KR101154178B1 - Manufacturing method of bio elastomer using vegetable oil - Google Patents
Manufacturing method of bio elastomer using vegetable oil Download PDFInfo
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Abstract
The present invention relates to a method for producing a bioelastomer, and more specifically, n-butyllithium as an initiator is added to a butadiene monomer and polymerized to form a polybutadiene; And it relates to a method for producing a bio-elastomer using a vegetable oil comprising the step of adding and synthesizing the vegetable oil to the polybutadiene. The production method according to the present invention can chemically modify the ends of the polymer to facilitate the synthesis with vegetable oil, using a living anion polymerization that can easily control the molecular weight and control the microstructure of the polymer. By efficiently synthesizing polymer and vegetable oil, it is possible to replace existing petroleum-derived polymer material, thereby providing an environment-friendly polymer material suitable for future industries.
Description
The present invention relates to a method for producing a bioelastomer that can chemically modify the end group of the polymer to be combined with a vegetable oil as an organic resource to produce a resource-circulating natural product-based elastomer, and improve physical properties.
Global trends in the 21st century are accelerating globalization, and international joint environmental regulations, oil resource depletion and rising demand, and climate change agreements are weakening the competitiveness of existing energy and chemical industries. In particular, the Kyoto Protocol, Europe's REACH, and the recent Bali Roadmap, which are part of a global effort to conserve the global environment by curbing greenhouse gas emissions such as carbon dioxide, It demands a fundamental solution to the existing energy / chemical industry which is centered. Natural gas or coal can be thought of as a substitute for petroleum in terms of price, but like oil, it is a finite resource and difficult to escape from environmental issues such as greenhouse gases.
On the other hand, as the plant resources are continuously produced in nature such as corn, sugar cane, woody plant resources, palm, and seaweed, biomass (generally referred to as organic matter of living organisms) is not only renewable but also environmentally friendly. It is emerging as an important resource to replace oil resources. Using biomass as a raw material, it combines biotechnological technology (using biocatalysts such as enzymes and yeast) with chemical technology to produce materials such as bio-based chemicals or biofuels. Biotechnology) is an area of a new industry, actively researching in the US and Europe.
Industrial biochemistry is a new type of bio-chemistry that uses biomass, which is produced by light energy repeatedly through plant photosynthesis, in contrast to the conventional chemical industry, which relies on petroleum resources, fossil raw materials. It can be called a convergence technology.
The chemical materials industry, including polymers, is now moving towards the development and production of bio-based plastics (bioplastics) that are manufactured using biomass as a raw material, in two respects: price and environmental protection. In the early stage of development, bioplastics have been neglected due to their lack of manufacturing technology due to their high price and poor physical properties, but recently, with the development of technology, manufacturing prices have decreased and quality improvement has progressed, so the market demand is rapidly increasing.
Bio-based polymers made from plant resources (renewable resources) such as biomass such as vegetable oils, woody plant resources, and starch are typical bioplastics, and these materials are called bioplastics (green plastics). Also do.
Existing petroleum-based chemical materials have a problem that generates a large amount of CO 2 when discarded after use, adversely affecting the human body and the environment, and there is a movement to convert petroleum-based chemical materials with these problems into bio-based chemical materials. . Under these circumstances, bioplastics are becoming an important industrial material.
Bio-based polymers are chemical materials that can minimize the generation of carbon dioxide, the main culprit of global warming, by using plant resources, which are representative biomass, as raw materials. Therefore, bio-based polymers can effectively cope with the carbon tax system under the Kyoto Protocol, which will enter into force in 2013, and thus become competitively priced chemicals. Representative of bio-based polymers using biomass, cellulose and starch, which are natural polymers, have already reached the stage of mature technology, and a large amount is used.
On the other hand, in the case of plant resource-based synthetic polymers, the technology has not reached the maturity stage, and only polylactide (PLA), which is recently evaluated as a representative biodegradable polymer, has been commercialized and entered the stage of mass production. Therefore, the current research and development to produce a variety of products required for the parts and materials industry using PLA is actively progressing around the world. In addition to PLA, there are various polymers that are currently entering the commercialization stage, and most biodegradable polyesters belong to them, and typical ones include PHB, PHA, and PTT. Polyurethane production using monomers derived from plant resources is also in the commercialization stage after much research. In addition, much research is being conducted on nylon, PBS, and PBT.
In order to solve the above problems, the present inventors have confirmed that the resource-based natural product-based elastomer can be prepared by modifying the end group of the polymer with a functional group and then combining with a vegetable oil. .
Accordingly, an object of the present invention is to modify the end of the polymer into a functional group to facilitate the synthesis with vegetable oil to produce a resource-recycling bio-elastomer, to improve the physical properties, to overcome the critical performance and environmentally friendly vegetable The present invention provides a method for producing a bioelastomer using oil.
In order to achieve the above object, the present invention comprises the steps of adding n-butyllithium as an initiator to the butadiene monomer and polymerizing to form a polybutadiene; And it provides a method of producing a bio-elastomer using a vegetable oil comprising the step of adding a vegetable oil to the polybutadiene and synthesized.
In one embodiment of the present invention, after the step of forming the polybutadiene, may further comprise the step of modifying the end of the polybutadiene carboxyl group or an amino group.
In one embodiment of the present invention, the modification may be performed for 1 to 2 hours at a temperature of 30 ~ 40 ℃.
In one embodiment of the present invention, when the carboxyl group is modified, carbon dioxide may be added to the polybutadiene to be modified by living anion polymerization.
In one embodiment of the present invention, when modifying the amino group, it can be modified by the living anion polymerization method by adding after synthesizing divinylbenzene and lithium-bis (trimethylsilylamide).
In one embodiment of the present invention, the vegetable oil may be any one selected from epoxidized soybean oil (ESO), epoxidized palm oil, epoxidized rapeseed oil and epoxidized sunflower seed oil.
In one embodiment of the present invention, the butadiene monomer is in the group consisting of 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene It may be any one selected.
In one embodiment of the present invention, the polybutadiene and vegetable oil is 1: 0.2 ~ 1 It can be mixed in proportion by weight.
In one embodiment of the present invention, the synthesizing step may be performed for 1 to 2 hours at a temperature of 30 ~ 40 ℃.
The bioelastomer manufacturing method using the vegetable oil according to the present invention can chemically modify the ends of the polymer to facilitate the synthesis with the vegetable oil, the molecular weight can be easily adjusted and the living can control the microstructure of the polymer (living) Anion polymerization has an effect of efficiently synthesizing polymers and vegetable oils.
In addition, the manufacturing method of the bioelastomer using the vegetable oil according to the present invention, by combining the polymer and the vegetable oil to produce a resource-circulating bioelastomer, the physical properties can be improved, the critical performance can be overcome, and the vegetable oil is used. By reducing the carbon dioxide emissions, it is possible to replace the existing petroleum-derived polymer material through this has the effect of providing an environmentally friendly polymer material suitable for future industries.
1 is a schematic diagram showing a method for producing a bioelastomer using a vegetable oil according to the present invention.
Figure 2 shows the IR spectrum of the epoxidized soybean oil (ESO) used in the present invention (C = O: 1820 ~ 1660cm -1 , epoxide (-COC-): 832.78 cm -1 ).
Figure 3 shows the results of GPC analysis of epoxidized soybean oil used in the present invention.
4 (a) to 4 (c) c show the results of GPC analysis of a polybutadiene modified with a carboxyl group according to the present invention. In FIG. 4 (a), the area ratio is (a)
5 and 6 show the results of GPC analysis of the bioelastomer according to the present invention.
Figure 7 shows the IR spectrum of the pure polybutadiene and the bioelastomer according to the present invention. Here, the blue peak represents pure polybutadiene and the red peak represents bioelastomer.
8 shows the results of NMR analysis of the bioelastomer according to the present invention, and FIG. 9 shows the results of NMR analysis of ESO.
The present invention is to reduce the CO 2 emissions through recycling the synthetic system of resource elastic materials in the future, and relates to the development of vegetable oil based to replace the polymer material derived from the existing petroleum.
Accordingly, the present inventors have secured a technology for manufacturing a resource-cycling bioelastomer using waste vegetable oil as a raw material of biomass, which is a renewable organic resource, and developed a technology for manufacturing an environmentally light polymer material suitable for future industries through a technology for overcoming critical performance. .
Accordingly, the present invention provides a method for producing a bioelastomer using a vegetable oil, characterized in that for producing a resource-recycling bioelastomer using a vegetable oil as a raw material.
In the present invention, 'bio elastomer' refers to a polymer produced using biomass, that is, a renewable organic resource, that is a vegetable oil, and a 'polymer manufactured using a vegetable oil' refers to canola, corn, cotton seed, Vegetable oils such as triglycerides obtained from plants such as linseed, olive, rapeseed, soybean, etc. are used as raw materials, and double bonds or other functional groups containing them are enzymatically and chemically A polymer prepared by converting the polymer into a state suitable for polymerization through a reaction, and polymerizing them using a ring-opening polymerization reaction, a condensation polymerization reaction, and a radical polymerization reaction.
Hereinafter, a method for producing a bioelastomer using the vegetable oil according to the present invention will be described in more detail.
The present invention provides a method that can be effectively combined with vegetable oil by introducing and modifying the functional group at the end of the polymer, and also living anion polymerization that can easily control the molecular weight and control the microstructure of the polymer It provides a method for synthesizing polybutadiene (polybutadiene) and vegetable oil.
More specifically, the method of preparing a bioelastomer using the vegetable oil of the present invention includes the steps of adding n-butyllithium as an initiator to the butadiene monomer and polymerizing to form a polybutadiene; And adding vegetable oil to the polybutadiene and synthesizing it.
In addition, after the step of forming the polybutadiene, further comprising the step of modifying the end of the polybutadiene carboxyl group or an amino group.
In the present invention, 'butadiene' is an unsaturated hydrocarbon (C 4 H 6 ) consisting of four carbon atoms and six hydrogen atoms, and has two double bonds in a straight chain structure composed of four carbon atoms. There are two isomers of 2-butadiene and 1,3-butadiene. 1,2-butadiene is also called methylalene, and generally, butadiene refers to 1,3-butadiene. It did not exist in nature and was first identified in 1863 in a gas produced by pyrolysis of fusel oil. When pressure is applied as a colorless and odorless flammable gas, it liquefies easily and is easy to ignite.
Industrially, a method of dehydrogenating normal butane is used, and there are a method of dehydrogenating normal butane in one step and a method of dehydrogenating in two steps (Philips method). In addition, the method of separating petroleum oil from the gas produced when ethylene is produced by pyrolysis, the method of dehydrogenating butylene (shell method and Dow method), and the method obtained from aldehyde and ethanol have been industrialized. Structurally, since they have the simplest paired double bond, π electrons of two double bonds interact with each other through a single bond. Thus, a single bond has a double bond and a double bond has a single bond, which is consistent with a structure derived from resonance theory. Diene synthesis is performed with maleic anhydride, and benzene derivatives are formed by thermal polymerization. It is an important material as a raw material of synthetic rubber, and it is a raw material of styrene-butadiene rubber (SBR), butadiene acrylonitrile rubber (NBR), polybutadiene, etc., and also as a raw material such as chloroprene, adiponitryl, maleic anhydride, etc. Used.
Butadiene polymers are highly dependent on the microstructure showing the position and stereochemical properties of -C = C- double bonds in the repeating units of the polymer chain, and the macrostructure indicating branching, molecular weight and molecular weight distribution. According to the stereoregular structure, the Tg of the butadiene polymer depends mainly on the 1,2 (vinyl) content rather than the cis and trans content. In order to be used as a rubber material, it is preferable to have a low Tg value, but to have a high cis-1,4- content, but is preferably polybutadiene mixed with cis / trans so as not to be crystalline. Butadiene polymer has a variety of microstructures and copolymer types in terms of molecular structure, it is possible to make an elastic body having a variety of physical properties and accordingly wide range of use.
For example, Carboxyl Terminated Poly Butadiene (CTPB), which is widely used at present, is widely used in rocket propellant binders, coating industries, etc., and Hydroxyl Terminated Poly Butadiene (HTPB) is used as a solid propellant. Used for binders, adhesives, wire coating, etc. However, to date, there is no commercially available technology for preparing elastomers using waste vegetable oils based on polybutadiene having carboxyl group (CTPB), hydroxyl group (HTPB) and amino group (NTPB) terminal.
In order to prepare a bioelastomer using the vegetable oil according to the present invention, first, an initiator is added to a butadiene monomer in a high pressure reactor and polymerized to form a polybutadiene. In this case, the butadiene monomer used in the present invention is selected from 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene And copolymers with styrene, acrylonitrile or other monomers.
In addition, n-butyllithium which is a bifunctional initiator can be used as an initiator of a polymerization reaction, and the molecular weight of polybutadiene can be adjusted.
Next, the present invention is characterized by chemically modifying the ends of the polybutadiene, through which the vegetable oil may be well bonded to the polybutadiene ends when the polybutadiene and the epoxidized vegetable oil are synthesized later. Specifically, the terminal of the polybutadiene may be modified with any one of a carboxyl group (-COOH), an amino group (-NH 2 , -NR 2 ), and a hydroxyl group (-OH), and can be prepared by free radical, living anion polymerization, or the like. Can be. In the present invention, when modifying the end of the polybutadiene, it is preferable to modify by reacting for 1 to 2 hours at a temperature of 30 ~ 40 ℃.
For example, when modifying the terminal of the polybutadiene to a carboxyl group, carbon dioxide is added to the polymerized polybutadiene to use an anionic polymerization method (see
<
<
In addition, when the terminal of the polybutadiene is modified with an amino group, divinylbenzene and lithium-bis (trimethylsilylamide) may be synthesized and added to be modified by living anion polymerization (see
<
Next, a vegetable oil is added to the polybutadiene modified at the end, and synthesized using a living anion polymerization method. At this time, the reaction is carried out for 1 to 2 hours at a temperature of 30 ~ 40 ℃.
In the present invention, polybutadiene and vegetable oil may be mixed at a ratio of 1: 0.2 to 1, but when mixed outside the above range, a bioelastomer of desired physical properties may not be obtained.
In the present invention, the vegetable oil may be a natural oil extracted from a plant such as canola, corn, cotton seed, linseed, olive, rapeseed, soybean, and the like, and is a waste vegetable oil that is used and disposed of. You can also use In the present invention, waste vegetable oil is used for environmentally-friendly effects and reduction of waste disposal costs. However, it will be apparent that the same effect can be obtained even when using ordinary vegetable oil. In the present invention, the term 'vegetable oil' and Use a combination of 'vegetable oil'.
The vegetable oil is preferably an epoxidized vegetable oil, and more specifically selected from epoxidized soybean oil (ESO), epoxidized palm oil, rapeseed oil, and epoxidized sunflower oil. Either one can be used.
It is preferable that all of the above series of reactions proceed in a high pressure reactor. Through the above method, the terminal of the polybutadiene and the epoxy group of the epoxidized vegetable oil may react to obtain a high molecular weight bioelastomer.
On the other hand, the manufacturing method according to the present invention as described above can be easily modified by chemically modifying the end of the polymer compound with vegetable oil, the molecular weight can be easily adjusted and can control the microstructure of the polymer (living Anionic polymerization can be used to efficiently synthesize polymers and vegetable oils. Accordingly, by combining the polymer and the vegetable oil to produce a bio-elastic material of the resource recycling type, it is possible to realize the improvement of physical properties, to overcome the critical performance, and to reduce the carbon dioxide emissions by using the vegetable oil, thereby It can replace petroleum-derived polymer materials to provide environmentally friendly polymer materials suitable for future industries.
Therefore, the bioelastomer according to the present invention has excellent market competitiveness in accordance with the trend of moving the macro trend of the polymer material industry to green growth-type environmentally friendly materials, and thus, the medical, footwear material industry, automobile parts, electrical and electronic parts industries. It can be applied and applied to various fields.
Hereinafter, the present invention will be described in detail with reference to embodiments and drawings. However, these examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.
< Example 1>
Component Analysis of Vegetable Oils Used in the Present Invention
The inventors selected palm oil, rapeseed oil, and soybean oil as vegetable oils and analyzed their components.
As a result, as shown in Table 1 below, fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid were detected as main components in vegetable oils.
Among them, as a result of measuring the IR spectrum of soybean oil, as shown in Figure 2, it was confirmed that it consists of four epoxy groups (epoxy group) and six carboxyl groups, the epoxy group at 832.78 cm -1 I could confirm it.
Accordingly, the present inventors selected and used soybean oil (ESO) having an epoxy group because the epoxy group has a property of reacting well with an amino group and a carboxyl group.
In addition, GPC analysis of the epoxidized soybean oil (ESO), the molecular weight is 4300, NMR analysis, the ratio of the epoxy group and carboxyl group was 4: 6 (see Fig. 3).
< Example 2>
Polybutadiene Terminal modification
The chain end reactor of the functional polybutadiene can be modified to have various functional groups such as -OH, -COOH, -NH 2 , -NR 2, and can be prepared by free radical and living anion polymerization.
<2-1> Carboxyl Modification to the end
In the present embodiment, the polybutadiene terminal was modified to a carboxyl group (-COOH) by living anion polymerization, and a polybutadiene was prepared by using a terminal blockade method of a living difunctional anion by CO 2 in
<
First, n-butyllithium was added as an initiator to the butadiene monomer in THF as a polar solvent and subjected to anionic polymerization. Next, carbon dioxide (CO 2 ) was added to the polybutadiene, and then reacted for 120 minutes at 30 ° C. under a pressure of 2.0 MPa in a high pressure reactor to modify the ends of the polybutadiene group with a carboxyl group. At this time, all conditions were the same, and the amount of THF was changed to 25, 50, and 100 ml as shown in Table 2, to prepare carboxyl terminal polybutadiene, respectively.
The molecular weights of the three materials thus prepared were measured. In the synthesis conditions of the carboxyl terminal polybutadiene having a low molecular weight, as the other conditions change the amount of THF in the same state, the area ratio of Example 1 is COOH 71% (FIG. 4A), and Example 2 is
Through the above results, in the present invention, it is thought that the elastomer can be prepared using a butadiene polymer having a reactive functional group attached to the chain terminal of the low molecular weight polymer, and the characteristics of the elastomer can be controlled by changing the purity of the carboxyl group. .
<2-2> Modification to amino terminus
In the present embodiment, the polybutadiene terminal was modified with an amino group (-NH 2 , -NR 2, etc.), and a process of modifying the terminal of the polybutadiene with an amino group was shown in <
First, n-butyllithium was added to the butadiene monomer and polymerized to prepare polybutadiene. Next, after synthesis of DVB (divinylbenzene) and Lithium-bis (trimethylsilylamide) was added, and then reacted for 60 minutes at 35 ℃ under a pressure of 2.0MPa in a high pressure reactor to modify the terminal of the polybutadiene to a carboxyl group. At this time, HCl / MeOH was added to terminate the reaction, washed with NaOH.
<Scheme 6>
< Example 3>
Reformed Polybutadiene ESO Synthesis of
The present inventors synthesized carboxyl-modified polybutadiene and ESO to prepare a bioelastomer, by adjusting the content of n-butyllithium and the content of ESO as shown in Table 3 below.
15,000
10,000
7,500
5,000
3,000
1,500
<Scheme 7> is a chemical scheme showing the synthesis process of polybutadiene and ESO.
<Reaction Scheme 7>
< Example 4>
Molecular Structure Design
The present inventors analyzed the arm chains and weight average molecular weights of the materials tested under the conditions of Table 3, and the results are shown in Tables 4 to 6 below.
76
10
1.1
18,500
62
16
1.2
11,360
49
13
2.1
9,523.6
52
14
2.2
7,000
52
14
3.2
9,523.6
67
13
3.1
7,000
As a result, when the molecular weight range of the polybutadiene is 10,000 to 15,000 (Table 4), most of the material was stabilized while increasing the content of ESO to 5 to 20% with bio polybutadiene having 1-arm. However, when the molecular weight ranges from 5,000 to 10,000 (Table 5), the substance is a polymer containing all of 1-arm, 2-arms and 3-arms, and the 2-arms star-branch polymer shows 60% and the molecular weight range. Is 1,000 to 5,000 (Table 6), most of the materials are 3-arms star-branch polymers, and the other part consists of 4-arms.
Depends on the star-branch polymer, the lower the molecular weight of polybutadiene, the more arm chains. Therefore, the lower the molecular weight of polybutadiene, the easier the synthesis of bioelastomers.
< Example 5>
Molecular weight control by temperature and catalyst
The present inventors experimented as follows to examine the effects of synthesis temperature and catalyst in the production of bioelastomers.
The experiment was performed by changing the temperature under the same conditions as in Table 7 to see the effect of the synthesis temperature, by changing the amount of catalyst by fixing the temperature to ℃ as shown in Table 8 to see the effect of the catalyst The experiment was performed.
As a result, the effect of synthesis temperature decreased when the temperature increased under the same conditions (see Table 7), and the effect of the catalyst was to change the amount of catalyst by fixing the temperature at ℃, and the amount of catalyst It was confirmed that the molecular weight increased with increasing (see Table 8).
< Example 6>
Of the bioelastomer according to the present invention GPC analysis
The GPC analysis results of the bioelastomer prepared when the molecular weight of polybutadiene is 10000 and the addition ratio of ESO is 10% are shown in FIG. The results are shown in FIG.
As a result, when the polybutadiene and ESO were polymerized, the molecular weight was increased than the general polybutadiene (right peak), and it was confirmed that various groups were bonded.
< Example 7>
Of the bioelastomer according to the present invention IR Spectral analysis
The IR spectra of the bioelastomer and pure polybutadiene prepared by synthesizing polybutadiene and ESO prepared according to the present invention are shown in FIG. 7.
As a result, referring to Figure 7, in the case of pure polybutadiene, no epoxy group was seen, and -C-OH group appeared at 1169 cm -1 . On the other hand, ESO can see the epoxy group at 832.78 cm -1 (see Fig. 2), it was confirmed that the epoxy group appears in a similar position in the bio-elastomer prepared by synthesizing polybutadiene and ESO.
Through the above results, it was confirmed that the ESO is bonded to the polybutadiene to prepare a bio-elastomer.
< Example 8>
Of the bioelastomer according to the present invention NMR Spectral analysis
The NMR spectra of bioelastomer and ESO prepared by synthesizing polybutadiene and ESO prepared according to the present invention were analyzed, and the results are shown in FIGS. 8 and 9.
As a result, as shown in Figure 8, the bio-elastomer according to the present invention was reduced in the movement of the epoxy group as shown in δ2.9 ~ 3.2 ppm, it was able to confirm the alkene of polybutadiene at δ4 ~ 6 ppm . In addition, it was confirmed that the (a) -OH group appeared at δ0.93 due to the ring-opening reaction.
So far I looked at the center of the preferred embodiment for the present invention. Those skilled in the art will appreciate that the present invention can be implemented in a modified form without departing from the essential features of the present invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.
Claims (9)
Modifying the terminal of the polybutadiene with a carboxyl group or an amino group; And
Adding and synthesizing a vegetable oil to the polybutadiene,
When modifying the end of the polybutadiene to a carboxyl group When carbon dioxide is added to the polybutadiene to modify by a living anion polymerization method and the end of the polybutadiene to modify the amino group divinylbenzene and lithium-bis (trimethylsilyl Amide) [Lithium-bis (trimethylsilylamide)] after the synthesis of the method of producing a bio-elastomer using a vegetable oil, characterized in that it is modified by a living anion polymerization method.
The modification is a method for producing a bio-elastomer using vegetable oil, characterized in that carried out for 1 to 2 hours at a temperature of 30 ~ 40 ℃.
The vegetable oil is any one selected from epoxidized soybean oil (ESO), epoxidized palm oil, epoxidized rapeseed oil and epoxidized sunflower seed oil.
The butadiene monomer is a vegetable, characterized in that any one selected from the group consisting of 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene Method for producing a bioelastomer using oil.
The polybutadiene and vegetable oil is 1: 0.2 ~ 1 Method for producing a bio-elastomer using a vegetable oil, characterized in that mixed in the ratio of weight ratio.
The synthesizing step is a method for producing a bio-elastomer using waste vegetable oil, characterized in that performed for 1 to 2 hours at a temperature of 30 ~ 40 ℃.
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| KR101409121B1 (en) * | 2011-04-13 | 2014-06-18 | 경상대학교산학협력단 | Preparation method of biomass-elastomer based on waste vegitable oils |
| KR102566313B1 (en) * | 2018-08-31 | 2023-08-10 | 주식회사 엘지화학 | Method for preparing a long chain aliphatic carboxylic acid |
| KR102555382B1 (en) * | 2018-09-28 | 2023-07-12 | 주식회사 엘지화학 | Method for preparing an long chain carboxylic acid |
| EP4276147A1 (en) * | 2021-11-12 | 2023-11-15 | LG Chem, Ltd. | Rubber composition comprising bioelastic body, and preparation method therefor |
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| KR100466200B1 (en) | 2002-09-02 | 2005-01-13 | 금호석유화학 주식회사 | End-modified styrene-diene block copolymer by multireactive coupling agent |
| US20060094800A1 (en) | 2004-10-29 | 2006-05-04 | Lei Jong | Material compositions for reinforcing ionic polymer composites |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101426606B1 (en) | 2012-10-02 | 2014-08-05 | 경상대학교산학협력단 | Method of preparing biomass elastomer based on vegetable oil |
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