CN115011261A - Method for bonding bulk material by using amino-containing insoluble polymer solution - Google Patents
Method for bonding bulk material by using amino-containing insoluble polymer solution Download PDFInfo
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- CN115011261A CN115011261A CN202210730646.XA CN202210730646A CN115011261A CN 115011261 A CN115011261 A CN 115011261A CN 202210730646 A CN202210730646 A CN 202210730646A CN 115011261 A CN115011261 A CN 115011261A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000013590 bulk material Substances 0.000 title claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 68
- 125000003277 amino group Chemical group 0.000 claims abstract description 44
- 150000005837 radical ions Chemical class 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011343 solid material Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 121
- 239000007787 solid Substances 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 239000006184 cosolvent Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017090 AlO 2 Inorganic materials 0.000 claims description 2
- 238000001599 direct drying Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 abstract description 98
- 239000012265 solid product Substances 0.000 abstract description 14
- 102000012422 Collagen Type I Human genes 0.000 abstract description 13
- 108010022452 Collagen Type I Proteins 0.000 abstract description 13
- 239000007767 bonding agent Substances 0.000 abstract description 7
- 229920002873 Polyethylenimine Polymers 0.000 abstract description 4
- 150000003949 imides Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- 229910004373 HOAc Inorganic materials 0.000 description 6
- 239000003752 hydrotrope Substances 0.000 description 6
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 108010022355 Fibroins Proteins 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920001184 polypeptide Polymers 0.000 description 4
- 102000004196 processed proteins & peptides Human genes 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 239000004115 Sodium Silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000008275 binding mechanism Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 sheets Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
-
- 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
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The application provides a method for bonding a bulk material by using an amino-containing insoluble polymer solution in the technical field of materials. Treating the amino-containing insoluble polymer (NH-R) such as chitosan, type I collagen, linear polyethyleneimine or imide to obtain polymer solution with amino group combined with weak acid radical ion, and dialyzing to remove impurities in the solution to obtain cosolvent-free NH-R solution. And soaking the NH-R solution into the body material to be bonded, or dripping the solution on the bonding surface of the body material to be bonded, removing the solvent in the solution and drying to complete the bonding of the body NH-R solid material. The solution only containing NH-R and solvent is used as the bonding agent of the NH-R bulk solid material, so that the bonding agent has the advantages of no introduction of extra materials and uniform components and properties of the whole bonded materials, can show excellent bonding effect when being bonded together, and the obtained NH-R solid product keeps original physical and chemical properties, such as water resistance and solvent resistance.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a method for bonding a bulk material by using an amino-containing insoluble polymer solution.
Background
The amino group-containing hardly soluble polymer (NH-R) is a polymer containing an amino group which is not directly dissolved by water or an organic solvent, and typically represents Chitosan (CS), type I collagen (COL-I), branched polyethyleneimine and polypeptide polymers, silk fibroin, polyamide, or the like. Among them, CS and COL-I are exemplified as natural polymers, which have excellent biocompatibility and can be applied to various fields such as medical treatment, food, beauty, health care, chemical industry, etc. Although CS and COL-I have huge application potential and excellent biological safety, products prepared from CS and COL-I materials are difficult to see in our lives. The main reason is that CS and COL-I molecules and molecules contain a large amount of hydrogen bonds which make the CS and COL-I molecules difficult to be dissolved and processed, and the addition of cosolvents such as acetic acid and the like can reduce the biocompatibility of the CS and COL-I and the solvent resistance after the solvent is removed. Therefore, the use of amino group-containing hardly soluble polymers such as CS and COL-I is limited to the solution obtainable only with a cosolvent. The chemical structure of CS is used for explaining the intermolecular and intramolecular hydrogen bond structures of the amino-containing insoluble polymer, and the chemical structure is as follows:
wherein the arrows indicate intermolecular and intramolecular hydrogen bonds of CS.
The method for preparing the NH-R solid product is based on the complex property, and the method for preparing the solid material product by bonding or compounding the NH-R in a solid state with a polymer solution is a common method for preparing the insoluble polymer solid material.
The high molecular species which can be used for bonding or compounding the NH-R solid material are abundant, and the solid material with abundant performance can be obtained by bonding or compounding NH-R by different high molecular materials. However, in actual production, solid products prepared from the same polymer material have more single and stable physicochemical properties, and are often more conducive to the production and application of the polymer material. Therefore, the bonding method is used for bonding the NH-R bulk solid material by using the solution only containing NH-R, so that the solid product only containing the same or the same type of high polymer material is obtained, and the popularization and the application of the NH-R type insoluble high polymer material are facilitated.
Because the commonly prepared NH-R solution contains a dissolving assistant which can dissolve NH-R solid, the commonly prepared NH-R solution containing the dissolving assistant can not be directly used for bonding or compounding NH-R. Therefore, at present, no invention patent about the NH-R solution for bonding the NH-R bulk material exists, and the invention patent is used for solving the problem that the NH-R material is bonded and a solid material containing only one NH-R is difficult to obtain.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for bonding a bulk material by using an amino-containing insoluble polymer solution, aiming at overcoming the problem that the use of the polymer material is influenced because a common NH-R solution containing a hydrotrope cannot be used for bonding or compounding NH-R due to the existence of the hydrotrope in the conventional preparation method of the amino-containing insoluble polymer.
One of the purposes of the invention is to dissolve an amino group-containing insoluble polymer by a dissolving aid, then add salt or acid consisting of weak acid radical ions to obtain a solution combining weak acid radical ions and amino groups in the amino group-containing insoluble polymer, remove impurities and only retain the amino group-containing insoluble polymer and a solvent to prepare an amino group-containing insoluble polymer solution, soak the amino group-containing insoluble polymer solution into a body material to be bonded or drip the amino group-containing insoluble polymer solution on a bonding surface of the body material to be bonded, remove the solvent in the solution and dry the solution to complete bonding of the body amino group-containing insoluble polymer solid material.
Further, the method for removing impurities is dialysis or extraction. In the extraction, a solvent which is insoluble in the solution but can dissolve NH-R is added to the solution of NH-R containing the hydrotrope, and the added solvent is also difficult to dissolve impurity components other than NH-R. The invention can remove over 99 percent of the cosolvent by means of extraction or dialysis.
Further, the cosolvent is an acid or an alkaline solution, when the cosolvent is an acid, the weak acid radical ions are different from the acid radical ions of the cosolvent, and the reaction activity of the weak acid radical ions is weaker than that of the acid radical ions.
Further, the cosolvent is formic acid, hydrochloric acid, acetic acid or a mixed solution containing sodium hydroxide. Further, the weak acidic radical ion is CO 3 2- 、HCO 3 - 、F-、ClO-、SiO 3 3- 、S 2- 、CN - 、SCN - 、NO 2 - 、SO 3 2- 、HPO 4 2- 、HS - 、AlO 2 - 、BrO - 、BO 3 3- Or one of the other acid ions.
The salt composed of weak acid radical ions is one of potassium borate, sodium silicate, ammonium borate, sodium sulfite, sodium hydrosulfide, ammonium carbonate, ammonium bicarbonate, sodium metaaluminate, sodium hypochlorite, magnesium bicarbonate, calcium bicarbonate or sodium hypochlorite, and the acid composed of weak acid radical ions is silicic acid, sulfurous acid, boric acid, hypochlorous acid or carbonic acid.
Further, the solid content of the amino group-containing hardly soluble polymer solution is less than 15%. The solid content is lower than 15 percent, and the bonding effect is best.
Further, the method specifically comprises the following steps: (1) dissolving an amino-containing insoluble polymer in a hydrotropy substance of an acid or alkaline solution;
(2) a, adding salt consisting of weak acid radical ions into an amino group-containing insoluble high molecular solution dissolved by acid serving as a dissolving aid, wherein the reaction capacity of the weak acid radical ions is weaker than that of acid radical ions of the dissolving aid, and cations containing the weak acid radical ions can be combined with the acid radical ions of the dissolving aid, so that the weak acid radical ions are combined with the amino group-containing insoluble high molecular solution and the solution state is kept; b. adding excessive weak acid composed of weak acid radical ions into an amino-containing insoluble high molecular solution dissolved in an alkaline solution as a cosolvent, wherein the weak acid can react with alkali to generate a salt with the weak acid radical ions, and in addition, the excessive weak acid is combined with the amino-containing insoluble high molecular solution to obtain a solution state in which the weak acid radical ions are combined with amino;
(3) removing impurities in the solution by dialysis or extraction to obtain a solution containing only the amino-containing insoluble polymer and the solvent without a cosolvent, namely the amino-containing insoluble polymer solution, and replacing the solvent in the amino-containing insoluble polymer solution by using organic solvents with different water contents to obtain amino-containing insoluble polymer solutions dissolved in different solvents;
(4) directly soaking the amino-containing insoluble polymer solution into the body material to be bonded, or dripping the amino-containing insoluble polymer solution on the bonding surface of the body material to be bonded, adjusting the bonded material into a required shape, removing the solvent, and directly drying to obtain a solid amino-containing insoluble polymer solution, thus completing the purpose of bonding the solid material of the body.
Further, the amino-containing insoluble polymer package is chitosan, type I collagen, linear polyethyleneimine or polypeptide polymer, silk fibroin, or polyamide. The salt or acid containing weak acid radical selected for different amino group-containing insoluble polymers cannot be used as a dissolving aid of the corresponding amino group-containing insoluble polymers, and also has the property of directly dissolving the amino group-containing insoluble polymers, for example, acetic acid can dissolve chitosan, and acetate cannot be selected to be used as salt or acid containing weak acid radical.
The working principle and the beneficial effects of the invention are as follows: because NH-R can not be directly dissolved by water or organic solvent to obtain solution, the invention firstly obtains solution of weak acid radical ions and amino groups of indissoluble macromolecules containing amino groups, and then removes the weak acid radical ions and other impurities in the solution by dialysis and the like to obtain the NH-R solution without hydrotropy matters. Note: by adjusting the anion component in the dialysate, a solution in which the anion is bonded to the amino group of NH-R can be obtained. By adjusting the solvent in the dialysate, NH-R solutions dissolved in different solvents can be obtained.
The NH-R solution without the cosolvent can fully ensure the original properties of the insoluble macromolecules containing the amino groups, and is suitable for the use scene of liquid materials. The liquid CS material can fully exert the molecular structure, and the antibacterial effect of the CS material is far beyond the solid state; and the NH-R solution can keep good biocompatibility without the aid of acetic acid and other solubilizing substances, so that the problem that the NH-R solution is difficult to use as a biomedical material can be solved.
The NH-R solution without the cosolvent can be recovered to be in a difficult-to-dissolve high molecular state after the solvent is removed, which is beneficial to the preparation of an NH-R solid product, but the NH-R liquid material in the prior art needs the existence of the cosolvent, so the NH-R solution still contains the cosolvent when being prepared to be in a solid state (containing a hydrogel state), the material can be dissolved in water or an organic solvent, the characteristic is not beneficial to the preparation of the solid product, the NH-R solution does not contain the cosolvent, the physical and chemical properties of the NH-R material can not be changed, and the prepared NH-R solution can still recover the property of being difficult to dissolve in water or the organic solvent after being in the solid state, and the NH-R solution is one of the advantages of the high molecular solution prepared by the invention.
The invention designs an amino group-containing insoluble polymer solution without a dissolving aid, and can solve the problem that the amino group-containing insoluble polymer solution can be obtained only by degrading the molecular weight of the amino group-containing insoluble polymer or depending on the dissolving aid. The amino-containing polymer solution without the cosolvent is favorable for solving the problem of difficult characterization of the substances, and is favorable for keeping the original properties of the polymer unaffected by the cosolvent.
The preparation of a solution of NH-R without hydrotrope is illustrated by way of example with CS. The invention firstly dissolves CS by a traditional method, comprising that CS is dissolved by an acid solution and a mixed solution containing alkali as a dissolving aid. Then, a CS solution containing a hydrotrope in the conventional form is obtained, and a salt having weak acid ion is added to the CS solution in which an acidic solution is used as the hydrotrope. The cation reaction capacity of the salt is stronger than that of the amino group of CS, and the reaction capacity of the weak acid radical ion is weaker than that of the anion formed by combining the acidic solution as a cosolvent and the amino group of CS. The CS solution containing the cosolvent is subjected to salt treatment to obtain a solution in which weak acid radical ions are combined with amino groups in NH-R, and the weak acid radical ions and other impurities can be removed through pure water dialysis. Dialyzing and purifying to obtain the amino-containing insoluble polymer solution without hydrotropy matters. The dialysate is replaced by other organic solvent to obtain the amino group-containing insoluble polymer solution dissolved by the organic solvent.
The NH-R solution after the impurities are removed only contains NH-R and solvent, does not contain dissolving-aid substances, and does not dissolve the NH-R bulk solid. Therefore, the NH-R solution can be bonded without changing the physical state of the bonded NH-R, and the bonded product containing only NH-R solids can be obtained by drying and removing the solvent.
The solution only containing NH-R and solvent is used as the bonding agent of the NH-R bulk solid material, so that the bonding agent has the advantages of no introduction of extra materials and uniform overall components and properties of the bonded materials. The same material is used as the NH-R adhesive, the chemical components are the same, the affinity between the liquid and the adhered solid is good, the acting force is strong, and the NH-R adhesive has good adhesion effect. The pure NH-R material can be obtained after the solvent is removed and dried, the same material has good affinity, and the excellent bonding effect can be shown when the materials are bonded together.
The NH-R solution is used for bonding the NH-R body solid, and parameters such as the using amount and solid content of the solid NH-R can be adjusted according to the requirements of density, a gap structure, mechanical properties and the like required by the bonded solid product, so that the bonded solid product is simpler and more controllable in molding. The solid content of the NH-R solution can be adjusted according to the increase and decrease of the solvent in the solution.
The NH-R solution can be used for bonding solid NH-R in different states, such as particles, fibers, sheets, layers and the like, so as to achieve different use effects. NH-R solid products with different morphologies can also be obtained by a bonding method.
Further, the direct drying method after removing the solvent includes drying by natural drying, heat drying, freeze drying or organic solvent treatment. After the NH-R solution is bonded with the bulk material and dried, the obtained NH-R solid product keeps the original physical and chemical properties, such as water resistance and solvent resistance.
The solid product obtained by bonding the NH-R solution with the body material is beneficial to the processing and preparation of the indissolvable high polymer material and the popularization and the application of the NH-R solid product with uniform chemical components.
The invention also aims to use the amino-containing insoluble polymer solution prepared by the method for bonding non-bulk solid materials. The NH-R solution can be used as a bonding agent for a bulk material and can also be used for bonding non-bulk materials.
Drawings
FIG. 1 is a schematic flow diagram of a bonding method of the present invention;
FIG. 2 is a graph showing the residual rate of solid CS in examples 1 to 3 after being soaked in the CS solution and left standing for 72 hours;
FIG. 3 is a graph showing the mass residue rate of the bonded CS solid in examples 1 to 3 after being soaked in water, ethanol and chloroform for 24 hours;
FIG. 4 is a graph showing tensile strength and elongation tests of the bonded solid CS of examples 1-3.
Detailed Description
The following is further detailed by way of specific embodiments:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments. It should be noted that all of these examples are intended to further illustrate the present invention and should not be construed as limiting the present invention. The invention is not limited to the above embodiments, but may be modified and modified within the scope of the invention.
Table 1 is a list of preparation conditions of the amino group-containing hardly soluble polymer solution of the present invention
It should be noted that: the molar parts of CS put in Table 1 refer to the molar parts of its repeating units, that is, the molar parts of nitrogen element in CS.
Preparation examples 1 to 18, CS is a typical example of a sparingly water-soluble polymer containing amino groups, and the present invention is directed to a sparingly water-soluble polymer containing amino groups as CS, and a method for bonding a bulk material with a sparingly water-soluble polymer containing amino groups in a solution.
The invention firstly dissolves CS by acid solution or alkali mixture, and then obtains solution combining weak acid radical ions and CS amino by chemical reaction.
The most common solution of CS in aqueous acetic acid (HOAc) is described here, by first dropwise adding 0.7mmol of 1% acetic acid to 1mmol of CS starting material (CS-starting material) under stirring, and stirring at 20 deg.C for 4h until the CS-starting material is completely dissolved. At this time, the aqueous solution of HOAc acted on the amino groups on the CS to break the hydrogen bonds in and between the CS molecules, and the resulting solution was CS-HOAc. 0.73mmol of ammonium bicarbonate (NH) is dropwise added into the CS-HOAc solution in a stirring state 4 HCO 3 ) Aqueous solution, NH 4 HCO 3 The activity of the ammonium group of (a) is higher than that of the amino group on the CS, so that the acetic acid bound with the CS can be replaced; and the hydrolyzed bicarbonate and carbonate components can be combined with CS to maintain a stable solution state. NH is added after dropwise addition 4 HCO 3 Then, the reaction is carried out for 2 hours at the temperature of 5-80 ℃. HOAc and NH during the whole reaction process 4 HCO 3 The molar amount of (c) can vary. Excess bicarbonate and carbonate in the ammonium bicarbonate will be replaced by CO 2 The gas is released. HOAc and NH 4 HCO 3 Ammonium groups are combined to form ammonium acetate impurities, and the ammonium acetate impurities are purified by extraction or dialysis and other modes to obtain a CS water solution only containing CS and water.
The CS aqueous solution is obtained by combining bicarbonate or carbonate with CS and then purifying, and the chemical flow of the whole process is as follows:
wherein, the ammonium bicarbonate represents salt containing weak acid radical ions, and can be replaced by other salts with similar functions.
Preparation examples 19 to 23, except for CS, solutions of NH-R (e.g., type I collagen, linear polyethyleneimine, polypeptide polymer, silk fibroin, polyamide, etc.) were prepared in a similar manner to the preparation of CS solutions, by combining an amino group-containing insoluble polymer with weak acid radical ions, and then removing impurities by dialysis or extraction, etc., to obtain an aqueous solution of NH-R.
For example, CS stands for NH-R, and CS solution is used as a binder, so that the binding mechanism is the same for solid CS in different states. In addition, the CS bulk solid bonded by the CS solution is dried after the solvent in the solution is removed in any way, and the chemical components of the high polymer material are not changed by the drying way under the condition that the chemical structural formula of the CS is not damaged. Therefore, the emphasis is given here to the case where only the CS solution is used to bond the granular CS, and then the molded CS solid product is dried after heating to remove the solvent.
Examples 1 to 11
The flow of the bonding method of the present invention is schematically shown in FIG. 1. For examples 1-3, the same was done for bonding granular CS bodies at room temperature with CS aqueous solutions of different CS solids content as the bonding agent. Taking example 1 as an example, 0.95g of granular CS and 2.5g of an aqueous CS solution having a CS solid content of 2% were mixed and subjected to a defoaming treatment. And then placing the sample mixed with the CS aqueous solution and the bulk into a mold to be prepared and molded, heating at 30-100 ℃ to release the water in the CS aqueous solution until the water is completely released, and finishing the mixture into a CS solid. The bonded CS solid is prepared into a water-resistant and solvent-resistant solid material with a required shape.
The bonding principle of the CS solution as solid CS with different morphologies is the same, and the way of removing the solvent from the CS solution does not change the chemical properties of CS, and there is no essential difference, so the bonding process of examples 4-6 is consistent with the method described in example 1.
For the non-CS NH-R solution as a binder for bulk solids in examples 7-11, the bonding principle and manner are consistent with the bonding of CS bulk solids with CS solution, and therefore, will not be described in detail.
Table 2 shows a list of bonding conditions of the present invention
FIG. 2 is a graph showing the residual ratio of solid CS in examples 1 to 3, in which 10g of the CS solution and 1g of the granular solid CS were mixed at room temperature and left standing for 72 hours, the granular solid CS was washed and dried with pure water, and then the change in mass of the solid CS before and after mixing was compared by weighing. As can be seen from the data of examples 1 to 3, the binder CS solution does not affect the quality of the solid CS, i.e., does not dissolve the solid CS. Therefore, the CS solution does not influence the physical appearance and chemical properties of the bonded solid CS, and can be used as a bonding agent of the solid CS.
As shown in fig. 3, after CS was bonded with the CS solution and dried, 1g of the bonded solid CS was subjected to 100mL of water, ethanol or chloroform solvent and immersed at room temperature for 24 hours, and almost no mass loss of the bonded CS solid was observed. The solid CS obtained after the CS solution bonding bulk material is dried still maintains the good water resistance and solvent resistance of the CS material.
In conclusion, it can be shown that the NH-R solution does not dissolve solid NH-R and can be used as a binder for solid NH-R, and the dried bonded solid product retains the properties of the solid NH-R itself.
Application example 1
As shown in fig. 4, in examples 1 to 3, the CS materials after bonding and drying all had tensile strengths of more than 20MPa and elongations of more than 5%, and the higher the solid content of the CS solution used for bonding, the greater the tensile strength and elongation of the CS solid after bonding. Compared with the granular solid CS before bonding, the solid CS obtained by bonding the CS solution has no tensile strength and elongation and has good mechanical property. Therefore, the method for bonding the bulk material by using the amino-containing insoluble polymer (NH-R) solution can be used for forming solid NH-R and endowing the bonded solid material with mechanical property. The method for obtaining NH-R by bonding does not change the chemical property of NH-R, and NH-R materials such as chitosan, type I collagen, polypeptide polymers, silk fibroin, polyamide and the like are widely applied to the chemical and medical fields, so the bonded and formed NH-R material is still suitable for the original application fields of various materials.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (8)
1. A method for bonding a bulk material by using an amino-containing insoluble polymer solution is characterized by comprising the following steps: dissolving the amino-containing insoluble polymer by using a dissolving aid, then adding salt or acid consisting of weak acid ions to obtain a solution combining the weak acid ions and amino groups in the amino-containing insoluble polymer, removing impurities, only retaining the amino-containing insoluble polymer and a solvent to prepare an amino-containing insoluble polymer solution, infiltrating the amino-containing insoluble polymer solution into a body material to be bonded, or dripping the amino-containing insoluble polymer solution on a bonding surface of the body material to be bonded, removing the solvent in the solution and drying to complete bonding of the solid amino-containing insoluble polymer material of the body.
2. The method of claim 1, wherein: the method for removing impurities is dialysis or extraction.
3. The method of claim 2, wherein: the cosolvent is an acid or an alkaline solution, when the cosolvent is an acid, the weak acid radical ions are different from the acid radical ions of the cosolvent, and the reaction activity of the weak acid radical ions is weaker than that of the acid radical ions.
4. The method of claim 3, wherein: the cosolvent is formic acid, hydrochloric acid, acetic acid or mixed solution containing sodium hydroxide.
5. The method of claim 4, wherein: weak acid radical ion is CO 3 2- 、HCO 3 - 、F - 、ClO - 、SiO 3 3- 、S 2- 、CN - 、SCN - 、NO 2 - 、SO 3 2- 、HPO 4 2- 、HS - 、AlO 2 - 、BrO - 、BO 3 3- Or one of other acid ions.
6. The method of claim 5, wherein: the method specifically comprises the following steps: (1) dissolving an amino-containing insoluble polymer in a hydrotropy substance of an acid or alkaline solution;
(2) a, adding salt consisting of weak acid radical ions into an amino group-containing insoluble high molecular solution dissolved by acid serving as a dissolving aid, wherein the reaction capacity of the weak acid radical ions is weaker than that of acid radical ions of the dissolving aid, and cations containing the weak acid radical ions can be combined with the acid radical ions of the dissolving aid, so that the weak acid radical ions are combined with the amino group-containing insoluble high molecular solution and the solution state is kept; b. adding excessive weak acid consisting of weak acid radical ions into an amino-containing insoluble polymer solution dissolved by using an alkaline solution as a cosolvent, wherein the weak acid can react with alkali to generate salt with the weak acid radical ions, and in addition, the excessive weak acid is combined with the amino-containing insoluble polymer to obtain a solution state in which the weak acid radical ions are combined with amino;
(3) removing impurities in the solution by dialysis or extraction to obtain a solution containing only the amino group-containing insoluble polymer and the solvent without a cosolvent, namely the amino group-containing insoluble polymer solution, and replacing the solvent in the amino group-containing insoluble polymer solution by using organic solvents with different water contents to obtain amino group-containing insoluble polymer solutions dissolved in different solvents;
(4) directly soaking the amino-containing insoluble polymer solution into the body material to be bonded, or dripping the amino-containing insoluble polymer solution on the bonding surface of the body material to be bonded, adjusting the bonded material into a required shape, removing the solvent, and directly drying to obtain a solid amino-containing insoluble polymer solution, thus completing the purpose of bonding the solid material of the body.
7. The method of claim 6, wherein: the direct drying method after removing the solvent comprises drying by natural drying, heating drying, freeze drying or organic solvent treatment.
8. Use of a solution of a poorly soluble polymer containing amino groups prepared by the process of any one of claims 1 to 7 for the bonding of non-bulk solid materials.
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| CN103249792A (en) * | 2010-07-16 | 2013-08-14 | 环境与农业科学技术国家研究所 | Adhesive composition including deacetylated chitosan |
| CN104789159A (en) * | 2014-01-17 | 2015-07-22 | 曲阜天博晶碳科技有限公司 | Preparation method of chitosan binder for formed activated carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103249792A (en) * | 2010-07-16 | 2013-08-14 | 环境与农业科学技术国家研究所 | Adhesive composition including deacetylated chitosan |
| CN104789159A (en) * | 2014-01-17 | 2015-07-22 | 曲阜天博晶碳科技有限公司 | Preparation method of chitosan binder for formed activated carbon |
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| Title |
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| 吴克刚, 中国轻工业出版社, pages: 143 * |
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