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WO2024177598A1 - Modification de la paroi de cellules ligneuses avec de l'acide polylactique hydrophobe - Google Patents

Modification de la paroi de cellules ligneuses avec de l'acide polylactique hydrophobe Download PDF

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Publication number
WO2024177598A1
WO2024177598A1 PCT/TR2024/050100 TR2024050100W WO2024177598A1 WO 2024177598 A1 WO2024177598 A1 WO 2024177598A1 TR 2024050100 W TR2024050100 W TR 2024050100W WO 2024177598 A1 WO2024177598 A1 WO 2024177598A1
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WO
WIPO (PCT)
Prior art keywords
wood
lactide
samples
modified
modification method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/TR2024/050100
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English (en)
Inventor
Mahmut Ali ERMEYDAN
Eylem DİZMAN TOMAK
Ahmet Can
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bursa Teknik Universitesi
Original Assignee
Bursa Teknik Universitesi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from TR2023/002022 external-priority patent/TR2023002022A1/tr
Application filed by Bursa Teknik Universitesi filed Critical Bursa Teknik Universitesi
Publication of WO2024177598A1 publication Critical patent/WO2024177598A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B27K3/0292—Processes; Apparatus involving an additional treatment during or after impregnation for improving fixation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/001—Heating
    • 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
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the invention relates to the grafting of lactide monomer, obtained from lactic acid obtained by fermentation of carbohydrate resources such as corn, into the wood cell wall by ring-opening reaction, thus modifying the cell walls by filling them with hydrophobic polylactic acid (PLA).
  • lactide monomer obtained from lactic acid obtained by fermentation of carbohydrate resources such as corn
  • Wood is one of the oldest building materials used in buildings and is used in many areas, but the fact that this material is hydrophilic, can be degraded by biological organisms, can change its dimensions by being affected by the humidity of the environmental conditions, and can be affected by ultraviolet (UV) light and undergo photo-degradation limits its utilization.
  • UV ultraviolet
  • One of these wood modification methods is heat treatment of wood material. Heat treatment of wooden material attracts great attention as it is an environmentally friendly wood preservation method. After being subjected to heat treatment, the water absorption of wood material may decrease and it may become more resistant to biological attacks. Additionally, it becomes more dimensionally stable compared to non-heat-treated material. However, there is a decrease in the mechanical properties of wood. Heat treatment has different effects on wood obtained from different species.
  • Biodegradable or natural compounds such as PCL, ACPC, low molecular weight PLA, PGA, PBS and PBA, polyglycerol succinate, sorbitol, citric acid, extractives, vegetable oils, waxes, natural resins, chitin and chitosan, as well as biobased renewable and/or biodegradable polymers.
  • Bio-polyesters such as PLA, PGA, PBS, PBA, PCL may enter the wood cell wall and block the hydroxyl groups of the wood.
  • PCL modification which is a biodegradable polymer that undergoes in-situ modification of wood through a ring-opening reaction like lactide, provides wood with a dimensional stability of up to 60% and a water repellency effect of up to 50%. It was determined that the sample surfaces retained their color better after UV aging compared to the reference samples. A very good resistance has been achieved against white and brown rot fungi that degrade wood. The need for further studies has been expressed in terms of making the modification conditions under lower temperature conditions, preventing the formation of cracks in the sample cross-sections and improving the conditions of repeated use of the solution.
  • CN1 15212985A discloses a polylactic acid modified plastic preparation device comprising a polylactic acid preparation technology area including a soaking tank. It is explained that lactic acid is produced through fermentation of corn.
  • CN1 15216129A The technical field of environmentally friendly biodegradable materials is explained in the patent document with application number. A heat-resistant bio-based degradable composite material and its preparation method are described. CN1 15109336A The patent document with application number describes the modified bauxite washing mud reinforced wood-plastic composite material and its preparation method.
  • CN1 15093716A The patent document belongs to the field of wood-plastic composite technology. Specifically, it includes a bio-based wood-plastic composite material and its preparation method.
  • CN1 15073902A The patent document describes an environmentally friendly method for the preparation of a lightweight thermal insulating polylactic acid foam material.
  • Wood paint coatings are included in the patent document. It includes a particularly anti-corrosion environmental protection wood paint coating and its preparation method.
  • CN1 14939917A Artificial fiber board technology is explained in the patent document. Particularly wet resistant wood was described as a three-layer board. Moisture-resistant three-layer wooden board is formed out of moisture-resistant magnesium sulfur cementitious material as an inorganic adhesive.
  • the present invention aims to eliminate the above-mentioned problems and make a technical innovation in the relevant field.
  • the main purpose of the invention is to graft the lactide monomer, which is generally obtained from lactic acid by fermentation of corn, into the wood cell wall through a ringopening reaction, thus modifying the cell wall by filling the voids with hydrophobic polylactic acid (PLA).
  • PLA polylactic acid
  • Another purpose of the invention is to provide a solution to the problem of swelling/shrinking cycle according to the humidity conditions of the environment in which it is located, which is attributed as the most important disadvantage of wood.
  • Another aim of the invention is to present an effective and permanent production method that provides resistance against fungi that cause rotting in wood and does not have any leaching problems.
  • Another purpose of the invention is to increase the service life of the wooden product in areas of use above flood level.
  • Another purpose of the invention is to offer an environmentally friendly approach to ensure more rational and efficient use of decreasing forest resources by extending the lifespan of wood.
  • the present invention aims to increase the water repellency and dimensional stabilization properties of wood; It is a wood modification method that aims to reduce water absorption and void ratio of wood in order to reduce the amount of moisture required for fungi that rot wood. According to this; a) impregnating wood samples with monomer solution under vacuum to cause the cell walls to swell, b) keeping the impregnated samples for at least 1 day for diffusion, c) heating the treated wood to a temperature in the range of 105-120°C in a closed system to carry out the polymerization process,
  • the production steps are determined by including the method steps above.
  • a preferred embodiment of the invention is to use lactide monomers dissolved in a polar solvent as the monomer solution mentioned in the process step 'a'.
  • Another preferred embodiment of the invention is the use of catalyst in process step 'a'.
  • a preferred embodiment of the invention is to characterize the catalyst as tin(ll)2- ethylhexanoate (Sn(Oct)2).
  • Another preferred embodiment of the invention is to swell the wood up to 15% in a polar solvent before the 'a' process step.
  • a preferred embodiment of the invention is to use dimethylformamide (DMF) as said polar solvent.
  • Another preferred embodiment of the invention is to characterize the polymerization process mentioned in process step 'c' as a lactide polymerization process.
  • Lactide modification of wood is shown in Figure 1 .
  • Figure 2 shows the Fourier transform infrared spectroscopy (FTIR) results according to the lactide percentages of modified wood.
  • Figure 3 shows the swelling values obtained according to lactide percentages of modified wood with lactide.
  • Figure 4 shows the dimensional stability (%) values obtained according to lactide percentages of modified wood with lactide.
  • Figure 5 shows the mass loss (%) values obtained after the fungal rot test ( Coniophora tenuna exposure) according to the lactide percentages of modified wood with lactide.
  • Figure 6 shows the scanning electron microscope (SEM) images of the cross-sectional surfaces of the wood material modified with 10% lactide before the fungal decay test.
  • Figure 7 shows the scanning electron microscope (SEM) images of the cross-sectional surfaces of the wood material modified with 20% lactide before the fungal decay test.
  • Figure 8 shows the scanning electron microscope (SEM) images of the cross-sectional surfaces of unleached 10% lactide-modified wood material after the fungal decay test.
  • Figure 9 shows the scanning electron microscope (SEM) images of the cross-sectional surfaces of unleached 20% lactide-modified wood material after the fungal decay test.
  • Figure 10 shows the scanning electron microscope (SEM) images of the cross-sectional surfaces of the leached 10% lactide-modified wood material after the fungal decay test.
  • Figure 1 1 shows the scanning electron microscope (SEM) images of the cross-sectional surfaces of leached wood material modified with 20% lactide after the fungal decay test. DESCRIPTION OF REFERENCE NUMBERS IN THE FIGURES
  • the subject of the invention relates to the grafting of lactide monomer, obtained from lactic acid obtained by the fermentation of corn, into the wood cell wall (1 ) through a ringopening reaction, thus modifying the voids in the cell wall (1 ) by filling them with hydrophobic polylactic acid (PLA).
  • lactide monomer obtained from lactic acid obtained by the fermentation of corn
  • the invention is a lactide modification process of wood and is implemented by introducing certain chemicals at certain stages.
  • the lactide used in the invention is obtained by lactic acid fermentation of carbohydrate sources such as sugar cane, corn, sugar beet and cassava.
  • Lactide monomer solution is prepared with dimethylformamide (4) (DMF) and organotin catalyst (3), expressed as tin(ll) 2-ethylhexanoate Sn(Oct)2. Swelled wooden samples are impregnated with monomer solution under vacuum. Then the diffusion phase begins. Lactide impregnation is carried out by keeping the samples in solution for 24 hours and allowing the monomer to penetrate the cell wall (1 ).
  • DMF dimethylformamide (4)
  • organotin catalyst (3) expressed as tin(ll) 2-ethylhexanoate Sn(Oct)2. Swelled wooden samples are impregnated with monomer solution under vacuum. Then the diffusion phase begins. Lactide impregnation is carried out by keeping the samples in solution for 24 hours and allowing the monomer to penetrate the cell wall (1 ).
  • Polymerization is carried out at high molecular weights by ring-opening reaction of lactide monomer in the ring structure in the presence of organotin catalyst (3). Polymerization is carried out at high molecular weights by the monomer ring opening reaction. The monomer is covalently bonded to the hydroxyl groups through the ring opening reaction. Since the organotin used for the polymerization of lactide initiates the polymerization reaction above 100°C, the wood impregnated with lactide monomer solution is left in a closed system at a temperature between 105-120°C (5). The polymerization process is carried out by lactide polymerization and PLA formation on the wood cell wall (1 ). Lactide modification can be applied to completely dry all wood species.
  • Figure 2 shows the chemical characterization result (FTIR) obtained according to lactide percentages in wood modified with lactide.
  • FTIR chemical characterization result
  • In-situ polymerization is achieved by lactide polymerization of the lactide solution impregnated on the cell wall.
  • Figure 2 also proves that the modification is stable against the accelerated aging test, which includes 2 cycles and 4 steps of drying and soaking processes, and fungal degradation test, because the polylactic acid is still attached to the wood surface that indicates the method is permanent.
  • the critical factor for wood-rotting fungi is the presence of 30% moisture in the wood, and thanks to the method within the scope of the protection of the invention, as the moisture and void ratio in the wood decreases, there is no suitable environment for the development of fungi, and thus the wood gains resistance against fungi that cause wood rot.
  • Figure 6, Figure 7, Figure 8, Figure 9, Figure 10 and Figure 1 1 show SEM images after the treatments applied on wooden surfaces following the method within the protection scope of the invention. Accordingly, SEM image of samples modified with 10% lactide (26) and SEM image of samples modified with 20% lactide before fungal degradation test (27), SEM image of unleached samples modified with 10% lactide (28) and SEM image of unleached 20% lactide modified samples after fungal degradation test (29), SEM image of leached 10% lactide modified samples (30) and SEM image of leached 20% lactide modified samples after the fungal degradation test (31 ) support the FTIR findings that indicates the presence of the polymer in wood structure.
  • the polymer was also seen in small amounts in the lumen region on the surface of the cell wall. Although no degradation of the cell wall is observed in the samples after the fungal degradation test, the presence of the polymer continues in the cell lumens (27-31). The presence of fungal cells can also be seen in the cell lumens, but when combined with the result of no mass loss, it was revealed that the fungi were unable to degrade the modified wood.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Forests & Forestry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

L'invention concerne un procédé de modification du bois consistant en des étapes méthodologiques telles que l'imprégnation d'échantillons de bois avec une solution monomère sous vide pour amener les parois cellulaires (1) à gonfler, le maintien des échantillons imprégnés pendant au moins 1 jour pour réaliser une diffusion, et le chauffage du bois traité à une température comprise entre 105 et 120°C dans un système fermé pour mettre en oeuvre le processus de polymérisation; l'invention vise à augmenter le caractère hydrofuge et les propriétés de stabilisation dimensionnelle du bois ainsi que réduire l'absorption d'eau et la teneur en interstices du bois qui sont à l'origine de la présence de champignons de pourriture du bois.
PCT/TR2024/050100 2023-02-23 2024-02-07 Modification de la paroi de cellules ligneuses avec de l'acide polylactique hydrophobe Ceased WO2024177598A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2023/002022 TR2023002022A1 (tr) 2023-02-23 Ahşap Hücre Çeperinin Hidrofobik Polilaktik Asit İle Modifiye Edilmesi
TR2023002022 2023-02-23

Publications (1)

Publication Number Publication Date
WO2024177598A1 true WO2024177598A1 (fr) 2024-08-29

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119412556A (zh) * 2024-12-04 2025-02-11 山东农业大学 一种原位浸渍改性木单板缠绕pvc复合管道

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160316754A1 (en) * 2011-12-23 2016-11-03 Arch Wood Protection Pty Ltd Wood preservative

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160316754A1 (en) * 2011-12-23 2016-11-03 Arch Wood Protection Pty Ltd Wood preservative

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Proje Yürütücüsü; Project No: 116O578", 27 February 2020, TR, article ERMEYDAN M.A.,TOMAK E.D. : "Üç Yeni Kimyasal Odun Modifikasyonu Yönteminin Yapay Dış Ortam Koşullarına ve Mantar Çürüklüğüne Karşı Dayanım Özelliklerinin İncelenmesi [Investigation of artificial weathering and decay resistance properties of three new wood chemical modification methods]", pages: 1 - 98, XP009557196 *
MARION NOIL ET AL.: "Lactic acid/ wood-based composite material . Part 2: Physical and mechanical performance", BIORESOURCE TECHNOLOGY, vol. 100, no. 20, 2009, pages 4717 - 4722, XP026237438, ISSN: 0960-8524, DOI: https:// doi.org/ 10.1 0 16/j. biortech. 2009.04.04 2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119412556A (zh) * 2024-12-04 2025-02-11 山东农业大学 一种原位浸渍改性木单板缠绕pvc复合管道

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