CN102604290B - Polyvinyl alcohol material of melt-processable and preparation method thereof - Google Patents
Polyvinyl alcohol material of melt-processable and preparation method thereof Download PDFInfo
- Publication number
- CN102604290B CN102604290B CN201210032307.0A CN201210032307A CN102604290B CN 102604290 B CN102604290 B CN 102604290B CN 201210032307 A CN201210032307 A CN 201210032307A CN 102604290 B CN102604290 B CN 102604290B
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- Prior art keywords
- polyvinyl alcohol
- melt
- processable
- calcium chloride
- alcohol material
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 90
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 89
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 18
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 26
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000001110 calcium chloride Substances 0.000 claims abstract description 19
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000006136 alcoholysis reaction Methods 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 7
- 235000013305 food Nutrition 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polynite Chemical compound 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of polyvinyl alcohol material of melt-processable, calculate by weight, it comprises 70 ~ 95 parts of polyvinyl alcohol, 0.75 ~ 5 part of calcium chloride and 5 ~ 25 parts of ethylene-acrylic acid copolymers (EAA).The present invention adopts in polyvinyl alcohol, adds EAA and calcium chloride, obtains polyvinyl alcohol material by common plastics processing units melt blending.Wherein EAA and calcium chloride can weaken the Intermolecular Forces of polyvinyl alcohol, reduce its melt temperature, are conducive to the melt-processed characteristic improving polyvinyl alcohol, make it realize melt-processed very well; Secondly, the method adopted have easy, environmental protection, with low cost, be easy to the advantages such as industrialization, the polyvinyl alcohol material prepared can meet the requirement of the industries such as food product pack.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinyl alcohol material, especially a kind of polyvinyl alcohol material can processed by melt blending and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is the water-soluble polymers obtained through alkali catalyzed alcoholysis by polyvinyl acetate (PVA).The physical properties of polyvinyl alcohol is larger by the impact of its chemical structure, alcoholysis degree, the polymerization degree.The polymerization degree of polyvinyl alcohol is generally divided into the superelevation polymerization degree (molecular weight 25-30 ten thousand), high-polymerization degree (molecular weight 17-22 ten thousand), the middle polymerization degree (molecular weight 12-15 ten thousand) and low polymerization degree (2.5-3.5 ten thousand).Alcoholysis degree generally has 78%, 88%, 98% 3 kind, the alcoholysis degree of partial alcoholysis is generally 87%-89%, and the alcoholysis degree of complete alcoholysis is 98%-100%.Polyvinyl alcohol has the constructional feature of poly-hydroxy, strong hydrogen bonding; The viscosity of the polymerization degree its solution higher of polyvinyl alcohol is larger, and alcoholysis degree its dissolution in low temperature lower is better.Therefore, impart the performances such as the resistance oxygen of its excellence, oil resistance, wear-resisting, anti tear, transparent, antistatic, resistance to chemical attack, be used in the industries such as coating, glue paste, fiber.But the fusing point of polyvinyl alcohol and decomposition temperature closely, easily thermolysis occur during melting, cause to carry out melt-processed easily.The non-thermal plasticity of polyvinyl alcohol makes its processing mode be only limitted to solution method spinning, curtain coating and mold processing, and complete processing is complicated, products production cost intensive, hinders it to apply widely.
At present, for the melt processing of polyvinyl alcohol material, a kind of novel method for plasticizing for thermoplastic processing polyvinyl alcohol material disclosed in CN1368515A, the method mainly have selected a kind of polymerisable amides monomer as softening agent, and by controlling the existence form of water in resin (Bound moisture), significantly reduce the processing temperature of polyvinyl alcohol material.But the softening agent that the method is selected has certain toxicity, the material of preparation is made to be not suitable for doing packaging material for food.
JP77110782 reports a kind of melt-blown polyvinyl alcohol film, its technical characterstic uses large water gaging (content is greater than 40%) as softening agent, to reduce the fusing point of polyvinyl alcohol, make it under the condition of the decomposition temperature lower than polyvinyl alcohol, realize Blown Film technique.But this preparation method stability in actual production is bad, there is a large amount of water in system in addition, make the resin extruded easily occur the phenomenon of bubbling, cause film cannot be evenly shaping.
Chinese patent ZL01131081 discloses a kind of homemade alcamines plasticizing modifier, this properties-correcting agent can reduce the plasticization temperature of polyvinyl alcohol, achieve the melting preparation of water-soluble poval material, but this patent homemade alcamines softening agent is also virose.
Summary of the invention
For solving the problem, the object of this invention is to provide a kind of polyvinyl alcohol material of melt-processable, not only reducing the plasticization temperature of polyvinyl alcohol material, make it be applicable to melt-processed, and process obtain good product quality, there is no toxicity.
Another object of the present invention is to provide the preparation method of the polyvinyl alcohol material of above-mentioned melt-processable.
The present invention is achieved in that a kind of polyvinyl alcohol material of melt-processable, it is characterized in that: calculate by weight, and formula comprises 70 ~ 95 parts of polyvinyl alcohol, 0.75 ~ 5 part of calcium chloride, 5 ~ 25 parts of ethylene-acrylic acid copolymers (EAA).
The polymerization degree of described polyvinyl alcohol is 300 ~ 7000.
The alcoholysis degree of described polyvinyl alcohol is 50 ~ 99%.
The vinylformic acid molar content of described ethylene-acrylic acid copolymer is 3 ~ 20.5%.
The preparation method of the polyvinyl alcohol material of above-mentioned melt-processable, it is characterized in that: first polyvinyl alcohol, calcium chloride and ethylene-acrylic acid copolymer are carried out pre-mixing, then mixed material is added in twin screw extruder and extrude, by the material pelletizing of extruding, namely obtain the polyvinyl alcohol material of modification.
When described twin screw extruder is extruded, extrusion temperature is 170 DEG C ~ 200 DEG C, screw speed 50 ~ 200rpm.
The present invention adopts and in polyvinyl alcohol, adds calcium chloride and EAA, by common plastics processing units---the polyvinyl alcohol material of the melt-processable that twin screw extruder melt blending obtains.Because wherein calcium chloride and EAA can weaken the Intermolecular Forces of polyvinyl alcohol, change its melt temperature, be conducive to the melt-processed characteristic improving polyvinyl alcohol, make it realize melt-processed very well.And adding of EAA can make the fragility of polyvinyl alcohol material improve.Secondly, the material adopted have nontoxic, environmental protection, with low cost, be easy to the advantages such as acquisitions, applicable mass industrial production, can meet the requirement of the industries such as food product pack by the preparation-obtained polyvinyl alcohol material of method of the present invention.
Accompanying drawing explanation
Fig. 1 is the first time intensification DSC graphic representation of the material of the listed formula of table 1 of the present invention;
Fig. 2 is the first time intensification DSC graphic representation of the material of the listed formula of table 2 of the present invention;
Fig. 3 is the thermogravimetric curve figure of the material of the listed formula of table 1 of the present invention;
Fig. 4 is the thermogravimetric curve figure of the material of the listed formula of table 2 of the present invention.
Embodiment
The present invention is a kind of polyvinyl alcohol material of melt-processable, calculates by weight, and formula comprises 70 ~ 95 parts of polyvinyl alcohol, 0.75 ~ 5 part of calcium chloride, 5 ~ 25 parts of ethylene-acrylic acid copolymers (EAA).In addition, in formula, also can add other conventional constituents according to practical situation, as the processing aid such as oxidation inhibitor, uv-absorbing agent and filler (as calcium carbonate, polynite, silicon-dioxide etc.).
Polyvinyl alcohol is water-soluble polymers, and molecule has strong polarity.The polymerization degree of the preferred polyvinyl alcohol of the present invention is 300 ~ 7000; Alcoholysis degree is 50 ~ 99%.
Preferably, the vinylformic acid molar content of ethylene-acrylic acid copolymer is 3 ~ 20.5%.
When preparing the polyvinyl alcohol material of above-mentioned melt-processable, first polyvinyl alcohol, calcium chloride and ethylene-acrylic acid copolymer are carried out pre-mixing, then mixed material is added in twin screw extruder and extrude, by the material pelletizing of extruding, namely obtain the polyvinyl alcohol material of modification.Preferably, when extruding, extrusion temperature is 170 DEG C ~ 200 DEG C, screw speed 50 ~ 200rpm.
Embodiment 1
The preparation of the polyvinyl alcohol material of melt-processable, calculates by weight, 95 parts of polyvinyl alcohol (alcoholysis degree of polyvinyl alcohol is 88%, the polymerization degree is 1500, the trade mark be 1588), 1 part of calcium chloride and 5 parts of EAA is fully mixed in mixing machine; Added by mixture in twin screw extruder, extrusion temperature is 185 DEG C, and the screw speed of twin screw extruder is 200rpm, carries out pelletizing, namely obtain the polyvinyl alcohol material of modification after being extruded by mixture.
Embodiment 2
The preparation of the polyvinyl alcohol material of melt-processable, calculate by weight, 90 parts of polyvinyl alcohol (alcoholysis degree of polyvinyl alcohol is 88%, the polymerization degree is 500, the trade mark be 0588), 1.8 parts of calcium chloride and 10 parts of EAA are fully mixed in mixing machine; Added by mixture in twin screw extruder, extrusion temperature is 170 DEG C, and the screw speed of twin screw extruder is 100rpm, carries out pelletizing, namely obtain the polyvinyl alcohol material of modification after being extruded by mixture.
Embodiment 3
The preparation of the polyvinyl alcohol material of melt-processable, calculate by weight, 80 parts of polyvinyl alcohol (alcoholysis degree of polyvinyl alcohol is 88%, the polymerization degree is 1700, the trade mark be 1788), 20 parts of EAA and 1.6 part calcium chloride are fully mixed in mixing machine; Added by mixture in twin screw extruder, extrusion temperature is 200 DEG C, and the screw speed of twin screw extruder is 200rpm, carries out pelletizing, namely obtain the polyvinyl alcohol material of modification after being extruded by mixture.
Embodiment 4
The preparation of the polyvinyl alcohol material of melt-processable, calculate by weight, 85 parts of polyvinyl alcohol (alcoholysis degree of polyvinyl alcohol is 50%, the polymerization degree is 1700, the trade mark be 1750), 15 parts of EAA and 0.85 part calcium chloride are fully mixed in mixing machine; Added by mixture in twin screw extruder, extrusion temperature is 200 DEG C, and the screw speed of twin screw extruder is 200rpm, carries out pelletizing, namely obtain the polyvinyl alcohol material of modification after being extruded by mixture.
Embodiment 5
The preparation of the polyvinyl alcohol material of melt-processable, calculate by weight, 80 parts of polyvinyl alcohol (alcoholysis degree of polyvinyl alcohol is 99%, the polymerization degree is 2400, the trade mark be 2499), 20 parts of EAA and 1.6 part calcium chloride are fully mixed in mixing machine; Added by mixture in twin screw extruder, extrusion temperature is 200 DEG C, and the screw speed of twin screw extruder is 200rpm, carries out pelletizing, namely obtain the polyvinyl alcohol material of modification after being extruded by mixture.
Embodiment 6
The preparation of the polyvinyl alcohol material of melt-processable, calculate by weight, 75 parts of polyvinyl alcohol (alcoholysis degree of polyvinyl alcohol is 99%, the polymerization degree is 2400, the trade mark be 2499), 20 parts of EAA, 1.6 parts of calcium chloride and 5 parts of calcium carbonate are fully mixed in mixing machine; Added by mixture in twin screw extruder, extrusion temperature is 200 DEG C, and the screw speed of twin screw extruder is 200rpm, carries out pelletizing, namely obtain the polyvinyl alcohol material of modification after being extruded by mixture.
Simultaneous test
Formula according to table 1, table 2 is 200 DEG C by the extrusion temperature of twin screw extruder, and screw speed is that the preparation condition of 200rpm obtains following goods, and carry out following experiment, the experimental data obtained is in table 1, table 2.
Table 1
Table 2
Show from the curve of Fig. 1, Fig. 2, Fig. 3 and Fig. 4, calcium chloride and adding of EAA make the melt temperature of polyvinyl alcohol reduce, and heat decomposition temperature improves.As can be seen from table 1 and table 2, calcium chloride and EAA add the reactive force reduced between polyvinyl alcohol macromole, thus make alcoholysis degree be that the melt temperature of the polyvinyl alcohol of 88% reduces, and improve polyvinyl alcohol thermostability, improve polyvinyl alcohol melt-processable.
Claims (6)
1. a polyvinyl alcohol material for melt-processable, is characterized in that: calculate by weight, fills a prescription to be made up of 70 ~ 95 parts of polyvinyl alcohol, 0.75 ~ 5 part of calcium chloride and 5 ~ 25 parts of ethylene-acrylic acid copolymers.
2. the polyvinyl alcohol material of melt-processable according to claim 1, is characterized in that: the polymerization degree of described polyvinyl alcohol is 300 ~ 7000.
3. the polyvinyl alcohol material of melt-processable according to claim 1, is characterized in that: the alcoholysis degree of described polyvinyl alcohol is 50 ~ 99%.
4. the polyvinyl alcohol material of melt-processable according to claim 1, is characterized in that: the vinylformic acid molar content of described ethylene-acrylic acid copolymer is 3 ~ 20.5%.
5. the preparation method of the polyvinyl alcohol material of the melt-processable in claim 1-4 described in arbitrary claim, it is characterized in that: first polyvinyl alcohol, calcium chloride and ethylene-acrylic acid copolymer are carried out pre-mixing, then mixed material is added in twin screw extruder and extrude, by the material pelletizing of extruding, namely obtain the polyvinyl alcohol material of modification.
6. the preparation method of the polyvinyl alcohol material of melt-processable according to claim 5, is characterized in that: when described twin screw extruder is extruded, and extrusion temperature is 170 DEG C ~ 200 DEG C, screw speed 50 ~ 200rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210032307.0A CN102604290B (en) | 2012-02-14 | 2012-02-14 | Polyvinyl alcohol material of melt-processable and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210032307.0A CN102604290B (en) | 2012-02-14 | 2012-02-14 | Polyvinyl alcohol material of melt-processable and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102604290A CN102604290A (en) | 2012-07-25 |
| CN102604290B true CN102604290B (en) | 2016-04-06 |
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| CN201210032307.0A Expired - Fee Related CN102604290B (en) | 2012-02-14 | 2012-02-14 | Polyvinyl alcohol material of melt-processable and preparation method thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104987440B (en) * | 2015-08-13 | 2017-09-15 | 四川大学 | A kind of modified polyvinylalcohol of melt-processable and preparation method and application |
| CN112724622A (en) * | 2020-12-24 | 2021-04-30 | 海南赛高新材料有限公司 | Modified PGA material compatibilized by adopting intercalation structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864132A (en) * | 2010-05-26 | 2010-10-20 | 四川大学 | Fusion preparation method of polyvinyl alcohol film |
| CN102321325A (en) * | 2011-08-16 | 2012-01-18 | 贵州省复合改性聚合物材料工程技术研究中心 | Polyvinyl alcohol material suitable for melt processing and preparation method thereof |
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2012
- 2012-02-14 CN CN201210032307.0A patent/CN102604290B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864132A (en) * | 2010-05-26 | 2010-10-20 | 四川大学 | Fusion preparation method of polyvinyl alcohol film |
| CN102321325A (en) * | 2011-08-16 | 2012-01-18 | 贵州省复合改性聚合物材料工程技术研究中心 | Polyvinyl alcohol material suitable for melt processing and preparation method thereof |
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| Publication number | Publication date |
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| CN102604290A (en) | 2012-07-25 |
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