CN117624664A - Method for preparing film from solution containing natural polymer and natural polymer film - Google Patents
Method for preparing film from solution containing natural polymer and natural polymer film Download PDFInfo
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- CN117624664A CN117624664A CN202310299454.2A CN202310299454A CN117624664A CN 117624664 A CN117624664 A CN 117624664A CN 202310299454 A CN202310299454 A CN 202310299454A CN 117624664 A CN117624664 A CN 117624664A
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- coagulating bath
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- 229920005615 natural polymer Polymers 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000001112 coagulating effect Effects 0.000 claims abstract description 68
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 64
- 108010025899 gelatin film Proteins 0.000 claims abstract description 29
- 239000004202 carbamide Substances 0.000 claims abstract description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 3
- 238000005345 coagulation Methods 0.000 claims description 41
- 230000015271 coagulation Effects 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229920002101 Chitin Polymers 0.000 claims description 11
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000008041 oiling agent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000004627 regenerated cellulose Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000003513 alkali Substances 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 229920000875 Dissolving pulp Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229940079826 hydrogen sulfite Drugs 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940069078 citric acid / sodium citrate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 1
- -1 zinc oxide) Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a solution film-forming method containing natural polymers, which comprises the following steps: extruding a solution containing natural polymers through a membrane head, and solidifying and forming a primary gel film through at least 1 coagulating bath, wherein the primary gel film is washed, oiled and dried to obtain a regenerated natural polymer film, the solution containing natural polymers contains metal hydroxide and an auxiliary agent, and the auxiliary agent is at least one selected from urea, zinc oxide and thiourea; the bicarbonate, or the combination of the bicarbonate and the carbonate, or the bisulphite, or the combination of the bisulphite and the sulphite is used as a coagulating bath component, which is favorable for uniformly coagulating and forming the natural polymer solution in the coagulating bath to form a primary gel film, thereby obtaining the natural polymer film with transparency, uniform thickness and excellent performance.
Description
Technical Field
The invention relates to the technical field of natural polymer solution film making, in particular to a solution film making method containing natural polymers and a natural polymer film.
Background
The problem of "white pollution" caused by the use of petrochemical-based plastic films in large quantities is a hot spot of concern in countries around the world. Therefore, the development of the green and degradable natural polymer film material from animals and plants is not only beneficial to alleviating the pollution problem of plastics, but also accords with sustainable and low-carbon national development strategy. The natural polymers from the nature mainly comprise cellulose, chitin, chitosan, hemicellulose, starch, sodium alginate and the like, and most of the natural polymers contain a large number of hydroxyl groups, amino groups, carboxyl groups and the like, so that the natural polymers have more strong hydrogen bonding actions among molecules and in the molecules, and are difficult to dissolve and utilize. At present, the solvent for dissolving natural polymers mainly comprises NaOH/CS 2 LiCl/DMAc, ionic liquids, N-methylmorpholine-N-oxide and aqueous alkali/urea solvent systems, etc. The alkali solution is a natural polymer solvent system with great development prospect at present, such as sodium hydroxide, sodium hydroxide/urea water, lithium hydroxide/urea, potassium hydroxide/urea and the like.
The coagulation bath has the function of rapidly coagulating and forming a homogeneous natural polymer solution, and has the effects of affecting the forming process, structure and performance of fibers and films, and simultaneously has the problems of salt separation recovery and treatment generated after the coagulation bath is reacted with a solvent. Alkali/urea is a rapid physical dissolution process, and the best way to achieve solvent recycling and cost reduction is physical solidification. However, the coagulation bath usually has a slow coagulation rate and incomplete reaction with hot water (CN 101921402 a) or a neutral high-temperature salt solution (CN 102443869A), and the high-temperature coagulation causes phase separation and poor strength of the fibers. And because of strong hydrogen bonding between cellulose and alkali, the residual amount of alkali in the film is high, the subsequent alkali removal process is increased, the production difficulty is improved, and the industrial production is not facilitated. The above problems occur also with solutions containing organic solvents as coagulation baths (CN 110129923 a), most importantly considering the safety production of organic solvents. For this purpose, the currently common methods are mainly acidic coagulation, such as sulfuric acid/sodium sulfate aqueous solution (patent application number 200510018799.8), sulfuric acid/sulfuric acid, sodium/ammonium sulfate aqueous solution (patent application number 200410013389. X), phosphoric acid/phosphate (CN 103757720A), citric acid/sodium citrate/glycol aqueous solution (CN 110042488A), phytic acid (CN 107653502A), and the like.
The coagulating bath consisting of the strong acid or the weak acid reacts with alkali/urea to generate various salts or mixed aqueous solutions of various salts and urea and the like, so that the consumption of chemical materials is high and the cost is high; and the mixed salt is difficult to separate, so that the solvent or the salt is difficult to recycle, and the difficulty and the cost of salt recovery and treatment are directly increased.
Disclosure of Invention
In order to solve the problems of poor product performance, high recovery and treatment cost of coagulation bath salt and the like in the prior art, the invention provides a solution film preparation method containing natural polymers and a natural polymer film.
The first aspect of the invention provides a method for preparing a membrane from a solution containing natural polymers, comprising the following steps:
extruding a solution containing natural polymers through a membrane head, and solidifying and forming a primary gel film through at least 1 coagulating bath, wherein the primary gel film is washed, oiled and dried to obtain a regenerated natural polymer film;
the coagulating bath is a first coagulating bath containing XHCO 3 And/or XHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); in the coagulation bath, XHCO 3 And/or XHSO 3 The mass concentration of (2) is 0.5-30wt%; or (b)
The coagulating bath is a second coagulating bath containing XHCO 3 And Y 2 CO 3 Or XHSO 3 And Y 2 SO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
The second aspect of the invention provides a natural polymer film prepared by the film preparation method.
Compared with the prior art, the natural polymer-containing film forming method disclosed by the invention has the advantages that bicarbonate or a composition of bicarbonate and carbonate, or bisulfite or a composition of bisulfite and sulfite is used as a coagulating bath component and is used as a moderate coagulating solution, so that the natural polymer-containing solution is uniformly coagulated and formed in the coagulating bath to form a primary gel film, the primary gel film is not completely formed into a cellulose intermolecular hydrogen bond network in the process, and the natural polymer film which is transparent, uniform in thickness and excellent in performance (the strength is up to 136MPa and the dry breaking elongation is higher than 13.7%) is obtained by fully curing and stretching in the coagulating bath and the subsequent stretching.
In the coagulating bath, the main component of the salt solution is alkalescent bicarbonate, the salt reacts with strong alkali, the auxiliary agent is urea and/or thiourea which are accumulated in the coagulating bath to be beneficial to improving the performance of products, and when the auxiliary agent is metal salt (such as zinc oxide), corresponding precipitate is generated in the coagulating bath, and the precipitate can be filtered and removed without influencing the regeneration of weak acid bicarbonate or bisulphite; the hydrogen carbonate or the hydrogen sulfite is regenerated by acidification of carbon dioxide or sulfur dioxide, so that urea and/or thiourea can be recycled, and the hydrogen carbonate, the hydrogen sulfite and the sulfite are easy to separate and recycle, so that the consumption of chemical materials is equivalent to or even lower than that of a viscose process, the recycling and treatment problems of high-concentration salt are solved, the production difficulty and the cost are reduced, and the application prospect is wide.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a method for preparing a membrane from a solution containing natural polymers, comprising the following steps:
extruding a solution containing natural polymers through a membrane head, and solidifying and forming a primary gel film through at least 1 coagulating bath, wherein the primary gel film is washed, oiled and dried to obtain a regenerated natural polymer film;
the coagulating bath is a first coagulating bath containing XHCO 3 And/or XHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); in the coagulation bath, XHCO 3 And/or XHSO 3 The mass concentration of (2) is 0.5-30wt%; or (b)
The coagulating bath is a second coagulating bath containing XHCO 3 And Y 2 CO 3 Or XHSO 3 And Y 2 SO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
In the present invention, the molding conditions are not particularly limited, and according to a preferred embodiment of the present invention, the molding conditions include: the temperature is 5-90 ℃, preferably 20-40 ℃.
In the present invention, the accumulation of urea and/or thiourea in the coagulation bath, which contributes to the improvement of the product properties, is an aid, and according to a preferred embodiment of the present invention, the coagulation bath further contains urea and/or thiourea, preferably in a mass concentration of 5-60wt%.
In the present invention, the mass concentration of the natural polymer material is not particularly limited, and according to a preferred embodiment of the present invention, the mass concentration of the natural polymer material in the solution containing the natural polymer is 5wt% to 9wt%; preferably, the natural polymer material has a polymerization degree of 200 to 800.
According to a preferred embodiment of the invention, the mass concentration of the auxiliary agent in the solution containing natural polymer is 0.01-15 wt%.
In the present invention, the natural polymer material is not particularly limited, and any natural polymer material conventional in the art can be used in the present invention, and according to a preferred embodiment of the present invention, the natural polymer material is selected from at least one of cellulose, chitin, chitosan and sodium alginate.
According to a preferred embodiment of the present invention, the metal hydroxide is selected from at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the present invention, the solution containing natural polymer is subjected to at least 1 coagulation bath, for example, may be subjected to 1, 2, 3, and 4 coagulation baths, and according to a preferred embodiment of the present invention, the solution containing natural polymer is subjected to 2 coagulation baths; is beneficial to improving the performance of the regenerated natural polymer film.
According to a preferred embodiment of the present invention, in the 1 st coagulation bath, XHCO when the coagulation bath is the first coagulation bath 3 Or XHSO 3 The mass concentration of (2) is 5-20wt%; when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-10wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 1-10wt% respectively.
According to a preferred embodiment of the invention, in the coagulation bath of lane 2, XHCO when the coagulation bath is the first coagulation bath 3 Or XHSO 3 The mass concentration of (2) is 0.5-5wt%; the coagulating bath is a second coagulating bathAt the time of XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-5wt%; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 2-5wt%.
According to a preferred embodiment of the present invention, the forming conditions in the coagulation bath 1 st pass include: the temperature is 20-40 ℃; the molding conditions in the 2 nd to coagulation bath include: the temperature is 40-60 ℃.
According to a preferred embodiment of the present invention, in the 1 st coagulation bath, XHCO when the coagulation bath is the first coagulation bath 3 Or XHSO 3 The mass concentration of (2) is 8-15wt% respectively; when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (C) is 5-10wt%, Y 2 CO 3 Or Y 2 SO 3 The mass concentrations of (2) to (6) wt.% each.
According to a preferred embodiment of the invention, in the coagulation bath 1, the coagulation bath is a second coagulation bath, wherein XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-10wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of urea and/or thiourea is respectively 2-6wt% and the mass concentration of urea and/or thiourea is 20-40wt%.
According to a preferred embodiment of the present invention, the film forming method further includes: the nascent gel film is drawn in a coagulating bath with a drawing rate of-50% -100%.
According to a preferred embodiment of the invention, the drawing ratio of the coagulation bath 1 is-50% to 100%, and the drawing ratio of the coagulation bath 2 is 0% to 100%.
In the present invention, the water washing conditions are not particularly limited as long as the salt is washed clean, and according to a preferred embodiment of the present invention, the water washing conditions include: the temperature is 25-90 ℃, preferably 40-80 ℃.
In the invention, oiling is used for water retention and plasticization; according to a preferred embodiment of the present invention, the oiling agent used for the oiling is at least one selected from the group consisting of glycerin and silicone oil.
In the present invention, the drying conditions are not particularly limited, and preferably include: the temperature is 60-130 ℃, preferably 80-110 ℃.
The second aspect of the invention provides a natural polymer film prepared by the film preparation method.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention in any way.
The performance test method of the regenerated cellulose film comprises the following steps: GB T22871-2008 plain cellophane.
Example 1
(i) Dissolving cellulose with DP of 300 into a sodium hydroxide/urea/water (mass ratio of 7:12:81) system, and filtering and defoaming to obtain a solution containing 8.0wt% cellulose;
(ii) Extruding the solution in the step (i) through a membrane head, and carrying out coagulating bath (containing 8wt% of sodium bicarbonate) at the temperature of 10 ℃ and 30% forward drawing to obtain a primary gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 30% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 60 ℃, 90 ℃ and 80 ℃ and is wound to obtain the regenerated cellulose film.
The regenerated cellulose film has high transparency and uniform thickness, the longitudinal strength is 108MPa, and the elongation at break is 10.7%; the transverse strength is 101MPa, and the elongation at break is 26.7%.
Example 2
(i) Dissolving cellulose with DP of 300 into a sodium hydroxide/urea/water (mass ratio of 7:5:87) system, and filtering and defoaming to obtain a solution containing 7wt% cellulose;
(ii) Extruding the solution in the step (i) through a membrane head, and performing coagulation bath (containing 10wt% of sodium bicarbonate, 2wt% of sodium carbonate and 20wt% of urea) at a temperature of 22 ℃ and performing 30% negative drawing to obtain a primary gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 50% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 60 ℃, 110 ℃ and 80 ℃ and is wound to obtain the regenerated cellulose film.
The regenerated cellulose film has high transparency and uniform thickness, the longitudinal strength is 125MPa, and the elongation at break is 15.6%; the transverse strength is 105MPa, and the elongation at break is 30.2%.
Example 3
(i) Chitin with DP of 250 was dissolved in potassium hydroxide/urea/water (mass ratio of 12.7:
5.7:81.6 Filtering and defoaming to obtain a solution containing 7.0wt% of chitin;
(ii) Extruding the solution in the step (i) through a membrane head, and performing coagulating bath (containing 15wt% of potassium bicarbonate and 15wt% of potassium carbonate) at the temperature of 10 ℃ and performing 30% negative drawing to obtain a primary gel film;
(iii) The nascent gel film is sequentially washed by hot water at 50 ℃, is subjected to 50% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 80 ℃, 130 ℃ and 70 ℃ and is wound to obtain the regenerated chitin film.
The regenerated chitin film has high transparency and uniform thickness, the longitudinal strength is 116MPa, and the elongation at break is 16.5%; the transverse strength is 98MPa, and the elongation at break is 31.8%.
Example 4
(i) Chitin with DP of 250 was dissolved in potassium hydroxide/urea/water (mass ratio of 12.7:
5.7:81.6 In the system, defoaming is carried out to obtain a solution containing 7 weight percent of chitin;
(ii) Extruding the solution in the step (i) through a membrane head, passing through a coagulating bath (the temperature of the coagulating bath is 20 ℃) which comprises 10wt% of potassium bicarbonate, 15wt% of potassium carbonate and 20wt% of urea, and carrying out 30% negative drawing to obtain a nascent gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 50% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 80 ℃, 130 ℃ and 70 ℃ and is wound to obtain the regenerated chitin film.
The regenerated chitin film has high transparency and uniform thickness, the longitudinal strength is 129MPa, and the elongation at break is 15.5%; the transverse strength is 110MPa, and the elongation at break is 24.0%.
Example 5
(i) Dissolving cellulose with DP of 300 into a sodium hydroxide/urea/water (mass ratio of 7:12:81) system, and defoaming to obtain a solution containing 8.0wt% cellulose;
(ii) Extruding the solution in the step (i) through a film head, passing through a 1 st coagulating bath (containing 8wt% of sodium bicarbonate) at 10 ℃ and carrying out 15% positive drawing,
then passing through a 2 nd coagulating bath (containing 5wt% sodium bicarbonate and 2wt% sodium carbonate) at 30 ℃ and carrying out 30% forward drawing to obtain a nascent gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 30% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 60 ℃, 90 ℃ and 80 ℃ and is wound to obtain the regenerated cellulose film.
The regenerated cellulose film has high transparency and uniform thickness, the longitudinal strength is 110MPa, and the elongation at break is 15.0%; the transverse strength is 105MPa, and the elongation at break is 20.5%.
Example 6
(i) Dissolving cellulose with DP of 300 into a sodium hydroxide/urea/water (mass ratio of 7:5:87) system, and defoaming to obtain a solution containing 8wt% cellulose;
(ii) Extruding the solution in the step (i) through a membrane head, passing through a 1 st coagulating bath (containing 6wt% sodium bicarbonate, 2wt% sodium carbonate and 20wt% urea), wherein the coagulating bath temperature is 22 ℃, and carrying out 15% negative drawing;
then passing through a 2 nd coagulating bath (containing 5wt% sodium bicarbonate and 2wt% sodium carbonate) at 22 ℃ and carrying out 45% forward drawing to obtain a nascent gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 50% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 60 ℃, 110 ℃ and 80 ℃ and is wound to obtain the regenerated cellulose film.
The regenerated cellulose film has high transparency and uniform thickness, the longitudinal strength is 136MPa, and the elongation at break is 13.7%; the transverse strength is 120MPa, and the elongation at break is 20.7%.
Example 7
(i) Dissolving cellulose with DP of 300 into a sodium hydroxide/urea/water (mass ratio of 7:5:87) system, and defoaming to obtain a solution containing 8wt% cellulose;
(ii) Extruding the solution in the step (i) through a membrane head, passing through a 1 st coagulating bath (containing 6wt% sodium bicarbonate and 2wt% sodium carbonate), wherein the temperature of the coagulating bath is 22 ℃, and carrying out 15% negative drawing;
then passing through a 2 nd coagulating bath (containing 5wt% sodium bicarbonate and 2wt% sodium carbonate) at 22 ℃ and carrying out 45% forward drawing to obtain a nascent gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 50% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 60 ℃, 110 ℃ and 80 ℃ and is wound to obtain the regenerated cellulose film.
The regenerated cellulose film has high transparency and uniform thickness, the longitudinal strength is 122MPa, and the elongation at break is 14.4%; the transverse strength is 116MPa, and the elongation at break is 20.5%.
Example 8
(i) Dissolving cellulose with DP of 300 into a sodium hydroxide/urea/water (mass ratio of 7:5:87) system, and defoaming to obtain a solution containing 8wt% cellulose;
(ii) Extruding the solution in the step (i) through a membrane head, passing through a 1 st coagulating bath (containing 16wt% sodium bicarbonate) at 60 ℃ and carrying out 15% negative drawing;
then passing through a 2 nd coagulating bath (containing 5wt% sodium bicarbonate and 2wt% sodium carbonate) at 22 ℃ and carrying out 45% forward drawing to obtain a nascent gel film;
(iii) The nascent gel film is sequentially washed by hot water at 55 ℃, is subjected to 50% positive draft, is soaked in 30% glycerol for oiling, and is finally sequentially dried by hot air at 60 ℃, 110 ℃ and 80 ℃ and is wound to obtain the regenerated cellulose film.
The regenerated cellulose film has high transparency and uniform thickness, the longitudinal strength is 108MPa, and the elongation at break is 14.3%; the transverse strength is 102MPa, and the elongation at break is 24.6%.
Comparative example 1
The procedure of example 1 was followed except that the coagulation bath was a sulfuric acid coagulation bath system (concrete composition: 110g/L of sulfuric acid and 150g/L of sodium sulfate), and the other conditions were the same as in example 1.
The longitudinal strength is 89MPa, and the elongation at break is 8.0%; the transverse strength is 65MPa, and the elongation at break is 16.0%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for preparing a membrane by using a solution containing natural polymers is characterized by comprising the following steps:
extruding a solution containing natural polymers through a membrane head, and solidifying and forming a primary gel film through at least 1 coagulating bath, wherein the primary gel film is washed, oiled and dried to obtain a regenerated natural polymer film;
the coagulating bath is a first coagulating bath containing XHCO 3 And/or XHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); in the coagulation bath, XHCO 3 And/or XHSO 3 The mass concentration of (2) is 0.5-30wt%; or (b)
The coagulating bath is a second coagulating bath containing XHCO 3 And Y 2 CO 3 Or XHSO 3 And Y 2 SO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5 each-30wt％；Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
2. The method for producing a film according to claim 1, wherein,
the molding conditions include: the temperature is 5-90 ℃, preferably 20-40 ℃; and/or
The coagulation bath also contains urea and/or thiourea, preferably in a mass concentration of 5-60wt%.
3. A film forming method according to claim 1 or 2, wherein,
in the solution containing the natural polymer, the mass concentration of the natural polymer material is 5-9 wt%; preferably, the polymerization degree of the natural high molecular material is 200-800; and/or
In the solution containing natural polymer, the mass concentration of the auxiliary agent is 0.01-15 wt%.
4. A film forming method according to claim 1 or 2, wherein,
the natural polymer material is at least one of cellulose, chitin, chitosan and sodium alginate; and/or
The metal hydroxide is selected from at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
5. A film forming method according to any one of claims 1 to 4, wherein,
the solution containing natural polymer passes through 2 coagulating baths;
in the 1 st coagulating bath, XHCO when the coagulating bath is the first coagulating bath 3 Or XHSO 3 The mass concentration of (2) is 5-20wt%;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-10wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 1-10wt% respectively;
in the 2 nd coagulating bath, when the coagulating bath is the first coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-5wt%;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-5wt%; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 2-5wt%;
preferably, the molding conditions in the coagulation bath of lane 1 include: the temperature is 20-40 ℃;
the molding conditions in the 2 nd to coagulation bath include: the temperature is 40-60 ℃.
6. A film forming method according to claim 5, wherein,
in the coagulation bath of the 1 st path,
when the coagulating bath is a first coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 8-15wt% respectively;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (C) is 5-10wt%, Y 2 CO 3 Or Y 2 SO 3 The mass concentrations of (2) to (6) wt.% each.
7. The method for producing a film according to claim 6, wherein,
in the 1 st coagulating bath, the coagulating bath is a second coagulating bath, wherein XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-10wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of urea and/or thiourea is respectively 2-6wt% and the mass concentration of urea and/or thiourea is 20-40wt%.
8. A film forming method according to claim 5, wherein,
the film making method also comprises the steps of drafting the nascent gel film in a coagulating bath, wherein the drafting rate is-50% -100%;
preferably, the drawing rate of the 1 st coagulation bath is-50% -100%, and the drawing rate of the 2 nd coagulation bath is 0-100%.
9. A film forming method according to any one of claims 1 to 7, wherein,
the oiling agent used for oiling is at least one of glycerol and silicone oil; and/or
The water washing conditions include: the temperature is 25-90 ℃, preferably 40-80 ℃; and/or
The drying conditions included: the temperature is 60-130 ℃, preferably 80-110 ℃.
10. A natural polymer film produced by the film-forming method according to any one of claims 1 to 8.
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