WO2022149646A1 - Résine de pva-lignine respectueuse de l'environnement estérifiée, procédé de préparation s'y rapportant et composite renforcé par des fibres naturelles respectueux de l'environnement obtenu à partir de celle-ci - Google Patents

Résine de pva-lignine respectueuse de l'environnement estérifiée, procédé de préparation s'y rapportant et composite renforcé par des fibres naturelles respectueux de l'environnement obtenu à partir de celle-ci Download PDF

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WO2022149646A1
WO2022149646A1 PCT/KR2021/000535 KR2021000535W WO2022149646A1 WO 2022149646 A1 WO2022149646 A1 WO 2022149646A1 KR 2021000535 W KR2021000535 W KR 2021000535W WO 2022149646 A1 WO2022149646 A1 WO 2022149646A1
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eco
lignin
pva
friendly
resin
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PCT/KR2021/000535
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English (en)
Korean (ko)
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김재환
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인하대학교 산학협력단
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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
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin

Definitions

  • the present invention relates to an esterified eco-friendly PVA-lignin resin, a manufacturing method thereof, and an eco-friendly natural fiber-reinforced composite obtained therefrom. More specifically, it relates to a method for producing an esterified lignin-based eco-friendly resin by mixing lignin and PVA, adding a crosslinking agent, and applying heat, and an eco-friendly natural fiber-reinforced composite using the resin.
  • the PVA-lignin resin of the present invention has excellent mechanical properties and adhesion to natural fibers while being environmentally friendly.
  • Eco-friendly fiber-reinforced composites are becoming increasingly important due to their potential to replace petroleum-based materials in an era where energy and the environment are important.
  • resins must also be eco-friendly.
  • As candidates for eco-friendly resins lignin, cardanol, vanilin, fatty acid, isosobide, tannin, and plant oil are thermosetting or thermoplastic. is used as a material.
  • lignin is an eco-friendly polymer that is produced the most in nature after cellulose, and is attracting attention as an eco-friendly material due to its sustainable resources, biodegradability, low price, and abundance.
  • lignin is mainly located between the cell wall and the adjacent cell wall.
  • Lignin a phenolic polymer
  • the thermosetting polymer using it has improved thermal and mechanical properties.
  • lignin has a free OH-group, has low solubility, and has a chemically complex structure, so it is not easy to make it into a thermoplastic polymer. Therefore, efforts are being made to improve the properties of lignin by modifying it.
  • lignin-based thermosetting polymers were prepared by allylation of kraft lignin and crosslinking with thiol-ene.
  • Polyvinyl alcohol (PVA) is often used to crosslink lignin to increase bonding strength, thermal stability, and mechanical strength.
  • PVA polyvinyl alcohol
  • eco-friendly fibers containing cellulose as a main component are used.
  • Cellulose is the most abundant organic material in nature, with about 150 billion tonnes of which is produced annually in nature.
  • Wood fibers are composed of macrofibers having a diameter of less than microns, which in turn are hierarchically composed of microfibers and nanofibers .
  • Cellulose is renewable, biodegradable, and has excellent thermal stability. In addition, it has various advantages such as low price and high strength.
  • Cellulose fibers are composed of microfibers called cellulose nanofibers (CNFs) of high crystalline quality. These highly crystalline cellulose nanofibers generally have a width of 5 to 200 nm and a length of several micrometers, and have unique physical and chemical properties.
  • CNF is very suitable for eco-friendly fiber-reinforced composites.
  • resin in order to manufacture such an eco-friendly fiber-reinforced composite, resin must also be an eco-friendly material.
  • Epoxy is widely used in fiber-reinforced composites because of its good mechanical properties and chemical and thermal stability.
  • commercial epoxies are not completely environmentally friendly, biodegradable, and expensive.
  • lignin-based resins developed through various modifications and functionalizations so far have disadvantages in that they have low mechanical properties and thermal stability for use in eco-friendly fiber-reinforced composites.
  • PVA-lignin resin has excellent eco-friendliness, but has problems in mechanical properties, adhesive strength, thermal stability and hydrophobicity still low, and therefore there is still a limit to use in natural fiber-reinforced composites.
  • the present invention is an economical, environmentally friendly, and easy mass production method, using citric acid (CA) as a crosslinking agent, adding it to the PVA-lignin compound and esterifying it,
  • An object of the present invention is to provide a method for manufacturing an esterified PVA-lignin eco-friendly resin with high mechanical properties and adhesive strength.
  • an object of the present invention is to provide an eco-friendly natural fiber-reinforced composite material obtained by using an esterified eco-friendly PVA-lignin resin.
  • the mixture and the crosslinking agent may be mixed in a weight ratio of 6:4 to 8:2.
  • the polyvinyl alcohol and the lignin may be mixed in a weight ratio of 6:4 to 7:3.
  • the object of the present invention is achieved by the environmentally friendly PVA-lignin resin produced by the above method.
  • the resin may have a tensile strength of 150 MPa or more, an elastic modulus of 5 GPa or more, a breaking strain of 6% or more, an adhesive strength of 20 MPa or more, and hydrophobicity.
  • the object of the present invention is achieved by a natural fiber-reinforced composite prepared by impregnating the composite made of natural fibers in the eco-friendly PVA-lignin resin prepared by the above method.
  • the present invention solves the disadvantages of the PVA-lignin resin, and in order to solve the problems of the prior art as described above, the PVA-lignin compound is esterified using a crosslinking agent such as citric acid to form a PVA-CA-lignin By strengthening the bond, the mechanical properties, adhesive strength, thermal stability, and hydrophobicity of e-PCL resin were improved.
  • the eco-friendly resin is esterified by applying temperature without using a catalyst, so it is economical, eco-friendly, and easy to mass-produce, so it will be used in more diverse fields.
  • 1 and 2 are FTIR spectra according to the citric acid crosslinking agent content of the e-PCL resin prepared according to Example 1 of the present invention and heating time to 180°C.
  • Example 3 is a tensile stress-strain curves according to the citric acid content of the e-PCL resin prepared according to Example 1 of the present invention.
  • Example 5 is a view showing the water contact angle results according to the citric acid content of the e-PCL resin prepared according to Example 1 of the present invention.
  • Example 7 shows the fractured cross-section of the e-PCL resin and CNF fiber-reinforced composite prepared according to Example 2 of the present invention.
  • the present invention relates to a method for producing an eco-friendly PVA-lignin resin.
  • the present invention comprises the steps of preparing hydrogenated PVA-lignin (H-PCL) by mixing polyvinyl alcohol (PVA) and lignin and then reacting with citric acid as a crosslinking agent; and preparing an esterified PVA-lignin (e-PCL) resin obtained by heating and esterifying the same.
  • H-PCL hydrogenated PVA-lignin
  • PVA polyvinyl alcohol
  • e-PCL esterified PVA-lignin
  • e-PCL is prepared by first mixing PVA-lignin and mixing a crosslinking agent such as citric acid to make H-PCL with hydrogen bonding, and esterification by raising the temperature to 160-200°C, preferably 180°C.
  • the present invention does not use any catalyst for esterification, and thus provides a manufacturing method that is economical, eco-friendly and easy to mass-produce.
  • the crosslinking agent (CA) represented in Scheme 1 is citric acid.
  • the eco-friendly resin prepared according to the present invention has a tensile strength of 150 MPa or more, preferably 200 MPa or more, more preferably 300 MPa or more, and an elastic modulus of 5 GPa or more, preferably 7 GPa or more, more preferably 10 GPa or more, the strain at break is 6% or more and 15% or less, and the adhesive strength is 20 MPa or more, preferably 30 MPa or more, more preferably 50 MPa or more.
  • the present invention provides a method of manufacturing an eco-friendly natural fiber-reinforced composite by impregnating a composite material made of natural fibers such as CNF in the esterified e-PCL resin, laminating it and drying it.
  • the method comprises the steps of wet spinning a cellulose nanofiber (CNF) suspension, followed by orientation, tensile, and drying to prepare a CNF filament (CLF), manufacturing a mat woven of the CLF; And after impregnating the mat with e-PCL resin, stacking 2 to 5 mats, drying at 60 to 100 ° C., and applying a pressure of 8 MPa and heat of 180 ° C to the dried mat to form and drying in a vacuum oven at 180° C. for 1 hour.
  • CNF cellulose nanofiber
  • CLF CNF filament
  • the flexural strength of the eco-friendly natural fiber-reinforced composite is 200 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, and the elastic modulus is 20 GPa or more, preferably 30 GPa or more, more preferably 50 GPa or more. More than that.
  • a 10% (w/w) PVA solution, a 10% (w/w) lignin solution, and a 10% (w/w) citric acid solution were prepared, respectively, and stirred with ultrasonic waves.
  • the prepared 10% (w/w) PVA solution and lignin solution are mixed in a weight ratio of 65:35 and centrifuged to remove undissolved particles.
  • the PVA-CA-lignin thus prepared is called hydrogen-bonded H-PCL resin.
  • the hydrogen-bonded H-PCL resin is placed in a vacuum oven and heated at 180° C. for 1 hour to 12 hours to perform esterification.
  • the esterified PVA-CA-lignin is named 'e-PCL resin'.
  • FTIR spectroscopy was measured to confirm the ester bond of the prepared H-PCL and e-PCL resins.
  • 1 is an FTIR spectra of e-PCL according to the content of citric acid (CA).
  • 2 is an FTIR spectra of e-PCL as a function of esterification time.
  • 'PL' indicates a mixture of PVA and lignin.
  • the e-PCL resin shows a new peak of ester bonds at 1729 cm -1 . It can be seen that the 1701 cm -1 peak corresponding to the hydrogen bond between the COOH and -OH groups in the H-PCL resin shifted to a high wavenumber of 1729 cm -1 . On the other hand, it can be seen that the broad peak of H-PCL was changed to a sharp peak at 3418 cm -1 , which was caused by elongation of the -OH group. It can be seen that the strength of the ester bond increases as the content of citric acid increases. As a result of the FTIR spectral spectrum, it can be seen that a crosslinking was formed between PVA and lignin by the crosslinking agent of citric acid.
  • Table 3 shows a stress-strain diagram according to the citric acid content (10-40% (w/w)) of E-PCL.
  • Table 1 shows a comparison of the tensile strength of conventional PVA-lignin-based resins. The tensile strength was measured according to the conventional film tensile test method (ASTM D1938) after casting the resin into a film and drying it to make a specimen. In the e-PCL resin of the present invention, the tensile strength increases until the content of citric acid is 30% (w/w) and decreases thereafter. Because.
  • the tensile strength at 30% (w/w) of citric acid is 184 MPa, which is the best among lignin-based resins, and is about 4.5 times higher than that of PVA-lignin resin.
  • the modulus of elasticity, elongation at break, and toughness of e-PCL resin containing 30% citric acid are 2.6 times, 4 times, and 20 times greater than those of PVA-lignin resin, respectively.
  • Such a large toughness modulus is a very advantageous property for natural fiber reinforced composites as a resin that can absorb a lot of breaking energy.
  • WCA water contact angle
  • FIG. 6 shows the test results of the adhesion strength of e-PCL resin with CNF.
  • Adhesive strength test followed the conventional Lap Shear Joint (LSJ) test, and after applying resin to the 2 mm part from the tip of the 10 mm x 30 mm CNF film, overlapping the ends of the two CNF films, and obtaining a tensile test.
  • the joint strength is obtained by dividing the breaking load by the contact area of the two films.
  • the bonding strength of e-PCL resin with a citric acid content of 30 wt% is 31.9 MPa, which is 7.4 and 4.7 times greater than 4.3 MPa of PVA-lignin resin and 6.8 MPa of PVA-lignin resin esterified with malic acid, respectively. .
  • This indicates that e-PCL resin has excellent bonding strength with natural fibers containing cellulose as a main component.
  • An embodiment of manufacturing a natural fiber-reinforced composite using a CNF filament (CNF Long Filament, CLF) and an e-PCL resin follows a conventional fiber-reinforced composite manufacturing process.
  • CLF manufactures eco-friendly high-strength long fibers by wet spinning a CNF suspension in an alcohol-based aqueous solution and then aligning, stretching, and drying the nanocellulose in the same manner as in the prior art of the present applicant (Korean Patent No. 10-2063100).
  • the CLF prepared in this way has a tensile strength of 480 MPa and an elastic modulus of 40 GPa.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne : une résine de PVA-lignine estérifiée obtenue par mélange d'un PVA, de lignine et d'un agent de réticulation et estérification du mélange par application de chaleur ; un composite renforcé par des fibres naturelles utilisant cette résine ; et un procédé de préparation respectueux de l'environnement s'y rapportant. La résine respectueuse de l'environnement et le composite renforcé par des fibres naturelles selon la présente invention ont une résistance à la traction élevée, un module d'élasticité élevé, une déformation à la rupture élevée et une force d'adhésion élevée et un excellent caractère hydrophobe.
PCT/KR2021/000535 2021-01-08 2021-01-14 Résine de pva-lignine respectueuse de l'environnement estérifiée, procédé de préparation s'y rapportant et composite renforcé par des fibres naturelles respectueux de l'environnement obtenu à partir de celle-ci WO2022149646A1 (fr)

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KR10-2021-0002589 2021-01-08
KR1020210002589A KR102434379B1 (ko) 2021-01-08 2021-01-08 에스테르화된 친환경 pva-리그닌 레진, 이의 제조 방법 및 이로부터 얻어지는 친환경 천연섬유강화 복합재

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103467759A (zh) * 2013-07-17 2013-12-25 东北林业大学 一种工业碱木质素/聚乙烯醇交联薄膜的制备方法
CN104497341A (zh) * 2015-01-08 2015-04-08 江南大学 一种光交联聚乙烯醇/木质素PVA/lignin复合膜的制备方法
US20160002467A1 (en) * 2013-02-11 2016-01-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermoplastic polymer compounds with low-molecular lignins, method for the production thereof, moulded articles and also uses
CN110240774A (zh) * 2019-06-21 2019-09-17 华南理工大学 一种高强度木质素/聚乙烯醇复合抗菌水凝胶及制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160002467A1 (en) * 2013-02-11 2016-01-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermoplastic polymer compounds with low-molecular lignins, method for the production thereof, moulded articles and also uses
CN103467759A (zh) * 2013-07-17 2013-12-25 东北林业大学 一种工业碱木质素/聚乙烯醇交联薄膜的制备方法
CN104497341A (zh) * 2015-01-08 2015-04-08 江南大学 一种光交联聚乙烯醇/木质素PVA/lignin复合膜的制备方法
CN110240774A (zh) * 2019-06-21 2019-09-17 华南理工大学 一种高强度木质素/聚乙烯醇复合抗菌水凝胶及制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KO HYUN-U, ET AL.: "Esterified PVA-lignin resin by maleic acid applicable for natural fiber reinforced composites", J. APPL. POLYM. SCI., vol. 137, no. 26, 27 December 2019 (2019-12-27), XP055949767, DOI: 10.1002/app.48836 *

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KR20220100299A (ko) 2022-07-15

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