CN112661638B - Toughening intermediate, preparation method thereof and toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing - Google Patents
Toughening intermediate, preparation method thereof and toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a toughening intermediate, a preparation method thereof and a toughening mosquito-repellent high polymer biodegradable composite material for 3D printing. The toughening intermediate is prepared from a mosquito repellent, anhydride and epoxidized vegetable oil under the action of a catalyst, wherein the mosquito repellent is extracted from plants and is one or more of geraniol, 4-terpene alcohol and eucalyptol which are bio-based sources. The toughening intermediate of the invention achieves the purpose of combination by using geraniol which is a bio-based source as a mosquito repellent and good compatibility between anhydride and epoxidized vegetable oil, and is used for the toughening mosquito repellent high polymer biodegradable composite material for 3D printing, in-situ reaction among components is initiated in the melting and blending process, so that the network structure of the material is greatly enhanced, the toughness of a 3D printing product prepared from the branched material is effectively improved, and the defect of poor impact toughness when the traditional high polymer material, especially PBS (Poly butylenes succinate) is used as the 3D material is overcome.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a toughening intermediate and a preparation method thereof, and a toughening mosquito-repellent high polymer biodegradable composite material for 3D printing.
Background
With the development of the concept of 'environmental protection and green', the degradable plastics are more and more widely used in the aspects of life because the degradable plastics can be rapidly degraded under the natural environment condition to finally form carbon dioxide and water. At present, 3D printing materials begin to be changed from the fields of industry, buildings, automobiles and the like to the daily life aspect, and the application development of high polymer materials as the 3D printing materials still has a great development space, and meanwhile, the degradability, the toughness, the strength and the additional performance need to be further improved.
The degradable material in the prior art is a low-cost toughened polylactic acid composite material disclosed in Chinese patent 201610810392.7 and a preparation method thereof, but the addition of a large amount of inorganic filler in the scheme can cause the degradation capability of the material to be reduced. For example, the high molecular weight polylactic acid disclosed in chinese patent 200810050861.5 uses isocyanate as a cross-linking agent in the scheme to improve the toughness of the composite material, but the isocyanate as a cross-linking agent has high toxicity and is harmful to human body.
The existing 3D printing material is a mosquito repellent type 3D printing material which is disclosed in patent 201510287329.5 and is added with a plant-derived mosquito repellent to provide a mosquito repellent effect, but the mosquito repellent in the invention is prepared by mixing multiple complex components and only by simple blending extrusion, and the mosquito repellent effect of the material can be remarkably reduced when the material is used for a long time.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a degradable toughening intermediate with a bio-based source and a toughened mosquito-repellent macromolecule biodegradable composite material for 3D printing, which has good toughening and mosquito-repellent effects.
The purpose of the invention can be realized by the following technical scheme: a toughening intermediate is prepared from a mosquito repellent, acid anhydride and epoxidized vegetable oil under the action of a catalyst, wherein the mosquito repellent is extracted from plants and is geraniol from a bio-based source.
In the toughening intermediate, the toughening intermediate is prepared from a mosquito repellent, anhydride and epoxidized vegetable oil under the action of a catalyst, wherein the mosquito repellent is extracted from plants and is one or more of geraniol, 4-terpene alcohol and eucalyptol which are bio-based sources.
Preferably, the toughening intermediate comprises 10-30 parts of epoxidized vegetable oil, 0.5-5 parts of a mosquito repellent, 0.3-3 parts of anhydride and 0.1-0.5 part of a catalyst.
More preferably, the epoxidized vegetable oil has an epoxy value of 4 to 8.
More preferably, the epoxidized vegetable oil is one or more of epoxidized soybean oil, epoxidized castor oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized cottonseed oil and epoxidized pistacia chinensis oil.
Further preferably, the acid anhydride is one or more of maleic anhydride, itaconic anhydride, phthalic anhydride, anhydride succinic anhydride and glutaric anhydride.
More preferably, the catalyst is one or more of zinc acetylacetonate, zinc glutarate, lithium chloride, diethyl zinc, dialkyl zinc, diethoxy magnesium and triisopropoxyaluminium.
The invention also provides a preparation method of the toughening intermediate, which comprises the following steps:
1) weighing a mosquito repellent, anhydride, epoxidized vegetable oil and a catalyst, and drying in an oven in advance;
2) slowly and uniformly stirring the mosquito repellent and the anhydride, and heating to T1 to obtain a mosquito repellent intermediate;
3) and adding epoxidized vegetable oil into the mosquito repelling intermediate, heating to T2, adding a catalyst, and reacting to obtain the toughening intermediate, wherein T2 is more than T1.
Preferably, T1 in step 2) is from 90 to 120 ℃.
Preferably, T2 in step 3) is 150-180 ℃.
The invention also provides an application of the toughening intermediate in 3D printing.
The invention also provides a toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing, which comprises a high-molecular material, an auxiliary agent and the toughened intermediate.
The toughening intermediate of the invention utilizes carboxyl on anhydride to react with epoxy oil by a catalyst at high temperature, improves the toughness of the composite material by the toughening effect and compatibility of the vegetable oil, and carries out mosquito repellent modification on the basis of the toughening effect.
Preferably 70-95 parts of high polymer material, 0.5-2 parts of auxiliary agent and 5-30 parts of toughening intermediate.
Further preferably, the polymer material is a polymer material with a carboxyl end group, and comprises one or more of PBS, PLA, PBAT, and PBSA.
More preferably, the polymer material is PBS, the PBS has a melt flow rate of less than 25, and a molecular weight of 5-10 ten thousand. Poly (butylene succinate) (PBS) is a typical completely biodegradable material, the synthetic raw material source of the poly (butylene succinate) (PBS) can be petroleum resources, and can also be obtained by fermentation of biological resources, and the poly (butylene succinate) (PBS) is outstanding in biodegradable plastic materials. Compared with PBSA and PBAT, the PBS has better temperature resistance, can resist the boiling water temperature within the usable temperature range of-30 to 100 ℃, has wider application range, and is more convenient to store, transport and use in the maritime and hotter environments; compared with PLA, PBS has better toughness and temperature resistance than PLA, but inferior hardness and transparency than PLA, and the two products are respectively good in mechanical property, but have obvious advantages in the application field, processing property, storage and the like.
Further preferably, the auxiliary agent comprises a cross-linking agent, a lubricant, an antibacterial agent, an anti-UV agent and an antioxidant.
Still more preferably, the crosslinking agent in the auxiliary agent is a peroxide crosslinking agent or a metal oxide crosslinking agent, the peroxide crosslinking agent is dicumyl peroxide or 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane, and the metal oxide crosslinking agent is zinc oxide or magnesium oxide.
More preferably, the lubricant in the auxiliary agent is one or more of silicone powder, pentaerythritol stearate and ethylene bis fatty acid amide.
More preferably, the antibacterial agent in the auxiliary is chitosan and derivatives thereof.
Even more preferably, the UV resistant agent in the adjuvant is UV-531.
Further preferably, the antioxidant in the additive is formed by compounding an antioxidant 1010 and an antioxidant 168. Still more preferably, the mass ratio of the antioxidant 1010 to the antioxidant 168 is (0.8-1.5): 1.
The invention also provides a preparation method of the toughening mosquito-repellent macromolecule biodegradable composite material for 3D printing, and the preparation method comprises the steps of blending the toughening intermediate and a macromolecule material, adding an auxiliary agent, and extruding to obtain the biodegradable composite material.
Preferably, the extrusion is carried out in a twin-screw extruder with the temperature of 120-200 ℃ and the rotating speed of 150-250 rpm.
Compared with the prior art, the toughening intermediate disclosed by the invention does not need a coupling agent, lignin and a catalyst 4-dimethylamino pyridine, achieves the purpose of combination by utilizing good compatibility among geraniol from a bio-based source as a mosquito repellent, anhydride and epoxidized vegetable oil, and is used for the toughening mosquito-repellent high-molecular biodegradable composite material for 3D printing, an in-situ reaction among components is initiated in the melt blending process, so that the network structure of the material is greatly enhanced, the toughness of a 3D printing product prepared from the branch material is effectively improved, and the defect of poor impact toughness of the traditional high-molecular material, especially PBS as the 3D material, is overcome. Moreover, the toughening intermediate, the mosquito repellent and the toughening component used in the toughening mosquito repellent high polymer biodegradable composite material for 3D printing are completely derived from natural plant resources, are non-toxic to human beings, and have the functions of repelling mosquitoes, resisting oxidation and inhibiting bacteria. Most importantly, the toughened mosquito-repellent macromolecule biodegradable composite material can be completely biodegraded under natural conditions, greatly reduces pollution caused by plastic waste, and conforms to the development strategy of 'green and environment-friendly' in China. The toughening intermediate and the degradable composite material provided by the invention can be widely used for 3D printing, mosquito-repellent pendants, indoor ornaments and the like, meet the requirements of military field training, summer fishing, summer indoor mosquito prevention and the like, greatly expand the application and development space of 3D printing from the aspect of 3D printing materials, and have remarkable significance.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Table 1: raw materials and parts by weight of toughening intermediates in examples 1-8
Example 1
Epoxidized vegetable oil, a mosquito repellent, acid anhydride and a catalyst are weighed according to the toughening intermediate raw materials and the parts by weight thereof in the example 1 in the table 1 and are respectively pre-dried in an oven.
And slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 90 ℃ within one hour to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 150 ℃, and keeping for 1 hour under the condition of the catalyst to obtain the toughening intermediate.
Example 2
The raw materials of the toughening intermediate described in table 1, example 2, and their parts by weight were weighed.
And then slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 95 ℃ within one hour to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 155 ℃, and keeping for 1 hour under the condition of the catalyst to obtain a toughening intermediate.
Example 3
The toughening intermediate raw materials and the parts by weight thereof are weighed as described in table 1, example 3.
And then slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 100 ℃ within one hour to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 160 ℃, and keeping for 2 hours under the condition of the catalyst to obtain a toughening intermediate.
Example 4
The toughening intermediate raw materials and the parts by weight thereof are weighed as described in example 4 of table 1.
And then slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 105 ℃ within one hour to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 165 ℃, and keeping for 1 hour under the condition of the catalyst to obtain the toughening intermediate.
Example 5
The raw materials of the toughening intermediate described in table 1, example 5, and their parts by weight were weighed.
And then slowly stirring the mosquito repellent and the anhydride uniformly, and gradually heating to 110 ℃ within 2 hours to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 170 ℃, and keeping for 2 hours under the condition of the catalyst to obtain a toughening intermediate.
Example 6
The raw materials of the toughening intermediate described in table 1, example 6, and their parts by weight were weighed.
And then slowly stirring the mosquito repellent and the anhydride uniformly, and gradually heating to 115 ℃ within one hour to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 170 ℃, and keeping for 1 hour under the condition of the catalyst to obtain a toughening intermediate.
Example 7
The toughening intermediate raw materials and the parts by weight thereof are weighed as described in table 1, example 7.
And then slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 100 ℃ within one hour to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 170 ℃, and keeping for 2 hours under the condition of the catalyst to obtain a toughening intermediate.
Example 8
The raw materials of the toughening intermediate described in table 1, example 8, and their parts by weight were weighed.
And then slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 120 ℃ within 2 hours to obtain a mosquito repellent intermediate.
And then adding epoxidized vegetable oil and a catalyst, heating to 180 ℃, and keeping for 2 hours under the condition of the catalyst to obtain a toughening intermediate.
Table 2: the components and parts by weight of the toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing in application examples 1-8
The toughening intermediates of application examples 1-8 were taken from examples 1-8, respectively.
Application example 1
Weighing the raw materials in the parts by weight shown in application example 1 in Table 2, blending the toughening intermediate with the high polymer material, adding an auxiliary agent, and extruding under the condition of a double-screw extruder shown in Table 2 to obtain the biodegradable composite material. Wherein the cross-linking agent is zinc oxide, the lubricant is a mixture of pentaerythritol stearate and ethylene bis fatty acid amide according to the mass ratio of 1:1, the antibacterial agent is chitosan, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 according to the mass ratio of 0.8: 1.
Application example 2
Weighing the raw materials in the parts by weight shown in application example 2 in Table 2, blending the toughening intermediate with the high polymer material, adding an auxiliary agent, and extruding under the condition of a double-screw extruder shown in Table 2 to obtain the biodegradable composite material. Wherein the cross-linking agent is magnesium oxide, the lubricant is ethylene bis-fatty acid amide, the antibacterial agent is carboxymethyl chitosan, and the antioxidant is antioxidant 1010.
Application example 3
Weighing the raw materials in the parts by weight shown in application example 3 in the table 2, blending the toughening intermediate with the high polymer material, adding the auxiliary agent, and extruding under the condition of the double-screw extruder in the table 2 to obtain the biodegradable composite material. Wherein the melt flow rate of PBS is less than 25, the molecular weight is 8 ten thousand, the cross-linking agent is 2, 5-dimethyl-2, 5-di (tert-butyl peroxide) hexane, the lubricant is silicone powder, the antibacterial agent is chitosan, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 according to the mass ratio of 1.2: 1.
Application example 4
Weighing the raw materials in the parts by weight in application example 4 in table 2, blending the toughening intermediate with the high polymer material, adding an auxiliary agent, and extruding under the condition of a double-screw extruder in table 2 to obtain the biodegradable composite material. Wherein the crosslinking agent is dicumyl peroxide, the lubricant is silicone powder, the antibacterial agent is chitosan, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1.
Application examples 5 to 8
The raw materials in parts by weight in application examples 5-8 in table 2 are respectively weighed, and the toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing is prepared according to the methods in application examples 1-4. Namely, the selection of the crosslinking agent, the lubricant, the antibacterial agent and the antioxidant in application example 5 was the same as that in application example 1. Application example 6 is the same as application example 2, application example 7 is the same as application example 3, and application example 8 is the same as application example 4.
Comparative example 1
100 parts of PBS were pre-dried in an oven. Heating and extruding in a double-screw extruder with the temperature of 150 ℃ and the rotating speed of 200rpm, and drying in vacuum to prepare the target product. The test shows that the notch impact strength of the material is 5.2KJ/m2。
Comparative example 2
The PBS70 parts and epoxidized soybean oil 30 parts were weighed and pre-dried in an oven.
PBS and epoxidized soybean oil were mixed well. Heating and extruding in a double-screw extruder with the temperature of 150 ℃ and the rotating speed of 200rpm, and drying in vacuum to prepare the target product. The test shows that the notch impact strength of the material is 3.5KJ/m2。
Comparative example 3
Weighing 85 parts of PBS, 15 parts of mosquito repellent eucalyptol and 0.2 part of zinc oxide, and drying in an oven in advance.
PBS, eucalyptol and zinc oxide were mixed well. Heating and extruding in a double-screw extruder with the temperature of 150 ℃ and the rotating speed of 200rpm, and drying in vacuum to prepare the target product. The test shows that the notch impact strength of the material is 3.4KJ/m2。
Comparative example 4
Weighing 85 parts of PBS, 1.5 parts of geraniol serving as a mosquito repellent, 30 parts of epoxidized soybean oil and 0.1 part of zinc acetylacetonate, and drying in an oven in advance.
Slowly and uniformly stirring the mosquito repellent, the epoxidized soybean oil and the catalyst, and gradually heating to 150 ℃ within one hour to obtain an intermediate product.
PBS and intermediate were mixed well. Heating and extruding in a double-screw extruder with the temperature of 150 ℃ and the rotating speed of 200rpm, and drying in vacuum to prepare the target product. The test detection shows that the notch impact strength of the material is 3.2KJ/m2。
Comparative example 5
85 parts of PBS and 15 parts of deet were weighed and pre-dried in an oven.
PBS and diethyltoluamide were mixed well. Heating and extruding in a double-screw extruder with the temperature of 150 ℃ and the rotating speed of 200rpm, and drying in vacuum to prepare the target product. The test shows that the notch impact strength of the material is 3.1KJ/m2。
The composite materials prepared in application examples 1 to 8 and comparative examples 1 to 5 were subjected to performance tests, and the results are shown in table 3 below.
1, carrying out density test on the modified material by adopting an electronic densimeter according to a GB/T1033 test method to obtain density data of the product.
And 2, testing the obtained material by using a differential scanning calorimeter to obtain the melting point data of the product.
3, carrying out melt flow rate test on the modified material by adopting a melt flow rate instrument according to a GB/T3682 test method to obtain melt flow rate data of the product.
And 4, carrying out tensile test on the modified material by adopting a computer system pressure control tester according to a GB/T1040 test method to obtain the tensile strength and elongation at break data of the product.
And 5, carrying out notch impact strength test on the modified material by adopting a cantilever beam impact tester according to a GB/T1843 test method to obtain notch impact strength data of the product.
6, adopting a GB/T13917.9-2009 test method, stretching a hand into the sealed mosquito cage filled with the modified material to carry out a mosquito repelling test, and obtaining the mosquito repelling time data of the product.
Table 3: performance testing of composites prepared in application examples 1-8 and comparative examples 1-5
In conclusion, the toughening intermediate disclosed by the invention does not need a coupling agent, lignin and a catalyst 4-dimethylamino pyridine, the aim of combination is achieved by utilizing good compatibility among geraniol from a biological base source as a mosquito repellent, anhydride and epoxidized vegetable oil, the toughening intermediate is used for the toughening mosquito-repellent high-molecular biodegradable composite material for 3D printing, in-situ reaction among components is initiated in the melting and blending process, the network structure of the material is greatly enhanced, the toughness of a 3D printing product prepared from the branched material is effectively improved, and the defect of poor impact toughness when the traditional high-molecular material, especially PBS, is used as the 3D material is overcome.
The technical scope of the present invention is not exhaustive, and new solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the technical scope of the present invention, and all the parameters involved in the solutions of the present invention do not have any mutually-replaceable unique combinations unless specifically stated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (6)
1. The toughening intermediate is characterized by being prepared from a mosquito repellent, anhydride and epoxidized vegetable oil under the action of a catalyst, wherein the mosquito repellent is extracted from plants and is one or more of geraniol, 4-terpene alcohol and eucalyptol which are bio-based sources; the epoxy value of the epoxidized vegetable oil is 4-8; the epoxidized vegetable oil is one or more of epoxidized soybean oil, epoxidized castor oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized cottonseed oil and epoxidized pistacia chinensis oil; the acid anhydride is one or more of maleic anhydride, itaconic anhydride, phthalic anhydride, anhydride succinic anhydride and glutaric anhydride; the catalyst is one or more of zinc acetylacetonate, zinc glutarate, lithium chloride, diethyl zinc, dialkyl zinc, diethoxy magnesium and triisopropoxyaluminium.
2. The toughening intermediate of claim 1, wherein the toughening intermediate comprises 10-30 parts of epoxidized vegetable oil, 0.5-5 parts of a mosquito repellent, 0.3-3 parts of an anhydride, and 0.1-0.5 part of a catalyst.
3. A process for the preparation of the toughened intermediate according to claim 1, comprising the steps of:
1) weighing a mosquito repellent, anhydride, epoxidized vegetable oil and a catalyst, and drying in an oven in advance;
2) slowly and uniformly stirring the mosquito repellent and the anhydride, and gradually heating to 90-120 ℃ to obtain a mosquito repellent intermediate;
3) then adding epoxidized vegetable oil, heating to 150-180 ℃, and then adding a catalyst to obtain a toughening intermediate.
4. The toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing is characterized by comprising a high-molecular material, an auxiliary agent and the toughened intermediate in claim 1, wherein the high-molecular material is a high-molecular material with a carboxyl end group and comprises one or more of PBS, PLA, PBAT and PBSA.
5. The toughened mosquito-repellent polymer biodegradable composite material for 3D printing according to claim 4, wherein the composite material comprises 70-95 parts of polymer material, 0.5-2 parts of auxiliary agent and 5-30 parts of toughened intermediate.
6. A preparation method of a toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing is characterized by comprising the steps of blending the toughened intermediate and a high-molecular material in claim 1, adding an auxiliary agent, and extruding to obtain the toughened mosquito-repellent biodegradable composite material for 3D printing.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0410899A (en) * | 2003-06-06 | 2006-07-04 | Basf Ag | ester f, processes for preparing the same and for preparing a cross-linked hydrogel, polymer, cross-linked hydrogel, use of a polymer, composition of matter, and, uses of a reaction mixture and ester f |
| CN103696126A (en) * | 2013-11-25 | 2014-04-02 | 芜湖跃飞新型吸音材料股份有限公司 | Sound-absorbing cotton with mosquito avoiding function and preparation method thereof |
| CN104877293A (en) * | 2015-05-29 | 2015-09-02 | 江苏浩宇电子科技有限公司 | Mosquito-repelling 3D (three-dimensional) printing material and application thereof |
| CN105821508A (en) * | 2016-05-19 | 2016-08-03 | 陆建益 | Sea mud-plant composite sterilizing and mosquito repelling polypropylene fiber and preparation method thereof |
| CN108484396A (en) * | 2018-05-09 | 2018-09-04 | 中国林业科学研究院林产化学工业研究所 | Maleic rosin tetrahydrogeraniol ester and its preparation method and application |
| JP2019214545A (en) * | 2018-06-13 | 2019-12-19 | 遠東新世紀股▲ふん▼有限公司 | Manufacturing method of terephthalic acid bis(2-hydroxyethyl) |
-
2020
- 2020-12-18 CN CN202011501049.7A patent/CN112661638B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0410899A (en) * | 2003-06-06 | 2006-07-04 | Basf Ag | ester f, processes for preparing the same and for preparing a cross-linked hydrogel, polymer, cross-linked hydrogel, use of a polymer, composition of matter, and, uses of a reaction mixture and ester f |
| CN103696126A (en) * | 2013-11-25 | 2014-04-02 | 芜湖跃飞新型吸音材料股份有限公司 | Sound-absorbing cotton with mosquito avoiding function and preparation method thereof |
| CN104877293A (en) * | 2015-05-29 | 2015-09-02 | 江苏浩宇电子科技有限公司 | Mosquito-repelling 3D (three-dimensional) printing material and application thereof |
| CN105821508A (en) * | 2016-05-19 | 2016-08-03 | 陆建益 | Sea mud-plant composite sterilizing and mosquito repelling polypropylene fiber and preparation method thereof |
| CN108484396A (en) * | 2018-05-09 | 2018-09-04 | 中国林业科学研究院林产化学工业研究所 | Maleic rosin tetrahydrogeraniol ester and its preparation method and application |
| JP2019214545A (en) * | 2018-06-13 | 2019-12-19 | 遠東新世紀股▲ふん▼有限公司 | Manufacturing method of terephthalic acid bis(2-hydroxyethyl) |
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