CN120248277B - A degradable resin and preparation method - Google Patents
A degradable resin and preparation methodInfo
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- CN120248277B CN120248277B CN202510740953.XA CN202510740953A CN120248277B CN 120248277 B CN120248277 B CN 120248277B CN 202510740953 A CN202510740953 A CN 202510740953A CN 120248277 B CN120248277 B CN 120248277B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及聚氨酯树脂技术领域，且公开了一种可降解树脂和制备方法，本发明的可降解树脂包括100重量份聚乳酸二元醇、24‑35重量份二异氰酸酯单体、4‑16重量份改性纤维素等。纤维素本身就具有良好的生物降解性能，同时改性纤维素含有大量的可生物降解的酯基，进一步提高了聚氨酯树脂的生物降解率，并且改性纤维素含有大量的亲水性磺酸阴离子和季铵盐阳离子，赋予了聚氨酯树脂很好的亲水吸水性，促进了聚氨酯树脂中聚乳酸分子链，以及纤维素酯基的水解，从而提高了树脂的水解失重率，表现出优异的降解性能。The present invention relates to the technical field of polyurethane resins and discloses a degradable resin and a preparation method. The degradable resin of the present invention comprises 100 parts by weight of polylactic acid diol, 24-35 parts by weight of diisocyanate monomer, 4-16 parts by weight of modified cellulose, etc. Cellulose itself has good biodegradability. At the same time, the modified cellulose contains a large number of biodegradable ester groups, which further improves the biodegradability of the polyurethane resin. The modified cellulose also contains a large number of hydrophilic sulfonic acid anions and quaternary ammonium salt cations, which endow the polyurethane resin with good hydrophilic water absorption, promote the hydrolysis of polylactic acid molecular chains and cellulose ester groups in the polyurethane resin, thereby improving the hydrolysis weight loss rate of the resin and showing excellent degradation performance.
Description
Technical Field
The invention relates to the technical field of polyurethane resin, in particular to degradable resin and a preparation method thereof.
Background
Polyurethane is a high molecular resin with excellent performance, high mechanical strength, high toughness and good heat resistance, and is widely applied to the aspects of paint, heat insulation materials, medical supplies, disposable sanitary nursing supplies and the like. The polyurethane prepared from polylactic acid dihydric alcohol, polyester polyol and the like as raw materials has good biodegradability, is environment-friendly, has little pollution, accords with the green chemistry concept, and has wide application prospect.
The performances such as degradability and the like of the polyurethane can be improved by adding biomass resources such as cellulose and the like into the polyurethane. Cellulose is cheap and easy to obtain, can be biodegraded, contains a large amount of active hydroxyl groups, and can react with reagents such as 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, chlorosulfonic acid and the like to generate cationic cellulose, sulfonated cellulose and the like. And the cellulose can also react with diisocyanate, acrylic ester and other pre-polymerized monomers to prepare polyurethane, acrylic resin, polylactic acid and other composite materials. The Chinese patent with publication number of CN106947051B discloses a polyurethane grafted cellulose nanocrystal and a preparation method thereof, and polyurethane chains are grafted on the surface of the cellulose nanocrystal, so that the problems of poor dispersibility of the cellulose nanocrystal in an organic solvent and a high polymer matrix and the like are solved, but the problem of poor biodegradability and hydrolyzability of a cellulose polyurethane composite material is not solved in the patent.
Disclosure of Invention
The invention provides a degradable resin and a preparation method thereof, which solve the problems of poor biodegradation and hydrolysis performance of polyurethane resin.
The technical scheme is that the degradable resin comprises 100 parts by weight of polylactic acid dihydric alcohol, 24-35 parts by weight of diisocyanate monomer, 2.1-3.3 parts by weight of glycol chain extender, 4-16 parts by weight of modified cellulose and 0.1-0.16 part by weight of organotin catalyst. The preparation method of the degradable resin comprises the following steps:
(1) Adding cellulose, a modifier and 4-dimethylaminopyridine into tetrahydrofuran, heating and stirring, cooling in ice water bath, adding dicyclohexylcarbodiimide, concentrating the solution under reduced pressure after reaction, washing with ethanol, and drying to obtain modified cellulose. The reaction formula is:
。
(2) Mixing the dried polylactic acid dihydric alcohol, diisocyanate monomer and organic tin catalyst, reacting for 2-3 hours in the nitrogen atmosphere at 70-80 ℃, then adding glycol chain extender, modified cellulose and acetone solvent, reducing the temperature to 40-50 ℃, reacting for 1-2 hours, removing the acetone solvent, and drying to obtain the degradable resin.
Further, the diisocyanate monomer includes isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, or diphenylmethane diisocyanate.
Further, the glycol chain extender includes ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, or diethylene glycol.
Further, the organotin catalyst is dibutyltin dilaurate.
Further, the amount of cellulose in (1) is 100 parts by weight, the modifier is 40 to 120 parts by weight, 4-dimethylaminopyridine is 12 to 40 parts by weight, and dicyclohexylcarbodiimide is 28 to 86 parts by weight.
Further, the reaction in (1) is stirred at 15-40℃for 18-36h.
Further, the preparation method of the modifier comprises the steps of adding 54-80 parts by weight of succinic anhydride, 100 parts by weight of hydroxyethyl betaine and 3-6 parts by weight of pyridine into toluene, heating to 70-90 ℃, stirring for reaction for 18-24 hours, concentrating under reduced pressure, washing a product with acetone, and then recrystallizing and purifying in water to obtain the modifier. The reaction formula is:
。
the invention has the beneficial technical effects that the carboxyl of the modifier and the hydroxyl of the cellulose are utilized to carry out esterification reaction to obtain the modified cellulose, so that a plurality of ester groups, sulfonic acid anions and quaternary ammonium salt cations are introduced into a cellulose matrix.
According to the invention, polylactic acid dihydric alcohol and diisocyanate monomers are used as polymerization monomers, modified cellulose is added during polyurethane chain extension reaction, the cellulose has good biodegradability, meanwhile, the modified cellulose contains a large amount of biodegradable ester groups, the biodegradation rate of polyurethane resin is further improved, the modified cellulose contains a large amount of hydrophilic sulfonic acid anions and quaternary ammonium salt cations, the polyurethane resin is endowed with good hydrophilic water absorption, polylactic acid molecular chains in the polyurethane resin and hydrolysis of cellulose ester groups are promoted, so that the hydrolysis weight loss rate of the resin is improved, and excellent degradation performance is shown.
Detailed Description
In order to make the technical solution of the present invention more clear, the following description will clearly and completely describe the technical solution of the embodiments of the present invention, and it should be noted that the following embodiments are only used for better understanding the technical solution of the present invention, and should not be construed as limiting the present invention.
Cellulose model TL-003, purchased from nanjing tianlu nanotechnology limited. The sulfonated modified cellulose has the model number TL-005 and is purchased from Nanjing Tianlu nano technology Co. Cationic cellulose, available from North Xinjie Chemie, inc. of Hubei.
The preparation method of the hydroxyethyl betaine according to the periodical J.chem.Sci.volume 128, pages 1277-1284 (2016), the preparation method of the literature "Functionalized dicationic ionic liquids: Green and efficient alternativesfor catalysts in phthalate plasticizers preparation" comprises the steps of adding 100mmol of N, N-dimethylethanolamine into 120mL of toluene, dropwise adding 100mmol of 1, 4-butanesultone into 0 ℃ after stirring, heating to 110 ℃, condensing and refluxing for 12 hours, filtering, washing the precipitate with diethyl ether, and drying to obtain the hydroxyethyl betaine with the structural formula。
Example 1
(1) 5.4G of succinic anhydride, 10g of hydroxyethyl betaine and 0.6g of pyridine are added into 150mL of toluene, the mixture is heated to 70 ℃, stirred and reacted for 24 hours, concentrated under reduced pressure, and the product is washed by acetone and then recrystallized and purified in water to obtain the modifier.
(2) 30G of cellulose, 12g of modifier and 3.6g of 4-dimethylaminopyridine are added into 2L of tetrahydrofuran, the mixture is heated and stirred, then cooled in an ice water bath, 8.4g of dicyclohexylcarbodiimide is added, the mixture is stirred and reacted for 18 hours at 20 ℃, the solution is concentrated under reduced pressure, washed by ethanol and dried, and the modified cellulose is obtained.
(3) 500G of dried polylactic acid dihydric alcohol 2000, 154g of isophorone diisocyanate and 0.6g of dibutyltin dilaurate are mixed and reacted for 2 hours in a nitrogen atmosphere at 80 ℃, then 16.5g of chain extender 1, 4-butanediol, 20g of modified cellulose and 0.9L of acetone solvent are added, the temperature is reduced to 45 ℃, the reaction is carried out for 1 hour, the acetone solvent is removed, and the degradable resin is obtained after drying.
Example 2
(1) To 200mL of toluene, 8g of succinic anhydride, 10g of hydroxyethyl betaine and 0.3g of pyridine were added, the mixture was heated to 90 ℃, stirred and reacted for 18 hours, concentrated under reduced pressure, and the product was washed with acetone, and then recrystallized and purified in water to obtain a modifier.
(2) 30G of cellulose, 20g of modifier and 6g of 4-dimethylaminopyridine are added into 2L of tetrahydrofuran, the mixture is heated and stirred, then cooled in an ice water bath, 14g of dicyclohexylcarbodiimide is added, the mixture is stirred and reacted for 36 hours at 15 ℃, the solution is concentrated under reduced pressure, washed by ethanol and dried, and the modified cellulose is obtained.
(3) 500G of dried polylactic acid dihydric alcohol 2000, 175g of diphenylmethane diisocyanate and 0.6g of dibutyltin dilaurate are mixed and reacted for 3 hours in a nitrogen atmosphere at 70 ℃, then 14.6g of chain extender 1, 6-hexanediol, 40g of modified cellulose and 1L of acetone solvent are added, the temperature is reduced to 40 ℃, the reaction is carried out for 2 hours, the acetone solvent is removed, and the degradable resin is obtained after drying.
Example 3
(1) The modifier was prepared as in example 1.
(2) 30G of cellulose, 28g of modifier and 9.3g of 4-dimethylaminopyridine are added into 2.5L of tetrahydrofuran, the mixture is heated and stirred, cooled in an ice water bath, 19.5g of dicyclohexylcarbodiimide is added, the mixture is stirred and reacted for 18 hours at 40 ℃, and the solution is decompressed and concentrated, washed by ethanol and dried to obtain the modified cellulose.
(3) 500G of dried polylactic acid dihydric alcohol 2000, 137g of toluene diisocyanate and 0.5g of dibutyltin dilaurate are mixed and reacted for 2 hours in a nitrogen atmosphere at 80 ℃, then 12.8g of chain extender diethylene glycol, 50g of modified cellulose and 1L of acetone solvent are added, the temperature is reduced to 50 ℃, the reaction is carried out for 1 hour, the acetone solvent is removed, and the degradable resin is obtained after drying.
Example 4
(1) The modifier was prepared as in example 1.
(2) 30G of cellulose, 36g of modifier and 12g of 4-dimethylaminopyridine are added into 2.5L of tetrahydrofuran, the mixture is heated and stirred, then cooled in an ice water bath, 25.8g of dicyclohexylcarbodiimide is added, the mixture is stirred and reacted for 36 hours at 30 ℃, and the solution is decompressed and concentrated, washed by ethanol and dried to obtain the modified cellulose.
(3) 500G of dried polylactic acid dihydric alcohol 2000, 120g of hexamethylene diisocyanate and 0.8g of dibutyltin dilaurate are mixed and reacted for 3 hours in a nitrogen atmosphere at the temperature of 75 ℃, then 10.5g of chain extender glycol, 80g of modified cellulose and 1L of acetone solvent are added, the temperature is reduced to 50 ℃, the acetone solvent is removed after the reaction for 1 hour, and the degradable resin is obtained after drying.
Comparative example 1
(1) 500G of dried polylactic acid dihydric alcohol 2000, 154g of isophorone diisocyanate and 0.6g of dibutyltin dilaurate are mixed and reacted for 2 hours in a nitrogen atmosphere at 80 ℃, then 16.5g of chain extender 1, 4-butanediol, 20g of cellulose and 0.9L of acetone solvent are added, the temperature is reduced to 45 ℃, the reaction is carried out for 1 hour, the acetone solvent is removed, and the degradable resin is obtained after drying.
Comparative example 2
(1) To 2L of tetrahydrofuran was added 30g of cellulose and 12g of monoethyl succinate (structural formula) 3.6G of 4-dimethylaminopyridine, heating and stirring, cooling in an ice water bath, adding 8.4g of dicyclohexylcarbodiimide, stirring and reacting for 18h at 20 ℃, concentrating the solution under reduced pressure, washing with ethanol, and drying to obtain the modified cellulose.
(2) 500G of dried polylactic acid dihydric alcohol 2000, 154g of isophorone diisocyanate and 0.6g of dibutyltin dilaurate are mixed and reacted for 2 hours in a nitrogen atmosphere at 80 ℃, then 16.5g of chain extender 1, 4-butanediol, 20g of modified cellulose and 0.9L of acetone solvent are added, the temperature is reduced to 45 ℃, the reaction is carried out for 1 hour, the acetone solvent is removed, and the degradable resin is obtained after drying.
Comparative example 3
(1) 500G of dried polylactic acid dihydric alcohol 2000, 154g of isophorone diisocyanate and 0.6g of dibutyltin dilaurate are mixed and reacted for 2 hours in a nitrogen atmosphere at 80 ℃, then 16.5g of chain extender 1, 4-butanediol, 20g of sulfonated modified cellulose and 0.9L of acetone solvent are added, the temperature is reduced to 45 ℃, the reaction is carried out for 1 hour, the acetone solvent is removed, and the degradable resin is obtained after drying.
Comparative example 4
(1) 500G of dried polylactic acid dihydric alcohol 2000, 154g of isophorone diisocyanate and 0.6g of dibutyltin dilaurate are mixed and reacted for 2 hours in a nitrogen atmosphere at 80 ℃, then 16.5g of chain extender 1, 4-butanediol, 20g of cationic cellulose and 0.9L of acetone solvent are added, the temperature is reduced to 45 ℃, the reaction is carried out for 1 hour, the acetone solvent is removed, and the degradable resin is obtained after drying.
The biodegradability and the biodegradation rate of the polyurethane resin are tested according to GB/T19277.2-2013 standard, and the test time is 30 days.
The polyurethane resin was weighed, added to deionized water, heated to 80 ℃, kept for 7 days, taken out of the polyurethane resin, washed with water, dried, weighed, and the hydrolysis weight loss ratio W, w= (m 0-m）/m0×100%.m0 is the mass before hydrolysis and m is the mass after hydrolysis, was calculated.
The tensile strength of the polyurethane resin was tested according to GB/T1040.1-2018 standard.
TABLE 1 degradation Properties of polyurethane resin
The 30-day biodegradation rate of the polyurethane resin of the examples 1-4 reaches 58.7-66.4%, the hydrolysis weight loss rate reaches 24.7-43.8%, and the polyurethane resin shows good biodegradability and hydrolytic performance mainly because the modified cellulose is added during the chain extension reaction, the cellulose has good biodegradability, and meanwhile, the modified cellulose contains a large amount of biodegradable ester groups, so that the biodegradation rate of the polyurethane resin is further improved, and the modified cellulose contains a large amount of hydrophilic sulfonic acid anions and quaternary ammonium salt cations, so that the polyurethane resin is endowed with good hydrophilic water absorption, the polylactic acid molecular chain in the polyurethane resin and the hydrolysis of cellulose ester groups are promoted, and the hydrolysis weight loss rate is further improved.
The cellulose of comparative example 1 does not contain a biodegradable ester group nor a hydrophilic sulfonate anion and a quaternary ammonium salt cation, resulting in lower biodegradation rate and hydrolysis weight loss rate of the polyurethane resin, the modified cellulose obtained by esterification of monoethyl succinate of comparative example 2 with cellulose also does not contain a hydrophilic sulfonate anion and a quaternary ammonium salt cation, resulting in lower hydrolysis weight loss rate of the polyurethane resin, the sulfonated modified cellulose of comparative example 3 does not contain a biodegradable ester group and a hydrophilic quaternary ammonium salt cation, and the cationic cellulose of comparative example 4 does not contain a biodegradable ester group and a hydrophilic sulfonate anion, resulting in lower biodegradation rate and hydrolysis weight loss rate of both.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present application should be included in the present application.
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| CN106675389A (en) * | 2016-12-16 | 2017-05-17 | 安徽荣玖智能装备科技有限公司 | Aluminum sol composite polyimide powder paint and preparation method thereof |
| CN112226216A (en) * | 2020-11-23 | 2021-01-15 | 扬州工业职业技术学院 | High-efficiency petroleum drilling fluid and preparation method thereof |
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| US5134035A (en) * | 1990-06-25 | 1992-07-28 | Minnesota Mining And Manufacturing Company | Magnetic recording medium containing a polyurethane copolymer with a free radically polymerized polymer segment grafted to the polyurethane through a sulfur atom |
| CA2761675A1 (en) * | 2009-05-11 | 2010-11-18 | Biomatrica, Inc. | Compositions and methods for biological sample storage |
| CN116606425B (en) * | 2023-05-05 | 2023-11-14 | 常熟威怡科技有限公司 | Cellulose antibacterial modified polylactic acid material and preparation method thereof |
| CN119639330B (en) * | 2025-02-18 | 2025-06-13 | 平原县农村公路发展中心 | A preparation process of waterproof coating for roads and bridges |
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| CN106675389A (en) * | 2016-12-16 | 2017-05-17 | 安徽荣玖智能装备科技有限公司 | Aluminum sol composite polyimide powder paint and preparation method thereof |
| CN112226216A (en) * | 2020-11-23 | 2021-01-15 | 扬州工业职业技术学院 | High-efficiency petroleum drilling fluid and preparation method thereof |
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