CN108676334B - Silica gel modified polylactic acid material and preparation method thereof - Google Patents
Silica gel modified polylactic acid material and preparation method thereof Download PDFInfo
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- CN108676334B CN108676334B CN201810465567.4A CN201810465567A CN108676334B CN 108676334 B CN108676334 B CN 108676334B CN 201810465567 A CN201810465567 A CN 201810465567A CN 108676334 B CN108676334 B CN 108676334B
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a silica gel modified polylactic acid material which is prepared from the following raw materials in parts by weight: 150 parts of polylactic acid 130-one, 4-6 parts of oleic acid, 10-12 parts of palm wax, 20-30 parts of chloroform, 1-2 parts of benzotriazole and 70-80 parts of activated silica gel dispersion liquid.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a silica gel modified polylactic acid material and a preparation method thereof.
Background
The polylactic acid is a biodegradable material which is widely researched and most developed in make internal disorder or usurp at present, has good biodegradability and environmental friendliness, is a green material, is prepared from renewable crops, has the most outstanding advantage of biodegradability, can be completely degraded to generate carbon dioxide and water after being used, and does not pollute the environment. The polylactic acid also has good mechanical property, thermoplasticity, fiber forming property and high transparency, is suitable for various processing methods such as blow molding, extrusion, injection molding and the like, is convenient to process, and is determined by the industry as a novel packaging material with the most development prospect in the new century;
however, with the continuous development of society, the requirements for the material performance are higher and higher, and especially, the research on the composite material is deeper and deeper, and how to obtain the composite material with good stability and high comprehensive performance is the focus of the current research.
Disclosure of Invention
The invention aims to provide a silica gel modified polylactic acid material and a preparation method thereof aiming at the defects and the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a silica gel modified polylactic acid material is composed of the following raw materials in parts by weight:
150 parts of polylactic acid 130, 4-6 parts of oleic acid, 10-12 parts of palm wax, 20-30 parts of chloroform, 1-2 parts of benzotriazole and 70-80 parts of activated silica gel dispersion liquid.
The activated silica gel dispersion liquid is prepared from the following raw materials in parts by weight:
90-100 parts of water glass, 15-20 parts of methyl methacrylate, 30-40 parts of butyl acrylate, 0.8-1 part of initiator, 10-13 parts of triethylamine and 2-4 parts of coconut diethanolamide.
The mole number of the water glass is 3-4, and the initiator is one of ammonium persulfate, sodium persulfate and potassium persulfate.
The preparation method of the activated silica gel dispersion comprises the following steps:
(1) adding an initiator into deionized water with the weight of 100-110 times that of the initiator, and uniformly stirring;
(2) taking glass, dropwise adding 0.9-1mol/l hydrochloric acid, adjusting the pH value to 2-3, standing for 4-5 hours, sending into an oven, drying at the temperature of 100-;
(3) mixing silica gel with methyl methacrylate and butyl acrylate, stirring uniformly, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 70-75 ℃, adding the initiator solution, keeping the temperature and stirring for 4-5 hours, discharging and cooling to obtain silica gel emulsion;
(4) mixing triethylamine and coconut diethanolamide, adding the mixture into deionized water which is 20-30 times of the weight of the mixture, and uniformly stirring to obtain an amine aqueous solution;
(5) mixing the silica gel emulsion with an amine aqueous solution, raising the temperature to 50-55 ℃, and carrying out ultrasonic treatment for 10-40 minutes to obtain the activated silica gel dispersion.
A preparation method of a silica gel modified polylactic acid material comprises the following steps:
(1) adding carnauba wax into chloroform, stirring uniformly, feeding into a constant-temperature water bath at 60-65 ℃, adding oleic acid, keeping the temperature and stirring for 20-30 minutes, discharging, and distilling to remove chloroform to obtain acidified carnauba wax;
(2) mixing polylactic acid and acidified palm wax, preheating for 5-10 minutes at the temperature of 100-105 ℃, adding into the activated silica gel dispersion, keeping the temperature and stirring for 2-3 hours at the temperature of 70-75 ℃, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain modified polylactic acid;
(3) and mixing benzotriazole with the latex modified polylactic acid, uniformly stirring, feeding into an extruder, performing melt extrusion, and cooling to obtain the silica gel modified polylactic acid material.
The invention has the advantages that:
according to the invention, firstly, water glass is used as a precursor to prepare silica gel, the silica gel, methyl methacrylate and butyl acrylate are used as blending monomers, polymerization is carried out under the action of an initiator, then triethylamine is adopted to treat polymer emulsion to obtain amine modified silica gel emulsion, and effective dispersion of the silica gel among polyesters is realized through the reaction;
according to the invention, the palm wax is treated by oleic acid, activated carboxyl groups are endowed on the surface of the wax, and then the wax is subjected to blending reaction with aminated silica gel emulsion, so that the bonding strength of silica gel and polylactic acid is improved, and the silica gel has good viscosity and thermal stability, so that the polylactic acid and the silica gel are compounded, so that the finished composite material has good viscosity and heat-resistant stability, and the thermal decomposition temperature is improved.
Detailed Description
Example 1
A silica gel modified polylactic acid material is composed of the following raw materials in parts by weight:
150 parts of polylactic acid, 6 parts of oleic acid, 12 parts of palm wax, 30 parts of chloroform, 2 parts of benzotriazole and 80 parts of activated silica gel dispersion.
The activated silica gel dispersion liquid is prepared from the following raw materials in parts by weight:
100 parts of water glass, 20 parts of methyl methacrylate, 40 parts of butyl acrylate, 1 part of initiator, 13 parts of triethylamine and 4 parts of coconut diethanolamide.
The mole number of the water glass is 4, and the initiator is potassium persulfate.
The preparation method of the activated silica gel dispersion comprises the following steps:
(1) adding an initiator into deionized water with the weight being 110 times of that of the initiator, and uniformly stirring;
(2) dropwise adding 1mol/l hydrochloric acid into water glass, adjusting the pH value to 3, standing for 5 hours, feeding into an oven, drying at 110 ℃ for 14 hours, discharging and cooling to obtain silica gel;
(3) mixing silica gel with methyl methacrylate and butyl acrylate, stirring uniformly, 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 4-5 hours, discharging and cooling to obtain silica gel emulsion;
(4) mixing triethylamine and coconut diethanolamide, adding the mixture into deionized water 30 times of the weight of the mixture, and uniformly stirring to obtain an amine aqueous solution;
(5) and mixing the silica gel emulsion with an amine aqueous solution, raising the temperature to 55 ℃, and performing ultrasonic treatment for 40 minutes to obtain the activated silica gel dispersion.
A preparation method of a silica gel modified polylactic acid material comprises the following steps:
(1) adding carnauba wax into chloroform, stirring uniformly, feeding into a constant-temperature water bath at 65 ℃, adding oleic acid, keeping the temperature and stirring for 30 minutes, discharging, and distilling to remove chloroform to obtain acidified carnauba wax;
(2) mixing polylactic acid and acidified palm wax, preheating for 10 minutes at 105 ℃, adding into the activated silica gel dispersion, keeping the temperature at 75 ℃, stirring for 3 hours, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain modified polylactic acid;
(3) and mixing benzotriazole with the latex modified polylactic acid, uniformly stirring, feeding into an extruder, performing melt extrusion, and cooling to obtain the silica gel modified polylactic acid material.
Example 2
A silica gel modified polylactic acid material is composed of the following raw materials in parts by weight:
polylactic acid 130, oleic acid 4, palm wax 10, chloroform 20, benzotriazole 1 and activated silica gel dispersion 70.
The activated silica gel dispersion liquid is prepared from the following raw materials in parts by weight:
water glass 90, methyl methacrylate 15, butyl acrylate 30, initiator 0.8, triethylamine 10 and coconut diethanolamide 2.
The mole number of the water glass is 3, and the initiator is ammonium persulfate.
The preparation method of the activated silica gel dispersion comprises the following steps:
(1) adding an initiator into deionized water with the weight of 100 times of that of the initiator, and uniformly stirring;
(2) taking water glass, dropwise adding 0.9mol/l hydrochloric acid, adjusting the pH value to 2, standing for 4 hours, sending into an oven, drying at 100 ℃ for 10 hours, discharging and cooling to obtain silica gel;
(3) mixing silica gel with methyl methacrylate and butyl acrylate, stirring uniformly, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 70 ℃, adding the initiator solution, keeping the temperature and stirring for 4 hours, discharging and cooling to obtain silica gel emulsion;
(4) mixing triethylamine and coconut diethanolamide, adding the mixture into deionized water which is 20 times of the weight of the mixture, and uniformly stirring to obtain an amine aqueous solution;
(5) and mixing the silica gel emulsion with an amine aqueous solution, raising the temperature to 50 ℃, and performing ultrasonic treatment for 10 minutes to obtain the activated silica gel dispersion.
A preparation method of a silica gel modified polylactic acid material comprises the following steps:
(1) adding carnauba wax into chloroform, stirring uniformly, feeding into a constant-temperature water bath at 60 ℃, adding oleic acid, keeping the temperature and stirring for 20 minutes, discharging, and distilling to remove chloroform to obtain acidified carnauba wax;
(2) mixing polylactic acid and acidified palm wax, preheating for 5 minutes at 100 ℃, adding into the activated silica gel dispersion, keeping the temperature at 70 ℃, stirring for 2 hours, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain modified polylactic acid;
(3) and mixing benzotriazole with the latex modified polylactic acid, uniformly stirring, feeding into an extruder, performing melt extrusion, and cooling to obtain the silica gel modified polylactic acid material.
And (3) performance testing:
the intrinsic viscosity of the silica gel modified polylactic acid material in the embodiment 1 of the invention is 0.85d L/g, and the glass transition temperature is 98 ℃;
the intrinsic viscosity of the silica gel modified polylactic acid material in the embodiment 2 of the invention is 0.88d L/g, and the glass transition temperature is 100 ℃.
Claims (3)
1. A silica gel modified polylactic acid material is characterized by comprising the following raw materials in parts by weight: 150 parts of polylactic acid 130, 4-6 parts of oleic acid, 10-12 parts of palm wax, 20-30 parts of chloroform, 1-2 parts of benzotriazole and 70-80 parts of activated silica gel dispersion liquid,
the activated silica gel dispersion liquid is prepared from the following raw materials in parts by weight:
90-100 parts of water glass, 15-20 parts of methyl methacrylate, 30-40 parts of butyl acrylate, 0.8-1 part of initiator, 10-13 parts of triethylamine, 2-4 parts of coconut diethanolamide,
the preparation method of the activated silica gel dispersion comprises the following steps:
(1) adding an initiator into deionized water with the weight of 100-110 times that of the initiator, and uniformly stirring;
(2) taking glass, dropwise adding 0.9-1mol/l hydrochloric acid, adjusting the pH value to 2-3, standing for 4-5 hours, sending into an oven, drying at the temperature of 100-;
(3) mixing silica gel with methyl methacrylate and butyl acrylate, stirring uniformly, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 70-75 ℃, adding the initiator solution, keeping the temperature and stirring for 4-5 hours, discharging and cooling to obtain silica gel emulsion;
(4) mixing triethylamine and coconut diethanolamide, adding the mixture into deionized water which is 20-30 times of the weight of the mixture, and uniformly stirring to obtain an amine aqueous solution;
(5) mixing the silica gel emulsion with an amine aqueous solution, raising the temperature to 50-55 ℃, and carrying out ultrasonic treatment for 10-40 minutes to obtain the activated silica gel dispersion.
2. The silica gel modified polylactic acid material according to claim 1, wherein the mole number of the water glass is 3 to 4, and the initiator is one of ammonium persulfate, sodium persulfate and potassium persulfate.
3. The preparation method of the silica gel modified polylactic acid material according to claim 1, which comprises the following steps:
(1) adding carnauba wax into chloroform, stirring uniformly, feeding into a constant-temperature water bath at 60-65 ℃, adding oleic acid, keeping the temperature and stirring for 20-30 minutes, discharging, and distilling to remove chloroform to obtain acidified carnauba wax;
(2) mixing polylactic acid and acidified palm wax, preheating for 5-10 minutes at the temperature of 100-105 ℃, adding into the activated silica gel dispersion, keeping the temperature and stirring for 2-3 hours at the temperature of 70-75 ℃, performing suction filtration, washing a filter cake with water, and drying at normal temperature to obtain modified polylactic acid;
(3) and mixing benzotriazole with the silica gel modified polylactic acid, uniformly stirring, feeding into an extruder, performing melt extrusion, and cooling to obtain the silica gel modified polylactic acid material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010016801A1 (en) * | 2008-08-07 | 2010-02-11 | Hydrochem (S) Pte Ltd | Melt-stable and hydrolysis resistant hydroxy acid polymer |
| CN106947373A (en) * | 2017-04-12 | 2017-07-14 | 浩力森化学科技（江苏）有限公司 | The SiO of surface-modified nano containing acrylate polymer2The cation electrodeposition coating of microballoon |
| CN107698967A (en) * | 2017-10-09 | 2018-02-16 | 朱沫 | A kind of 3D printing material for colour print |
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2018
- 2018-05-16 CN CN201810465567.4A patent/CN108676334B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010016801A1 (en) * | 2008-08-07 | 2010-02-11 | Hydrochem (S) Pte Ltd | Melt-stable and hydrolysis resistant hydroxy acid polymer |
| CN106947373A (en) * | 2017-04-12 | 2017-07-14 | 浩力森化学科技（江苏）有限公司 | The SiO of surface-modified nano containing acrylate polymer2The cation electrodeposition coating of microballoon |
| CN107698967A (en) * | 2017-10-09 | 2018-02-16 | 朱沫 | A kind of 3D printing material for colour print |
Non-Patent Citations (1)
| Title |
|---|
| 聚乳酸/二氧化硅有机无机杂化材料的制备和表征;周海鸥等;《高分子材料科学与工程》;20060331;第22卷(第2期);第220-226页 * |
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Effective date of registration: 20191211 Address after: 312000 room 1107, 11 building, 683 North Road, Yangming Road, Yuecheng District, Shaoxing, Zhejiang, China Applicant after: SHAOXING GREEN STAR NEW MATERIAL Co.,Ltd. Applicant after: SHAOXING LYUSIDA NEW MATERIAL Co.,Ltd. Applicant after: SHANGHAI LYUJI BIOMATERIAL Co.,Ltd. Address before: 312000 room 1107, 11 building, 683 North Road, Yangming Road, Yuecheng District, Shaoxing, Zhejiang, China Applicant before: SHAOXING GREEN STAR NEW MATERIAL Co.,Ltd. Applicant before: NINGBO KEEN BIOLOGICAL MATERIALS Co.,Ltd. Applicant before: SHAOXING LYUSIDA NEW MATERIAL Co.,Ltd. Applicant before: SHANGHAI LYUJI BIOMATERIAL Co.,Ltd. |
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