CN108659424B - Water-soluble granulation method of modified polyvinyl alcohol - Google Patents
Water-soluble granulation method of modified polyvinyl alcohol Download PDFInfo
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- CN108659424B CN108659424B CN201810505293.7A CN201810505293A CN108659424B CN 108659424 B CN108659424 B CN 108659424B CN 201810505293 A CN201810505293 A CN 201810505293A CN 108659424 B CN108659424 B CN 108659424B
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 75
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005469 granulation Methods 0.000 title claims abstract description 20
- 230000003179 granulation Effects 0.000 title claims abstract description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000001035 drying Methods 0.000 claims abstract description 46
- 239000004014 plasticizer Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000004760 aramid Substances 0.000 claims abstract description 22
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000004202 carbamide Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 abstract description 18
- 230000008018 melting Effects 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 64
- 239000000243 solution Substances 0.000 description 37
- 235000011187 glycerol Nutrition 0.000 description 20
- 230000009467 reduction Effects 0.000 description 11
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QPKFVRWIISEVCW-UHFFFAOYSA-N 1-butane boronic acid Chemical compound CCCCB(O)O QPKFVRWIISEVCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a water-soluble granulation method of modified polyvinyl alcohol, which comprises the following steps: adding polyvinyl alcohol into water, heating and dissolving, sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the obtained solution, stirring, cooling the solution, adding an auxiliary agent, sealing, drying the obtained product for the first time, extruding and granulating, and drying the obtained granules for the second time, wherein the mass fraction of the polyvinyl alcohol is 10-20%, and the heating temperature is 80-100 ℃. According to the water-soluble preparation method provided by the invention, each component is uniformly distributed in the preparation process, the prepared product has high transparency and good toughness, and the compounding of the trimethylolpropane and the glycerol produces a synergistic effect, so that the granulation molding is good, the touch feeling of the surface of the product is fresh and not greasy, harsh conditions are not required in the preparation process, high-temperature melting is not required, the operation is simple, the safety is high, and the production is easy.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a water-soluble granulation method of modified polyvinyl alcohol.
Background
Polyvinyl alcohol (PVA) is a water-soluble polymer having excellent overall properties. PVA has excellent oil resistance, solvent resistance and gas barrier performance, and has unique advantages in packaging organic solvent, food, medicine, etc. Since the PVA polymer chain contains a large amount of active hydroxyl groups, a large amount of intramolecular and intermolecular hydrogen bonds are easily formed, so that the melting temperature of the PVA is quite close to the thermal decomposition temperature thereof, and the PVA is melted and decomposed, thereby being difficult to carry out thermoplastic processing. PVA begins to change color when heated to more than 200 ℃, begins to decompose at 240-250 ℃, and violently decomposes at 300 ℃, so that the PVA cannot be processed by a conventional melting method. The solution processing and forming process is complex, the cost is high, the environmental pollution is large, and the products with thick walls and complex shapes are difficult to prepare. Therefore, the reduction of the melting temperature and the improvement of the thermal stability are necessary conditions for realizing the melt processing and molding of PVA.
According to the above principle, in order to improve the melt processability, it is necessary to modify the PVA, for example, to destroy the hydrogen bonds, weaken the interaction between PVA macromolecules or change the flexibility of the chain, to lower the melting point, or to reduce the number of hydrogen bonds. In view of the above, researchers at home and abroad have conducted a lot of research, mainly including copolymerization modification, high polymer blending and solution plasticization. And (4) copolymerization modification. As for copolymerization modification, by copolymerization, other monomers with weaker acting force, such as vinyl, are introduced into the molecular chain of PVA, so that the acting force among molecules can be weakened, and the melting point of the PVA can be reduced. The higher the molecular chain flexibility of the comonomer, the poorer the regularity and the better the modification effect. The PVA modified by vinyl monomers can effectively reduce the melting point, and companies such as Mitsubishi chemical and Sumitomo chemical all have patents in the aspect of the melting point. In their patents, vinyl monomers and vinyl acetate are copolymerized, modified PVA is obtained by alkaline saponification, and then melt spinning is carried out at a temperature of more than 150 ℃, wherein the mass percentage content of PVA in the copolymer is not less than 50%. The Japanese Coly company synthesizes thermoplastically processable PVA which contains alpha-olefin units and/or vinyl ether units with the carbon number less than 4 and the melting point of 160-230 ℃; regarding blending modification, blending can make the performances of high polymers complement each other, make good use of advantages and avoid disadvantages, but must solve the problem of compatibility. The materials capable of being blended with PVA include water soluble natural polymer and synthetic polymer, the former is corn starch, animal glue, etc. and the latter is polyamide (PA6), water soluble polyurethane, etc. because they have radical capable of generating hydrogen bond with hydroxyl radical, the powerful acting force between PVA molecules is destroyed and the modification is performed. After PVA, polyamide and waxy polyethylene are mixed, the product obtained through melt extrusion and pressing has good fusion and uniformity. The n-butyl boronic acid and the phenyl boronic acid can also react with the hydroxyl group of PVA to obtain a PVA-boronic acid composite, the composite has a lower melting point, and the reduction of the melting point is related to the boric acid content. With the increase of the content of boric acid, the melting temperature of the compound is reduced, and the degradation temperature is increased, so that the compound can be subjected to melt processing; for the plasticization of the solution, the addition of the plasticizer can swell or dilute the high polymer, thereby changing the acting force between the high polymers and reducing the melting point, and the common plasticizers for PVA include water, glycerin, polyhydric alcohol and oligomer thereof, alcohol amine modifier and the like.
CN101864084A discloses a hydroxyethyl cellulose/polyvinyl alcohol blend film and a preparation method thereof, the blend film is prepared by a tape casting method and then is crosslinked with phosphoric acid, the blend film with good mechanical property, thermal stability, hydrolysis resistance and ageing resistance and excellent biodegradability is obtained, and the blend film can be widely used in the fields of medicine, cosmetics, food packaging and the like, however, the invention does not explicitly describe the thermal stability of the polyvinyl alcohol modified blend film. CN101210075 discloses a polymer film containing ionic liquid and a preparation method thereof, the polymer film is prepared from a film material and ionic liquid adsorbed and supported on the film material, the weight of the ionic liquid accounts for 0.1-70% of the weight of the polymer film, the ionic liquid is dissolved into a polyvinyl alcohol aqueous solution to form a uniform solution, the uniform solution is dried at room temperature to form a film, and then the film is crosslinked by a crosslinking agent to obtain the polymer film. The film of the invention has better thermal stability and mechanical stability, simple synthesis operation, potential application value in the processes of catalytic esterification and separation of organic sulfide, aromatic hydrocarbon and alkane, and wide application prospect in the aspects of membrane catalysis, separation analysis, and the like. However, the ionic liquid used in this method is expensive, and the thermal stability of the film is not specifically disclosed. CN1786302A discloses a method for preparing high-performance polyvinyl alcohol fiber by melt spinning, which adopts a composite modifier composed of a nitrogen-containing compound, a hydrophilic auxiliary additive and water to carry out intermolecular hydrogen bond compounding with polyvinyl alcohol to prepare modified polyvinyl alcohol.
In summary, in the existing PVA modification methods, the modification method of copolymerization modification has high requirements on equipment and technology, and cannot modify the conventional PVA products which are already commercialized in a large scale, the existing blending modification method also has some technical bottlenecks, the compatibility of the system during blending is not completely solved, and industrialization is difficult to realize, the existing solution plasticizing method generally only reduces the melting temperature, and the conventional plasticizer is easy to vaporize under the high-temperature melting condition, escapes from the modification system, pollutes the production environment, and brings negative effects on the material composition and the processing flow. Therefore, there is a need to develop a new method for preparing modified PVA.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a water-soluble granulation method of modified polyvinyl alcohol.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
Preferably, in the solution obtained in the step (1), the mass fraction of the polyvinyl alcohol is 10-20%.
Preferably, in the solution obtained in the step (1), the heating temperature is 80-100 ℃, and the heating time is 4-12 h.
Preferably, the plasticizer of step (2) is at least one of an oily plasticizer and an aqueous plasticizer.
Preferably, the oily plasticizer is glycerin, and the aqueous plasticizer is trimethylolpropane.
Preferably, the addition amount of the glycerol is 2-20% of the mass of the solution, and the addition amount of the trimethylolpropane is 1-15% of the mass of the solution.
Preferably, the addition amount of the hyperbranched aromatic polyamide polymer in the step (2) is 0.5-0.7% of the solution mass, and the hyperbranched aromatic polyamide polymer refers to a series of hyperbranched polymers containing hydroxyl groups.
Preferably, the temperature of the temperature reduction in the step (3) is less than or equal to 60 ℃.
Preferably, the auxiliary agent in the step (3) is a mixture of N, N-dimethylformamide and urea, and the mass fraction of the auxiliary agent is 3-15%.
Preferably, the mass ratio of the N, N-dimethylformamide to the urea in the mixture is (1-5): 1.
preferably, the temperature of the first drying in the step (4) is 40-60 ℃, the drying time is 3-12 hours, the moisture content in the dried product is 10-30%, and the product is a soft solid substance.
Preferably, the temperature of the second drying in the step (5) is 40-60 ℃, and the drying time is 4-24 h.
Preferably, after the second drying in the step (5), the moisture content in the product is less than or equal to 5%.
Preferably, after the step (3), the vacuum pumping can be carried out, and then the product is dried and extruded for granulation.
And (4) sealing after the addition of the auxiliary agent in the step (3) to prevent the urea from volatilizing out of the system.
If the water content is less than or equal to 5 percent after one-time drying, the colloid can be hardened and is not suitable for extrusion granulation without heating.
In the assistant, N, N-dimethylformamide is an aprotic polar solvent, can be randomly mixed with water except halogenated hydrocarbon and a plurality of organic solvents, has good dissolving capacity for various organic compounds and inorganic compounds, and has good chemical stability in the absence of alkali, acid and water.
The invention has the advantages of
1. According to the water-soluble preparation method provided by the invention, each component is uniformly distributed in the preparation process, and the prepared product has high transparency and good toughness;
2. in the preparation process, the hyperbranched polymer is introduced, so that the fluidity of the product is improved, the melting temperature is reduced, and the difference between the melting temperature and the decomposition temperature reaches 65 ℃;
3. by compounding the trimethylolpropane and the glycerol, a synergistic effect is generated, granulation and molding are good, and the touch feeling of the product surface is fresh and not greasy;
4. the modified polyvinyl alcohol prepared by the invention is convenient for film blowing, can be used for preparing washing balls and the like, and has wide application range;
5. the preparation process has no harsh conditions, does not need high-temperature melting, and has simple operation, high safety and easy production.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the addition amount of glycerol is 2%, the addition amount of trimethylolpropane is 1%, the addition amount of hyperbranched aromatic polyamide polymer is 0.5%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 3%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 1: 1, the temperature of the first drying in the step (4) is 50 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Example 2
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the adding amount of glycerol is 20%, the adding amount of trimethylolpropane is 15%, the adding amount of hyperbranched aromatic polyamide polymer is 0.7%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 15%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 5: 1, the temperature of the first drying in the step (4) is 50 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Example 3
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 15%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the adding amount of glycerol is 10%, the adding amount of trimethylolpropane is 7%, the adding amount of hyperbranched aromatic polyamide polymer is 0.6%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 9%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 3: 1, the temperature of the first drying in the step (4) is 50 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Example 4
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) vacuumizing the product obtained in the step (3);
(5) drying the product obtained in the step (4) for the first time, and then extruding and granulating;
(6) and (5) drying the particles obtained in the step (5) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the adding amount of glycerol is 20%, the adding amount of trimethylolpropane is 15%, the adding amount of hyperbranched aromatic polyamide polymer is 0.7%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 15%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 5: 1, the temperature of the first drying in the step (5) is 50 ℃, and the temperature of the second drying in the step (6) is 50 ℃.
Comparative example 1
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizer in the step (2) is glycerol, the addition amount of glycerol is 20%, the addition amount of hyperbranched aromatic polyamide polymer is 0.7%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 15%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of N, N-dimethylformamide to urea in the mixture is 5: 1, the temperature of the first drying in the step (4) is 50 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Comparative example 2
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the adding amount of glycerol is 20%, the adding amount of trimethylolpropane is 15%, the adding amount of hyperbranched aromatic polyamide polymer is 0.7%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 15%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 5: 1, the temperature of the first drying in the step (4) is 100 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Comparative example 3
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the adding amount of glycerol is 20%, the adding amount of trimethylolpropane is 15%, the adding amount of hyperbranched aromatic polyamide polymer is 0.7%, the temperature after the temperature reduction in the step (3) is 70 ℃, the mass fraction of the auxiliary in the step (3) is 15%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 5: 1, the temperature of the first drying in the step (4) is 50 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Comparative example 4
A water-soluble granulation method of modified polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) and (4) drying the particles obtained in the step (4) for the second time.
In the solution obtained in the step (1), the mass fraction of polyvinyl alcohol is 10%, the heating temperature is 90 ℃, the plasticizers in the step (2) are glycerol and trimethylolpropane, the adding amount of glycerol is 20%, the adding amount of trimethylolpropane is 15%, the adding amount of hyperbranched aromatic polyamide polymer is 0.2%, the temperature after the temperature reduction in the step (3) is 50 ℃, the mass fraction of the auxiliary in the step (3) is 15%, the auxiliary is a mixture of N, N-dimethylformamide and urea, and the mass ratio of the N, N-dimethylformamide to the urea in the mixture is 5: 1, the temperature of the first drying in the step (4) is 50 ℃, and the temperature of the second drying in the step (5) is 50 ℃.
Test example 1
The modified polyvinyl alcohols obtained in examples 1 to 3 and comparative examples 1 to 4 were compared, and the specific results are shown in table 1.
TABLE 1 comparison of Properties of modified polyvinyl alcohols obtained in examples and comparative examples
Claims (6)
1. A water-soluble granulation method of modified polyvinyl alcohol is characterized by comprising the following steps:
(1) adding polyvinyl alcohol into water, and heating to dissolve;
(2) sequentially adding a plasticizer and a hyperbranched aromatic polyamide polymer into the solution obtained in the step (1) and stirring;
(3) cooling the solution obtained in the step (2), adding an auxiliary agent, and sealing;
(4) drying the product obtained in the step (3) for the first time, and then extruding and granulating;
(5) drying the particles obtained in the step (4) for the second time;
the plasticizer in the step (2) is an oily plasticizer and a water-based plasticizer;
the oily plasticizer is glycerol, and the aqueous plasticizer is trimethylolpropane;
based on the mass of the solution, the addition amount of the glycerol is 2-20 wt%, the addition amount of the trimethylolpropane is 1-15 wt%, and the addition amount of the hyperbranched aromatic polyamide polymer is 0.5-0.7 wt%.
2. The method for granulating a modified polyvinyl alcohol in water, according to claim 1, wherein the solution obtained in step (1) contains 10 to 20% by mass of polyvinyl alcohol, and the heating temperature is 80 to 100 ℃.
3. The method for granulating modified polyvinyl alcohol in water as claimed in claim 1, wherein the temperature of said step (3) is 60 ℃ or lower.
4. The water-soluble granulation method of the modified polyvinyl alcohol according to claim 1, wherein the mass fraction of the auxiliary agent in the step (3) is 3-15%, and the auxiliary agent is a mixture of N, N-dimethylformamide and urea.
5. The granulating method of claim 4, wherein the mass ratio of N, N-dimethylformamide to urea in the mixture is (1-5): 1.
6. the method for granulating a modified polyvinyl alcohol in a water-soluble form as claimed in claim 1, wherein the temperature for the first drying in the step (4) is 40 to 60 ℃ and the temperature for the second drying in the step (5) is 40 to 60 ℃.
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| WO2005073284A2 (en) * | 2004-01-28 | 2005-08-11 | The University Of Sheffield | Hyperbranched polymers |
| CN102432968A (en) * | 2011-10-12 | 2012-05-02 | 江苏博特新材料有限公司 | Modified polyvinyl alcohol and preparation method thereof |
| CN103724901A (en) * | 2014-01-03 | 2014-04-16 | 北京化工大学常州先进材料研究院 | Preparation method of fully degradable biological mulch film |
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| WO2005073284A2 (en) * | 2004-01-28 | 2005-08-11 | The University Of Sheffield | Hyperbranched polymers |
| CN102432968A (en) * | 2011-10-12 | 2012-05-02 | 江苏博特新材料有限公司 | Modified polyvinyl alcohol and preparation method thereof |
| CN103724901A (en) * | 2014-01-03 | 2014-04-16 | 北京化工大学常州先进材料研究院 | Preparation method of fully degradable biological mulch film |
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