature resistance (60 ℃), easy curling in water and easy moisture absorption at normal temperature and wrinkling is developed, and the defects cause that downstream products cannot be continuously researched and developed, so that the popularization and the use of the PVA film are limited. The development of domestic high-temperature polyvinyl alcohol films is not broken through, the sources only depend on import, and the use cost is greatly improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and materials, and provides the high-temperature water-soluble PVA master batch composition and the high-temperature water-soluble PVA particles.
In order to achieve the above purpose, the invention provides, in a first aspect, a high-temperature water-soluble PVA master batch composition, wherein the master batch composition is composed of the following raw materials in parts by weight:
relative to 100 parts by weight of PVA resin, 10-40 parts by weight of plasticizer, 1-6 parts by weight of thermoplastic elastomer, 2-8 parts by weight of heat stabilizer, 1-6 parts by weight of lubricant and 0.5-3 parts by weight of antioxidant.
Preferably, the master batch composition is prepared from the following raw materials in parts by weight:
relative to 100 parts by weight of PVA resin, 10-40 parts by weight of plasticizer, 2-5 parts by weight of thermoplastic elastomer, 2-6 parts by weight of heat stabilizer, 2-6 parts by weight of lubricant and 1-2.5 parts by weight of antioxidant.
Preferably, the degree of polymerization of the PVA is 500-2400.
Preferably, the alcoholysis degree of the PVA is more than or equal to 98 percent.
Preferably, the particle size of the PVA is 100-200 meshes.
Preferably, the plasticizer is selected from one or more of propylene glycol, glycerol, sorbitol, polyethylene glycol 200, polyethylene glycol 400, span 20, span 60, span 80, tween 20, tween 40 and tween 60, triglycerol, neopentyl glycol, mannitol, pentaerythritol, diethanolamine and triethanolamine.
Preferably, the plasticizer comprises A, B components, wherein the content of the A component is 60-100 wt% based on the total weight of the plasticizer, the A component is propylene glycol and/or glycerol, and the B component is selected from sorbitol, polyethylene glycol 200, neopentyl glycol and pentaerythritol.
Preferably, the thermoplastic elastomer is selected from one or more of EMA, EVA, EAA, EEA.
Preferably, the thermal stabilizer is selected from one or more of glyceryl monostearate, glyceryl triglycerol monostearate, laurate and sorbitan stearate, zinc stearate, magnesium distearate, calcium stearate, cerium stearate, barium stearate, stearic acid and sodium stearate.
Preferably, the lubricant is selected from one or more of stearyl alcohol, stearamide, erucamide, oleamide, hydroxystearic acid, myristic acid, glyceryl monostearate, triglycerol monostearate, pentaerythritol stearate and hydroxystearic acid.
Preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697, antioxidant 565, antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168 and antioxidant 626.
Preferably, the antioxidant comprises a component a and a component b, wherein the content of the component a is 60-100 wt% based on the total weight of the antioxidant, the component a is antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697 or antioxidant 565, and the component b is antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168 or antioxidant 626.
The invention provides high-temperature water-soluble PVA particles, which are obtained by mixing and granulating the high-temperature water-soluble PVA master batch composition.
The invention provides a high-temperature water-soluble PVA master batch composition and high-temperature water-soluble PVA particles which are stable in heating, and can realize the feasibility of granulation of high-temperature water-soluble PVA resin.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a high-temperature water-soluble PVA master batch composition, which is composed of the following raw materials in parts by weight:
relative to 100 parts by weight of PVA resin, 10-40 parts by weight of plasticizer, 1-6 parts by weight of thermoplastic elastomer, 2-8 parts by weight of heat stabilizer, 1-6 parts by weight of lubricant and 0.5-3 parts by weight of antioxidant.
PVA is modified at a granulation process source, and the high-temperature water-soluble PVA master batch is provided, so that the feasibility of high-temperature water-soluble PVA granulation can be realized, and the cost is reduced while the environmental protection is realized.
In order to further improve the performance of the high-temperature water-soluble PVA master batch composition, in the invention, preferably, the master batch composition is composed of the following raw materials in parts by weight:
relative to 100 parts by weight of PVA resin, 10-40 parts by weight of plasticizer, 2-5 parts by weight of thermoplastic elastomer, 2-6 parts by weight of heat stabilizer, 2-6 parts by weight of lubricant and 1-2.5 parts by weight of antioxidant.
The PVA is not particularly limited, and in the present invention, the degree of polymerization of the PVA is preferably 500-2400.
In the present invention, it is preferable that the degree of alcoholysis of PVA is 98% or more. In the practice of the present invention, the PVA resin is selected from one or more of PVA0599, PVA1099, PVA1599, PVA1799, PVA2099, PVA2299, PVA2499 and PVA 2699.
The particle size of the PVA resin is not particularly limited, and in the present invention, the particle size of the PVA is preferably 100-200 mesh.
Since PVA belongs to a polyhydroxy high molecular polymer and contains a large number of hydrogen bonds between molecules, which begin to decompose when melted or not melted, in the present invention, it is preferable that the plasticizer is selected from one or more of propylene glycol, glycerol, sorbitol, polyethylene glycol 200, polyethylene glycol 400, span 20, span 60, span 80, tween 20, tween 40, tween 60, triglycerol, neopentyl glycol, mannitol, pentaerythritol, diethanolamine and triethanolamine.
In order to further solve the problem of poor plasticizing effect of a single plasticizer, break hydrogen bonds between PVA molecules and PVA molecules, make small molecular plasticizers more easily enter the interior of molecules for plasticizing, and widen the processing window of PVA, in the invention, preferably, the plasticizer comprises A, B component, the content of the A component is 60-100 wt% based on the total weight of the plasticizer, wherein the A component is propylene glycol and/or glycerol, and the B component is selected from sorbitol, polyethylene glycol 200, neopentyl glycol and pentaerythritol. By adopting the compound plasticizer, the hydrogen bonds between PVA molecules and between PVA molecules are further destroyed, and the micromolecular plasticizer can enter the inside of the molecules for plasticizing, so that the processing window of PVA is widened.
In the present invention, preferably, the thermoplastic elastomer is selected from one or more of EMA, EVA, EAA and EEA.
In the present invention, preferably, the heat stabilizer is selected from one or more of glyceryl monostearate, glyceryl triglycerol monostearate, laurate, sorbitan stearate, zinc stearate, magnesium distearate, calcium stearate, cerium stearate, barium stearate, stearic acid and sodium stearate. The problem of decomposition and yellowing of PVA in the processing process is solved by introducing a plurality of heat stabilizers.
The above lubricant is not particularly limited and may be various lubricants commonly used in the art, and in the present invention, preferably, the lubricant is selected from one or more of stearyl alcohol, stearamide, erucamide, oleamide, hydroxystearic acid, myristic acid, glycerol monostearate, triglycerol monostearate, pentaerythritol stearate, and hydroxystearic acid.
The antioxidant is not particularly limited, and may be various antioxidants commonly used in the art, and in the present invention, it is preferable that the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697, antioxidant 565, antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168 and antioxidant 626.
In order to further improve the performance of the high-temperature water-soluble PVA master batch composition, in the invention, preferably, the antioxidant comprises a component a and a component b, the content of the component a is 60-100 wt% based on the total weight of the antioxidant, wherein the component a is antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697 or antioxidant 565, and the component b is antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168 or antioxidant 626. The performance of the composition is further improved by the synergistic use of the antioxidant a and the antioxidant b.
In a second aspect, the invention provides a high-temperature water-soluble PVA particle which can be formed by blow molding and is prepared by mixing and granulating the high-temperature water-soluble PVA master batch composition.
In a specific embodiment of the invention, the preparation is carried out by the following steps:
1) plasticizing PVA and plasticizer in a high-speed mixer at 40-75 deg.c for 5-10 min;
2) adding other auxiliary agents at 80-100 ℃, mixing and dispersing for 5-8 minutes, cooling the mixed powder to room temperature, and discharging for later use;
3) adding the mixed powder into a screw with the length-diameter ratio of (44-52): 1 in a double-screw 35 granulator with forced feeding, the main feeding speed is 15-38r/min, the main machine rotating speed is 300-.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
1799100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol, 2005 parts of polyethylene glycol, 5 parts of EVA, 3 parts of glyceryl monostearate, 1 part of calcium stearate, 1 part of magnesium stearate, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Example 2
1799100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 8 parts of glycerol, 2005 parts of polyethylene glycol, 5 parts of EAA, 3 parts of glyceryl monostearate, 1 part of calcium stearate, 1 part of magnesium stearate, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Example 3
2499100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol, 2008 parts of polyethylene glycol, 5 parts of EVA, 3 parts of glyceryl monostearate, 1 part of calcium stearate, 1 part of magnesium stearate, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Example 4
2499100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol, 5 parts of pentaerythritol, 3 parts of glyceryl monostearate, 1 part of calcium stearate, 1 part of magnesium stearate, 10100.8 parts of antioxidant and 0.5 part of antioxidant DLTP.
Example 5
1799100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol and pentaerythritol
8 parts by weight, 5 parts by weight of EMA, 3 parts by weight of glyceryl monostearate, 1 part by weight of calcium stearate, 1 part by weight of magnesium stearate, 10100.8 parts by weight of antioxidant and 0.5 part by weight of antioxidant DSTDP.
Example 6
1799100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol, 5 parts of pentaerythritol, 3 parts of EEA, 3 parts of glyceryl monostearate, 1 part of hydroxystearic acid, 1 part of erucamide, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Example 7
059990 parts of polyvinyl alcohol, 179910 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol, 5 parts of neopentyl glycol, 3 parts of EAA, 3 parts of glyceryl monostearate, 1 part of hydroxystearic acid, 1 part of erucamide, 10980.8 parts of antioxidant and 6260.5 parts of antioxidant.
Example 8
059920 parts of polyvinyl alcohol, 179980 parts of PVA, 5 parts of propylene glycol, 5 parts of glycerol, 8 parts of neopentyl glycol, 3 parts of EAA, 1 part of glyceryl monostearate, 1 part of hydroxystearic acid, 1 part of erucamide, 10980.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Example 9
059920 parts of polyvinyl alcohol, 179980 parts of PVA, 5 parts of propylene glycol, 5 parts of glycerol, 8 parts of pentaerythritol, 3 parts of EMA, 2 parts of glyceryl monostearate, 1 part of hydroxystearic acid, 1 part of erucamide, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Example 10
059920 parts of polyvinyl alcohol, 179980 parts of PVA, 5 parts of propylene glycol, 8 parts of glycerol, 5 parts of sorbitol, 3 parts of EVA (ethylene vinyl acetate), 3 parts of glycerin monostearate, 1 part of hydroxystearic acid, 1 part of erucamide, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Comparative example 1
1799100 parts of polyvinyl alcohol, 5 parts of propylene glycol, 5 parts of glycerol, 8 parts of pentaerythritol, 3 parts of glyceryl monostearate, 1 part of calcium stearate, 1 part of magnesium stearate, 10100.8 parts of antioxidant and 0.5 part of antioxidant DSTDP.
Comparative example 2
059920% of polyvinyl alcohol, 179980% of PVA, 5% of propylene glycol, 5% of glycerol, 8% of neopentyl glycol, 1% of glyceryl monostearate, 1% of hydroxystearic acid, 1% of erucamide, 10980.8% of antioxidant and 0.5% of antioxidant DSTDP.
According to the proportion shown in examples 1-10 and comparative examples 1-2, PVA is plasticized with compound plasticizer in a high-speed mixer for 10 minutes at 70 ℃, then mixed with other auxiliary agents and dispersed for 8 minutes at 90 ℃, and the mixed powder is cooled to room temperature and discharged for standby. Then adding the mixed and dried powder into a screw with the length-diameter ratio of 44: 1 in a double-screw 35 granulator with forced feeding, the main feeding speed is 28r/min, the main machine rotating speed is 380r/min, and the temperature of each area of the double-screw extruder is set as follows: the PVA master batch is prepared by melting and extruding at 90 ℃ in the first area, 140 ℃ in the second area, 150 ℃ in the third area, 150 ℃ in the fourth area, 160 ℃ in the fifth area, 160 ℃ in the sixth area, 170 ℃ in the seventh area, 175 ℃ in the eighth area, 175 ℃ in the ninth area, 170 ℃ in the tenth area, 180 ℃ in the eleventh area, 185 ℃ in the twelfth area, 185 ℃ in the thirteenth area and 190 ℃ in a machine head, air-cooling and drawing strips, and granulating to obtain the.
Performance evaluation method:
the above examples 1 to 10 were tested in comparison with comparative examples 1 and 2, and the test results are shown in Table 1.
TABLE 1
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The high-temperature water-soluble PVA master batch composition is characterized by comprising the following raw materials in parts by weight:
relative to 100 parts by weight of PVA resin, 10-40 parts by weight of plasticizer, 1-6 parts by weight of thermoplastic elastomer, 2-8 parts by weight of heat stabilizer, 1-6 parts by weight of lubricant and 0.5-3 parts by weight of antioxidant.
2. The high-temperature water-soluble PVA master batch composition according to claim 1, wherein the master batch composition is prepared from the following raw materials in parts by weight:
relative to 100 parts by weight of PVA resin, 10-40 parts by weight of plasticizer, 2-5 parts by weight of thermoplastic elastomer, 2-6 parts by weight of heat stabilizer, 2-6 parts by weight of lubricant and 1-2.5 parts by weight of antioxidant.
3. The high-temperature water-soluble PVA master batch composition according to claim 1 or 2, wherein the PVA has a polymerization degree of 500-2400;
preferably, the alcoholysis degree of the PVA is more than or equal to 98 percent;
preferably, the particle size of the PVA is 100-200 meshes.
4. The high temperature water soluble PVA masterbatch composition according to claim 1 or 2, wherein the plasticizer is selected from one or more of propylene glycol, glycerol, sorbitol, polyethylene glycol 200, polyethylene glycol 400, span 20, span 60, span 80, Tween 20, Tween 40, Tween 60, triglycerol, neopentyl glycol, mannitol, pentaerythritol, diethanolamine and triethanolamine.
5. The high temperature water-soluble PVA masterbatch composition according to claim 4, wherein the plasticizer comprises A, B component, the content of the A component is 60-100 wt% based on the total weight of the plasticizer, the A component is propylene glycol and/or glycerol, and the B component is selected from sorbitol, polyethylene glycol 200, neopentyl glycol and pentaerythritol.
6. The high temperature water-soluble PVA masterbatch composition according to claim 1 or 2, wherein the thermoplastic elastomer is one or more of EMA, EVA, EAA and EEA.
7. A high temperature water soluble PVA masterbatch composition according to claim 1 or 2, wherein said thermal stabilizer is selected from one or more of glyceryl monostearate, glyceryl tristearin monostearate, laurate, sorbitan stearate, zinc stearate, magnesium distearate, calcium stearate, cerium stearate, barium stearate, stearic acid and sodium stearate.
8. The high temperature water-soluble PVA masterbatch composition according to claim 1 or 2, wherein the lubricant is one or more of stearyl alcohol, stearamide, erucamide, oleamide, hydroxystearic acid, myristic acid, glycerol monostearate, triglycerol monostearate, pentaerythritol stearate and hydroxystearic acid.
9. The high temperature water soluble PVA masterbatch composition according to claim 1, wherein the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697, antioxidant 565, antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168 and antioxidant 626;
preferably, the antioxidant comprises a component a and a component b, wherein the content of the component a is 60-100 wt% based on the total weight of the antioxidant, the component a is antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697 or antioxidant 565, and the component b is antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168 or antioxidant 626.
10. The high-temperature water-soluble PVA masterbatch composition as defined in any one of claims 1 to 9 is mixed and granulated to prepare the high-temperature water-soluble PVA particles capable of being blow-molded.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940313A (en) * | 2020-10-30 | 2021-06-11 | 北京一撕得物流技术有限公司 | Biodegradable high-temperature water-soluble colored PVA film and preparation method thereof |
| CN112940425A (en) * | 2020-10-30 | 2021-06-11 | 北京一撕得物流技术有限公司 | High-temperature water-soluble PVA composition for blow molding and particles and film thereof |
-
2020
- 2020-04-26 CN CN202010339130.3A patent/CN111518352A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940313A (en) * | 2020-10-30 | 2021-06-11 | 北京一撕得物流技术有限公司 | Biodegradable high-temperature water-soluble colored PVA film and preparation method thereof |
| CN112940425A (en) * | 2020-10-30 | 2021-06-11 | 北京一撕得物流技术有限公司 | High-temperature water-soluble PVA composition for blow molding and particles and film thereof |
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Application publication date: 20200811 |
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