CN111732805A - Chitosan-doped polyester material and preparation method thereof - Google Patents
Chitosan-doped polyester material and preparation method thereof Download PDFInfo
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- CN111732805A CN111732805A CN202010602271.XA CN202010602271A CN111732805A CN 111732805 A CN111732805 A CN 111732805A CN 202010602271 A CN202010602271 A CN 202010602271A CN 111732805 A CN111732805 A CN 111732805A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- Polymers & Plastics (AREA)
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- Materials Engineering (AREA)
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Abstract
The invention discloses a chitosan-doped polyester material which is prepared from the following raw materials in parts by weight: the invention adopts chitosan as reinforcing agent, which not only has good heat preservation performance, but also has light weight and can improve the quality of finished products.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a chitosan-doped polyester material and a preparation method thereof.
Background
The polymethyl methacrylate has excellent weather resistance, higher surface hardness and surface gloss, better high-temperature performance and good processability, and can be subjected to thermoforming or machining; however, polymethyl methacrylate has no ultraviolet-proof function, so that the polymethyl methacrylate has short outdoor service life, is not suitable for being used as a material of an outdoor identification product, is only suitable for being used as indoor products such as crystal words or product supports and the like, and is gradually faded in color and easy to embrittle until being cracked; therefore, the invention aims to provide the polymethyl methacrylate resin with good ultraviolet resistance and high stability so as to expand the application of the polymethyl methacrylate resin in the outdoor field and prolong the service life of the polymethyl methacrylate resin.
Disclosure of Invention
The invention aims to provide a chitosan-doped polyester material and a preparation method thereof aiming at the defects and shortcomings of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chitosan-doped polyester material is prepared from the following raw materials in parts by weight:
200-240 chitosan modified monomer, 3-5 initiator, 4-7 diethylene glycol dibenzoate, 10-15 bisphenol A phosphite ester and 1-2 tributyltin trichloride.
The chitosan modified monomer is prepared from the following raw materials in parts by weight:
10-18 parts of chitosan, 100-130 parts of methyl methacrylate, 0.1-0.14 part of acid binding agent, 30-40 parts of thionyl chloride, 10-13 parts of ricinoleic acid, 20-30 parts of dimethylformamide and 1-3 parts of diacetone acrylamide.
The acid-binding agent is pyridine.
The initiator is dicumyl peroxide.
The preparation method of the chitosan modified monomer comprises the following steps:
(1) mixing ricinoleic acid and methyl methacrylate, adding into dimethylformamide, heating to 50-55 deg.C, stirring for 1-2 hr to obtain methyl methacrylate dispersion;
(2) mixing the methyl methacrylate dispersion with thionyl chloride, feeding the mixture into a constant-temperature water bath at the temperature of 65-75 ℃, preserving the temperature, stirring for 20-25 hours, and performing rotary evaporation to remove dimethylformamide and thionyl chloride to obtain acyl chloride methyl methacrylate;
(3) mixing chitosan and diacetone acrylamide, adding into deionized water 4-7 times of the weight of the mixture, performing ultrasonic treatment for 10-20 minutes, sending into a drying oven, drying at 70-80 deg.C for 3-5 hours, discharging, and cooling to obtain an activated solution;
(4) mixing the activated solution with acyl chloride methyl methacrylate, stirring uniformly, feeding into a reaction kettle, dropwise adding an acid binding agent, adjusting the temperature of the reaction kettle to 3-5 ℃, reacting for 6-8 hours after dropwise adding, discharging and cooling to obtain the chitosan modified monomer.
A preparation method of a chitosan-doped polyester material comprises the following steps:
(1) adding an initiator into isopropanol of which the weight is 10-13 times that of the initiator, and uniformly stirring;
(2) mixing the chitosan modified monomer with diethylene glycol dibenzoate, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to be 60-75 ℃, adding the initiator solution, keeping the temperature and stirring for 3-5 hours, discharging, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain a chitosan modified polymer;
(3) and (2) mixing the chitosan modified polymer with bisphenol A phosphite and tributyl tin trichloride, uniformly stirring, feeding into an extruder, and carrying out melt extrusion to obtain the chitosan-doped polyester material.
The invention has the advantages that:
according to the invention, methyl methacrylate is firstly subjected to acyl chlorination reaction, then the diacetone acrylamide is adopted to treat chitosan, and then the chitosan and acyl chlorinated methyl methacrylate are mixed, so that the reaction of acyl chloride and phenolic hydroxyl in chitosan is promoted under the action of an acid binding agent, and the dispersion performance of chitosan in methyl methacrylate monomers is improved.
Detailed Description
Example 1
A chitosan-doped polyester material is prepared from the following raw materials in parts by weight:
the modified chitosan comprises a chitosan modified monomer 240, an initiator 5, diethylene glycol dibenzoate 7, bisphenol A phosphite 15 and tributyltin trichloride 2.
The chitosan modified monomer is prepared from the following raw materials in parts by weight:
chitosan 18, methyl methacrylate 130, an acid-binding agent 0.14, thionyl chloride 40, ricinoleic acid 13, dimethylformamide 30 and diacetone acrylamide 3.
The acid-binding agent is pyridine.
The initiator is dicumyl peroxide.
The preparation method of the chitosan modified monomer comprises the following steps:
(1) mixing ricinoleic acid and methyl methacrylate, adding into dimethylformamide, raising the temperature to 55 ℃, and stirring for 2 hours under the condition of heat preservation to obtain methyl methacrylate dispersion;
(2) mixing the methyl methacrylate dispersion with thionyl chloride, feeding the mixture into a thermostatic water bath at the temperature of 75 ℃, preserving heat, stirring for 25 hours, and performing rotary evaporation to remove dimethylformamide and thionyl chloride to obtain acyl chlorinated methyl methacrylate;
(3) mixing chitosan and diacetone acrylamide, adding the mixture into deionized water 7 times the weight of the mixture, carrying out ultrasonic treatment for 20 minutes, sending the mixture into a drying oven, drying the mixture for 5 hours at 80 ℃, discharging the mixture, and cooling the mixture to obtain an activated solution;
(4) mixing the activated solution with acyl chloride methyl methacrylate, stirring uniformly, feeding into a reaction kettle, dropwise adding an acid binding agent, adjusting the temperature of the reaction kettle to 5 ℃, reacting for 8 hours after the dropwise adding is finished, discharging and cooling to obtain the chitosan modified monomer.
A preparation method of a chitosan-doped polyester material comprises the following steps:
(1) adding an initiator into isopropanol with the weight 13 times that of the initiator, and uniformly stirring;
(2) mixing the chitosan modified monomer with diethylene glycol dibenzoate, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 75 ℃, adding the initiator solution, keeping the temperature and stirring for 5 hours, discharging, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain a chitosan modified polymer;
(3) and (2) mixing the chitosan modified polymer with bisphenol A phosphite and tributyl tin trichloride, uniformly stirring, feeding into an extruder, and carrying out melt extrusion to obtain the chitosan-doped polyester material.
Example 2
A chitosan-doped polyester material is prepared from the following raw materials in parts by weight:
chitosan modified monomer 200, initiator 3, diethylene glycol dibenzoate 4, bisphenol A phosphite 15 and tributyltin trichloride 1.
The chitosan modified monomer is prepared from the following raw materials in parts by weight:
10 parts of chitosan, 100 parts of methyl methacrylate, 0.1 part of an acid-binding agent, 30 parts of thionyl chloride, 10 parts of ricinoleic acid, 20 parts of dimethylformamide and 1 part of diacetone acrylamide.
The acid-binding agent is pyridine.
The initiator is dicumyl peroxide.
The preparation method of the chitosan modified monomer comprises the following steps:
(1) mixing ricinoleic acid and methyl methacrylate, adding into dimethylformamide, raising the temperature to 50 ℃, and stirring for 1 hour under the condition of heat preservation to obtain methyl methacrylate dispersion;
(2) mixing the methyl methacrylate dispersion with thionyl chloride, feeding the mixture into a constant-temperature water bath at 65 ℃, preserving heat, stirring for 20 hours, and performing rotary evaporation to remove dimethylformamide and thionyl chloride to obtain acyl chlorinated methyl methacrylate;
(3) mixing chitosan and diacetone acrylamide, adding into deionized water 4 times of the weight of the mixture, performing ultrasonic treatment for 10 minutes, sending into a drying oven, drying at 70 ℃ for 3 hours, discharging, and cooling to obtain an activated solution;
(4) mixing the activated solution with acyl chloride methyl methacrylate, stirring uniformly, feeding into a reaction kettle, dropwise adding an acid binding agent, adjusting the temperature of the reaction kettle to 3 ℃, reacting for 6 hours after the dropwise adding is finished, discharging and cooling to obtain the chitosan modified monomer.
A preparation method of a chitosan-doped polyester material comprises the following steps:
(1) adding an initiator into isopropanol with the weight being 10 times of that of the initiator, and uniformly stirring;
(2) mixing the chitosan modified monomer with diethylene glycol dibenzoate, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 60 ℃, adding the initiator solution, keeping the temperature and stirring for 3 hours, discharging, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain a chitosan modified polymer;
(3) and (2) mixing the chitosan modified polymer with bisphenol A phosphite and tributyl tin trichloride, uniformly stirring, feeding into an extruder, and carrying out melt extrusion to obtain the chitosan-doped polyester material.
And (3) performance testing:
the chitosan-doped polyester material of embodiment 1 of the present invention:
a tensile strength (MPa) of 13.9;
elongation at break (%): 71;
impact strength (J/m) of simply supported beam notch2):20.9；
Specific gravity of 0.73g/cm3；
The chitosan-doped polyester material of embodiment 2 of the present invention:
a tensile strength (MPa) of 13.6;
elongation at break (%): 80;
impact strength (J/m) of simply supported beam notch2):21.7；
Specific gravity of 0.66g/cm3；
The tensile strength of the commercially available polymethyl methacrylate material is less than or equal to 10Mpa, the elongation at break is less than or equal to 50 percent, and the impact strength of a simply supported beam notch is less than or equal to 15J/m2Specific gravity of 1.05-1.1g/cm3。
Claims (6)
1. The chitosan-doped polyester material is characterized by being prepared from the following raw materials in parts by weight:
200-240 chitosan modified monomer, 3-5 initiator, 4-7 diethylene glycol dibenzoate, 10-15 bisphenol A phosphite ester and 1-2 tributyltin trichloride.
2. The chitosan-doped polyester material as claimed in claim 1, wherein the chitosan modified monomer is prepared from the following raw materials in parts by weight:
10-18 parts of chitosan, 100-130 parts of methyl methacrylate, 0.1-0.14 part of acid binding agent, 30-40 parts of thionyl chloride, 10-13 parts of ricinoleic acid, 20-30 parts of dimethylformamide and 1-3 parts of diacetone acrylamide.
3. A chitosan-doped polyester material as claimed in claim 2, wherein said acid-binding agent is pyridine.
4. The chitosan-doped polyester material of claim 1, wherein the initiator is dicumyl peroxide.
5. The chitosan-doped polyester material as claimed in claim 2, wherein the preparation method of the chitosan modified monomer comprises the following steps:
(1) mixing ricinoleic acid and methyl methacrylate, adding into dimethylformamide, heating to 50-55 deg.C, stirring for 1-2 hr to obtain methyl methacrylate dispersion;
(2) mixing the methyl methacrylate dispersion with thionyl chloride, feeding the mixture into a constant-temperature water bath at the temperature of 65-75 ℃, preserving the temperature, stirring for 20-25 hours, and performing rotary evaporation to remove dimethylformamide and thionyl chloride to obtain acyl chloride methyl methacrylate;
(3) mixing chitosan and diacetone acrylamide, adding into deionized water 4-7 times of the weight of the mixture, performing ultrasonic treatment for 10-20 minutes, sending into a drying oven, drying at 70-80 deg.C for 3-5 hours, discharging, and cooling to obtain an activated solution;
(4) mixing the activated solution with acyl chloride methyl methacrylate, stirring uniformly, feeding into a reaction kettle, dropwise adding an acid binding agent, adjusting the temperature of the reaction kettle to 3-5 ℃, reacting for 6-8 hours after dropwise adding, discharging and cooling to obtain the chitosan modified monomer.
6. A method for preparing the chitosan-doped polyester material as claimed in claim 1, comprising the following steps:
(1) adding an initiator into isopropanol of which the weight is 10-13 times that of the initiator, and uniformly stirring;
(2) mixing the chitosan modified monomer with diethylene glycol dibenzoate, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to be 60-75 ℃, adding the initiator solution, keeping the temperature and stirring for 3-5 hours, discharging, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain a chitosan modified polymer;
(3) and (2) mixing the chitosan modified polymer with bisphenol A phosphite and tributyl tin trichloride, uniformly stirring, feeding into an extruder, and carrying out melt extrusion to obtain the chitosan-doped polyester material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010602271.XA CN111732805A (en) | 2020-06-28 | 2020-06-28 | Chitosan-doped polyester material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010602271.XA CN111732805A (en) | 2020-06-28 | 2020-06-28 | Chitosan-doped polyester material and preparation method thereof |
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| CN111732805A true CN111732805A (en) | 2020-10-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601846A (en) * | 2015-09-10 | 2016-05-25 | 河北科技师范学院 | Chitosan surface molecularly imprinted rod-like material |
| CN108014756A (en) * | 2017-12-12 | 2018-05-11 | 成都育芽科技有限公司 | A kind of macroporous absorption type water pollution inorganic agent and preparation method thereof |
| CN108816197A (en) * | 2018-06-27 | 2018-11-16 | 湖北省农业科学院农产品加工与核农技术研究所 | A kind of radiation modification Graft Copolymerization of MMA onto Chitosan heavy metal absorbent and preparation method thereof |
| CN108864589A (en) * | 2018-08-01 | 2018-11-23 | 安徽省绩溪县华宇防火滤料有限公司 | A kind of lightweight polyphenyl ethylene thermal insulation material and preparation method thereof |
-
2020
- 2020-06-28 CN CN202010602271.XA patent/CN111732805A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601846A (en) * | 2015-09-10 | 2016-05-25 | 河北科技师范学院 | Chitosan surface molecularly imprinted rod-like material |
| CN108014756A (en) * | 2017-12-12 | 2018-05-11 | 成都育芽科技有限公司 | A kind of macroporous absorption type water pollution inorganic agent and preparation method thereof |
| CN108816197A (en) * | 2018-06-27 | 2018-11-16 | 湖北省农业科学院农产品加工与核农技术研究所 | A kind of radiation modification Graft Copolymerization of MMA onto Chitosan heavy metal absorbent and preparation method thereof |
| CN108864589A (en) * | 2018-08-01 | 2018-11-23 | 安徽省绩溪县华宇防火滤料有限公司 | A kind of lightweight polyphenyl ethylene thermal insulation material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨爱华 等: "壳聚糖接枝甲基丙烯酸甲酯的研究", 《化工新型材料》 * |
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