Board made of acetylated rubber wood
阅读说明：本技术 乙酰化橡胶木材制成的板材 (Board made of acetylated rubber wood ) 是由 斯特凡·范多梅尔 特奥杜鲁斯·格拉德乌斯·马里纳斯·玛利亚·卡彭 于 2020-02-03 设计创作，主要内容包括：公开了由乙酰化橡胶木材元件制成的板材及其制造方法。乙酰化橡胶木材元件具有至少17％的乙酰基含量和/或通过使用呈汽相的乙酰化试剂乙酰化橡胶木材元件来制备。本发明还涉及通过使用呈汽相的乙酰化试剂制备的乙酰化橡胶木材元件。(Disclosed are panels made from acetylated rubber wood elements and methods of making the same. Acetylated rubberwood elements have an acetyl content of at least 17% and/or are prepared by acetylating rubberwood elements using an acetylating agent in the vapour phase. The invention also relates to acetylated rubber wood elements prepared by using an acetylation agent in the vapour phase.)
1. A panel comprising acetylated wood elements, wherein the acetylated wood elements are obtained from a rubber wood, wherein the acetylated wood elements have an acetyl content of at least 17%, and wherein the acetylated wood elements are selected from the group consisting of fibers, chips, particles, strands and bundles of fibers; fibers are preferred.
2. A panel comprising acetylated wood elements, wherein the acetylated wood elements are obtained from a rubber wood, and wherein the acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting the wood elements with an acetylation agent;
wherein the acetylation agent is in the vapor phase, and wherein the acetylated wood elements are selected from the group consisting of fibers, chips, particles, slivers, and bundles of fibers; fibers are preferred.
3. A panel according to any one of the preceding claims, wherein the acetylated wood elements are present in an amount of at least 50 wt%, preferably at least 80 wt%, compared to the total weight of wood elements comprised in the panel.
4. A panel according to any one of the preceding claims, wherein the acetylated wood elements have an acetyl content of at most 35%.
5. A panel according to any one of the preceding claims, wherein the panel is selected from medium density fibreboard, low density fibreboard, high density fibreboard, particleboard and flakeboard; medium density fiberboard is preferred.
6. A panel according to any of claims 2 to 5, wherein the acetylated wood elements have an acetyl content of at least 8%, preferably at least 17%.
7. Acetylated wood elements, wherein the acetylated wood elements are rubber woods, wherein the acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting said wood elements with an acetylation agent,
wherein the acetylation agent is in the vapor phase, and wherein the acetylated wood elements are selected from the group consisting of fibers, chips, particles, slivers, and bundles of fibers; fibers are preferred.
8. Acetylated wood elements according to claim 7 wherein the acetylation agent is selected from the group consisting of acetic anhydride, acetic acid, ketene, acetyl chloride and combinations thereof.
9. Acetylated wood element according to any of claims 7 and 8, wherein the acetylated wood element has an acetyl content of at least 8%, preferably at least 17%, and preferably an acetyl content of at most 35%.
10. Acetylated wood elements according to any of claims 7 to 9 wherein the wood elements are wood fibres.
11. Acetylated wood elements according to any of claims 7 to 9 wherein the wood elements are wood chips.
12. A process for the manufacture of acetylated rubberwood elements, wherein the process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are selected from the group consisting of fibers, chips, particles, slivers, and fiber bundles; preferably a fiber; and
b) contacting the wood elements with an acetylation agent;
wherein the acetylating agent is in the vapor phase.
13. A process for the manufacture of acetylated rubberwood elements, wherein the process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are selected from the group consisting of fibers, particles, slivers, and fiber bundles; preferably a fiber; and
b) contacting the wood elements with an acetylation agent to obtain acetylated rubber wood elements having an acetyl content of at least 17%, wherein preferably the acetylation agent is in the vapour phase.
14. A process for the manufacture of acetylated rubberwood elements, wherein the process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are chips; and
b) contacting the wood elements with an acetylation agent to obtain acetylated rubber wood elements having an acetyl content of at least 17%, wherein preferably the acetylation agent is in the vapour phase;
c) refining the acetylated shea elements to obtain fibers.
15. Method for manufacturing a panel according to any one of claims 1 to 6, wherein the method comprises the following sequential steps:
a) providing an acetylated wood element according to any of claims 7 to 11 and a glue; and
b) forming the plate.
16. The method according to claim 15, wherein the acetylated wood elements have a moisture content of 4 to 8 wt% compared to the total weight of the acetylated wood fibres.
Technical Field
The invention disclosed herein relates to a panel comprising acetylated rubberwood elements, a method of making the same and acetylated rubberwood elements.
Background
Board material, such as MDF (medium density fiberboard), refers to a composite product comprising wood elements pressed and glued together with a glue, typically a phenol-formaldehyde or urea-formaldehyde resin, or a polymeric diphenylmethane diisocyanate glue. Typically, boards such as MDF boards also contain wax. Boards such as MDF are typically manufactured in various thicknesses (typically 3mm to 25mm) and densities and may provide a visually attractive paper or wood veneer or plastic surface finish or coating. It is a hard, very rigid, virtually inflexible material. This is generally advantageous because relatively thin plates at the low end of the above thickness range, with the most typical thicknesses being 6mm and 9mm, are also highly suitable for applications where rigidity is desired. As a result, these panels have a wide range of end use applications, such as in furniture, decorative interior wall liners, doors, divider walls, and many other typical indoor applications where it is desirable to use panels with good rigidity.
Wood fibre board typically has a thickness of 2mm to 60mm and 600kg/m3To 1000kg/m3The density of (c). The MDF preferably involved in the invention has a value of 650kg/m in the strict sense of the word MDF3To 800kg/m3The density of (c). Higher than 800kg/m3Commonly referred to as High Density Fiberboard (HDF). Less than 650kg/m3It is called light MDF or ultra-light MDF: (<550kg/m3)。
An important feature of wood fiberboard and MDF is the size of the wood elements used. In this respect, it is possible to distinguish between different kinds of products, each with their own specific field of use. Thus, wood fibre board is a different product than for example wood particle board. The latter have larger wood particles, typically having a length of 1.5mm to 15mm, a width of 0.15mm to 1.30mm and a thickness of 0.15mm to 1.25 mm. The fibers in the fiberboard (e.g., MDF) are quite small, typically having a length of 7mm or less, preferably 1mm to 5mm, a width of 0.05mm to 0.1mm, and a thickness of 0.05mm to 0.1 mm.
The wood elements in the wood panels may be derived from essentially any fibrous lignocellulosic material, the commonly used wood being spruce (genus picea), various types of pine (genus pinus) or eucalyptus (genus eucalyptus). The present invention relates to a panel comprising wood elements derived from rubberwood (Hevea brasiliensis).
As with other engineered wood products, such as particle board or oriented strand board (oriented strand board), fiberboard may also be made from modified wood, such as steam treated wood or acetylated wood. Acetylation of wood is commonly used to increase the sustainability of wood.
Furthermore, most boards, especially MDF boards, preferably have good mechanical properties, such as high internal bond strength. Internal bond strength is defined as the "ultimate failure stress of a wood composite panel under a tensile load perpendicular to the plane of the panel". (J.Rathke et al, Materials,2012, Vol.5, p.1115-.
In this context, particle boards are known in the art to be constructed differently from other panels and generally have other mechanical properties than other panels, in particular MDF panels. For particle board, for example, good mechanical properties are determined by the oriented strands in multiple directions, as a result of which limited deflection and warpage are obtained. These properties are different from the internal bond strength, which is the tensile strength. In other panels, in particular MDF, the good mechanical properties are determined mainly by the internal bond strength, compared to particle board.
A known problem in the art is that boards made of acetylated rubberwood, in particular MDF, often have inferior mechanical properties, such as internal bond strength, than boards made of non-acetylated rubberwood.
In particular, Tomimura et al ("Journal of thermoplastic Forest Science", 1989, Vol.1, p.312-317) reported that the internal bond strength of MDF made of acetylated rubber-wood was much lower than that of MDF made of non-acetylated rubber-wood. Wherein, the weight percentage of the acetylated rubber wood fiber increased by 15.4 percent is used. Acetylated rubber wood fibers were prepared by placing the fibers in an Erlenmeyer flask, adding a mixture of acetic anhydride-pyridine (10:1, w/w). The flask was then placed in a water bath at 60 ℃ for 12h, after which the fiber was washed with water.
Background art related to the internal bond strength of MDF comprising acetylated rubberwood fibers includes articles by Ayrilmis et al (j. trop. for. sci.2011, vol.23, p.10-16). Among them, the internal bond strength of the rubber wood MDF board was studied, in which rubber wood fibers were heat-treated. According to Ayrilmis et al, the internal bond strength of MDF boards comprising heat treated fibers (i.e., more hydrophobic fibers) is reduced compared to MDF made with untreated rubber wood fibers. Without wishing to be bound by theory, Ayrilmis et al assert that the increase in hydrophobicity due to heat treatment results in a decrease in the adhesion and penetration of the adhesive during the preparation of MDF boards.
Other preferred properties of the board, particularly MDF board, include, but are not limited to, good dimensional stability, required durability, and ease of manufacture.
It is desirable to provide a panel made of acetylated rubber wood elements with suitable properties and a method for making the same. Preferably, these boards, in particular MDF boards, have better mechanical properties, preferably higher internal bond strength, than known boards made of acetylated rubber wood elements. Furthermore, it would be desirable to provide acetylated rubberwood elements, in particular acetylated rubberwood fibres, which can be used to prepare boards having suitable properties, in particular better mechanical properties, preferably higher internal bond strength, compared to known boards made from acetylated rubberwood elements.
Disclosure of Invention
In one aspect, the present invention relates to a panel comprising acetylated wood elements, wherein the acetylated wood elements are obtained from a softwood, wherein the acetylated wood elements have an acetyl content of at least 17%, and wherein the acetylated wood elements are selected from the group consisting of fibers, chips (chips), particles, slivers (spleens), and fiber bundles; fibers are preferred.
In another aspect, the present invention relates to a panel comprising acetylated wood elements, wherein the acetylated wood elements are obtained from a softwood, and wherein the acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting the wood elements with an acetylation agent;
wherein the acetylation agent is in the vapor phase, and wherein the acetylated wood elements are selected from the group consisting of fibers, chips, particles, slivers, and bundles of fibers; fibers are preferred.
In a further aspect, the present invention relates to acetylated wood elements, wherein said acetylated wood elements are a rubber wood, wherein said acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting said wood elements with an acetylation agent, wherein said acetylation agent is in the vapor phase, and wherein said acetylated wood elements are selected from the group consisting of fibers, chips, particles, strands, and bundles of fibers; fibers are preferred.
In a further aspect, the present invention relates to a process for the manufacture of acetylated rubberwood elements, wherein the process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are selected from the group consisting of fibers, chips, particles, slivers, and fiber bundles; preferably a fiber; and
b) contacting the wood elements with an acetylation agent;
wherein the acetylating agent is in the vapor phase.
In a further aspect, the present invention relates to a process for the manufacture of acetylated rubberwood elements, wherein the process comprises the sequential steps of:
a) providing wood elements from a rubber-wood, wherein the wood elements are selected from the group consisting of fibers, particles, slivers, and fiber bundles; preferably a fiber; and
b) contacting the wood elements with an acetylation agent to obtain acetylated rubber wood elements having an acetyl content of at least 17%, wherein preferably the acetylation agent is in the vapour phase.
In a further aspect, the invention relates to a method for manufacturing a panel according to the invention, wherein the method comprises the following sequential steps:
a) providing an acetylated wood element and an adhesive according to the invention; and
b) forming the plate.
Detailed Description
The present invention is broadly based on the judicious insight that at least one of the above-mentioned desires is met by providing a panel comprising acetylated rubberwood elements having an acetyl content of at least 17%.
Furthermore, the inventors have surprisingly found that at least one of the above-mentioned desires is met by providing a board material comprising acetylated rubberwood elements obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber wood, and the acetylated wood elements are selected from the group consisting of fibers, chips, particles, slivers, and bundles of fibers; preferably a fiber; and
b) contacting said wood elements with an acetylation agent, wherein said acetylation agent is in the vapor phase.
This is surprising because acetylation increases the hydrophobicity of wood. Nevertheless, the inventors have found that the board according to the invention, in particular MDF board, better solves at least one of the above mentioned desires. In general, they show improved mechanical properties, more particularly increased internal bond strength, compared to boards not comprising acetylated wood fibres.
In a preferred embodiment, the panel of the invention comprises acetylated wood elements, wherein the acetylated wood elements are obtained from a softwood, wherein the acetylated wood elements have an acetyl content of at least 8%, preferably at least 17%, wherein the acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting said wood elements with an acetylation agent,
wherein the acetylating agent is in the vapor phase.
In a preferred embodiment, the board according to the invention comprises acetylated rubberwood elements as defined herein in an amount of at least 50 wt%, preferably at least 65 wt%, more preferably at least 80 wt%, even more preferably at least 90 wt%, still more preferably at least 95 wt%, most preferably at least 99 wt% compared to the total weight of the wood elements comprised in the board. The remaining amount of wood elements may comprise non-acetylated rubber material elements. Optionally, the remaining amount of wood elements comprises acetylated and/or non-acetylated wood elements, preferably made of wood selected from the group consisting of spruce (spruce), sago (sitka spruce), maritime pine (maritime pine), scots pine (scots pine), radiata pine (radiata pine), eucalyptus (eucalyptus), red poplar (red alder), European alder (European alder), beech (beech), birch (birch), loblolly pine (lobolly pine), small rod pine (logpole pine), north american pine (pitch pine), red pine (red pine), Southern yellow pine (Southern yellow pine), Japanese cedar (Japanese cedar), hemlock (hemlock), palm (palm pauli), Paulownia (paulnia), teak (teak), maple (oak), and combinations thereof.
Most preferably, substantially all wood elements comprised in the board according to the invention are acetylated rubber wood elements as defined herein. In another preferred embodiment, all wood elements comprised in the board according to the invention are acetylated rubber wood elements as defined herein.
In a preferred embodiment, the board according to the invention comprises acetylated rubberwood elements having an acetyl content of at least 17%, more preferably at least 17.5%, even more preferably at least 18%, even more preferably at least 19%, still more preferably at least 20% and most preferably at least 21%. In another preferred embodiment, the board according to the invention comprises acetylated rubberwood elements having an acetyl content of more than 21%, more preferably more than 22%.
In a preferred embodiment, the board according to the invention comprises acetylated rubberwood elements having an acetyl content of at most 35%. More preferably, the board according to the invention comprises acetylated rubberwood elements having an acetyl content of at most 32%, even more preferably at most 30%, still more preferably at most 27%, most preferably at most 25%.
In a preferred embodiment, the board according to the invention comprises acetylated rubberwood elements having an acetyl content of 17% to 35%, more preferably 18% to 32%, even more preferably 19% to 30%, still more preferably 20% to 27%, most preferably 21% to 25%. In another preferred embodiment, the board according to the invention comprises acetylated shea elements having an acetyl content of 22% to 23%.
In a preferred embodiment, the board according to the invention is selected from the group consisting of medium density fibreboard, low density fibreboard, high density fibreboard, particle board (particle board) and flake board (flakeboard). Most preferably, the board according to the invention is a medium density fiberboard.
In a preferred embodiment, the board according to the invention is selected from medium density fibreboard and high density fibreboard; wherein the medium or high density fiberboard comprises acetylated shea elements having an acetyl content of at least 14%, preferably at least 15%, more preferably at least 16%, most preferably at least 17%.
In a preferred embodiment, the board according to the invention is selected from the group consisting of medium density fibreboard, high density fibreboard and sheetboard; wherein the medium density fiberboard, high density fiberboard or thin sheet board comprises acetylated wood elements having an acetyl content of at least 16%, preferably at least 17%.
The board according to the invention comprises acetylated wood elements selected from the group consisting of fibres, chips, particles, slivers and fibre tows.
Most preferably, the board according to the invention comprises acetylated wood elements, wherein the acetylated wood elements are fibres or fibre bundles, preferably fibres. Preferably, substantially all acetylated wood elements comprised in the board of the invention are fibres or fibre bundles, most preferably fibres. More preferably, all acetylated wood elements comprised in the board of the invention are fibres or fibre bundles, most preferably fibres. In a preferred embodiment, the board according to the invention comprises acetylated wood elements, wherein the acetylated wood elements are fibres, and wherein the board is a medium density fibreboard.
In another preferred embodiment, the board according to the invention comprises acetylated wood elements, wherein the acetylated wood elements are particles. Preferably, substantially all acetylated wood elements comprised in the board of the invention are particles. More preferably, all acetylated wood elements comprised in the board of the invention are particles. In a preferred embodiment, the board according to the invention comprises acetylated wood elements, wherein the acetylated wood elements are particles, and wherein the board is a particle board.
The present invention also relates to acetylated wood elements, wherein said acetylated wood elements are gum wood, wherein said acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting said wood elements with an acetylation agent, wherein said acetylation agent is in the vapor phase.
The acetylation of wood elements is described further below, wherein the acetylation agent is in the vapor phase. Without wishing to be bound by theory, the inventors believe that acetylation in the liquid phase will leach more resin than acetylation in the vapor phase (the gum wood typically contains a significant amount of resin). Thus, it is believed that the softwood acetylated from the vapor phase contains more virgin resin content than the softwood acetylated in the liquid phase.
Typical dimensions of the wood elements defined according to the invention are given in table 1.
TABLE 1
In some embodiments, the wood elements have a length of 1.0mm to 75mm, a width of 0.05mm to 50mm, and a thickness of 0.05mm to 25 mm.
With respect to the present invention, the term "wood elements" is understood to exclude solid wood (solid wood). The wood elements relevant to the present invention typically have a length of 1mm to 120mm, a width of 0.05mm to 50mm and a thickness of 0.05mm to 25 mm.
In a preferred embodiment, the acetylated wood elements of the invention are wood chips, wood particles or wood fibres. Preferably, the acetylated wood elements of the invention are wood particles. Most preferably, the acetylated wood elements of the invention are wood fibres.
It should be understood that the acetylated rubberwood elements of the present invention may be obtained in several ways. For example, solid gum wood may be acetylated as described herein, then cut to obtain acetylated gum wood chips, which may then be refined to obtain acetylated gum wood fibers. Alternatively, solid gum wood may be first cut to obtain gum wood chips. These rubber wood chips may then be acetylated as described herein and refined to form acetylated rubber wood fibers. As another alternative, the softwood chips are refined to form softwood fibers, which are then acetylated as described herein.
Thus, the acetylated shea fibers of the invention may be obtained by acetylation of shea fibers or by refining acetylated shea chips.
In a preferred embodiment, the acetylated rubberwood elements, preferably acetylated rubberwood fibres, according to the invention have an acetyl content of at least 8%, more preferably at least 10%, still more preferably at least 12%, still more preferably at least 14%, even more preferably at least 15%, even more preferably at least 16%, at least 17%, at least 18%, at least 19% or at least 20% and most preferably at least 21%. In another preferred embodiment, the acetylated rubberwood elements according to the invention, preferably acetylated rubberwood fibres, have an acetyl content of more than 21%, such as at least 22%.
In a preferred embodiment, the acetylated rubberwood elements, preferably acetylated rubberwood fibres according to the invention have an acetyl content of at most 35%. More preferably, the acetylated rubberwood elements according to the invention have an acetyl content of at most 32%, even more preferably at most 30%, still more preferably at most 27% and most preferably at most 25%.
In a preferred embodiment, the acetylated rubberwood elements, preferably acetylated rubberwood fibres, according to the invention have an acetyl content of from 8% to 35%, more preferably from 12% to 32%, even more preferably from 14% to 30%, still more preferably from 16% to 27%, and most preferably from 17% to 25%. In another preferred embodiment, the acetylated rubberwood elements according to the invention, preferably acetylated rubberwood fibres, have an acetyl content of 22% to 23%.
The acetylation of wood elements according to the invention is generally carried out according to optimized acetylation methods known in the art. These processes generally utilize an acetylating agent in the liquid or vapor phase.
Preferably, the panel according to the invention comprises wood elements acetylated by the use of an acetylation agent in the vapour phase. Suitable processes for the acetylation of wood elements using an acetylation agent in the vapour phase are described in US 3,403,145, US 5,431,868, US 5,525,721, US 6,376,582, which are incorporated herein by reference. Typical acetylating agents used in these processes are acetic anhydride, acetic acid, acetyl chloride, ketene and mixtures thereof; among them, acetic anhydride is preferable. The initial acetylation fluid preferably has a composition as described herein.
In a preferred embodiment, the rubber-wood elements are dried before impregnation, preferably in an oven. Preferably, the drying is carried out at a temperature of 80 ℃ to 130 ℃, more preferably 90 ℃ to 115 ℃. Preferably, the drying of the rubber-wood elements is carried out for a duration of at least 30 minutes, more preferably at least 1 hour. It will be appreciated that the drying time required may depend on the size of the wood elements to be dried. Preferably, for solid gum wood, drying is carried out for a duration of 8 to 25 hours, more preferably 12 to 20 hours. For the rubber wood chips or the rubber wood fibers, the drying is preferably performed for 30 minutes to 4 hours, more preferably 1 hour to 3 hours.
In a preferred embodiment, prior to the acetylation reaction, the rubber wood elements are impregnated as described herein.
Preferably, the rubber wood elements are acetylated in the vapour phase at a temperature of 150 ℃ to 220 ℃, more preferably 180 ℃ to 205 ℃. In a preferred embodiment, the rubber wood elements are acetylated in the vapour phase at a pressure of 0 to 6 bar, preferably 1.5 to 4 bar. In a preferred embodiment, the rubber wood elements are acetylated in the vapor phase at atmospheric pressure. Preferably, the rubber wood elements are acetylated in the vapour phase for a duration of 10 to 90 minutes, more preferably 15 to 60 minutes.
Preferably, after the acetylation reaction, the reaction vessel containing the acetylated gum wood elements is brought back to ambient conditions. In a preferred embodiment, the acetylated gum wood elements are then subjected to a chemical recovery step at a temperature of 130 ℃ to 220 ℃, preferably 150 ℃ to 200 ℃. Preferably, the chemical recovery step is carried out for a duration of 20 minutes to 90 minutes, more preferably 30 minutes to 60 minutes.
A preferred method of acetylation using an acetylation agent in liquid phase comprises the steps of:
-providing wood elements;
-controlling and if necessary adjusting the moisture content of the wood elements;
-impregnating wood elements with an acetylation fluid;
-subjecting the impregnated wood elements to one or more heating steps for achieving acetylation of the wood elements; and
-separating the acetylated wood elements from the excess acetylation fluid.
The acetylated wood elements thus obtained may be directly further processed (e.g. in case the manufacturing of boards according to the invention comprising acetylated wood elements, in particular MDF boards, is performed in series with the acetylation process), or they may be post-treated (e.g. by drying or cooling) for storage and/or transport.
Prior to acetylation, the wood elements are typically subjected to a step that allows controlling the moisture content of the wood elements. This can be done by any method known in the wood industry, either in a continuous or batch process. Typically, the required moisture content prior to acetylation is less than 15 wt%. Preferably, the moisture content of the wood is brought to a value of less than 8%, more preferably 0.01% to 5%, most preferably 0.5% to 4%.
The acetylation process itself may be carried out using liquid and/or gaseous acetylation fluids, as is known in the art. Typical acetylating agents are acetic anhydride, acetic acid, acetyl chloride, ketene and mixtures thereof. Acetic anhydride is preferred as the acetylating agent. Preferably, the initial acetylation fluid used comprises acetic anhydride.
In a preferred embodiment, the initial acetylation fluid comprises acetic anhydride in an amount of 70 wt% to 99 wt%, more preferably 80 wt% to 95 wt%, wherein the weight percentage (wt%) is compared to the total weight of the initial acetylation fluid. In another preferred embodiment, the initial acetylation fluid comprises acetic acid in an amount of 1 wt% to 30 wt%, more preferably 3 wt% to 15 wt%, wherein the weight percentage (wt%) is compared to the total weight of the initial acetylation fluid.
In a particularly preferred embodiment, the initial acetylation fluid comprises acetic anhydride and acetic acid. More preferably, the initial acetylation fluid comprises acetic anhydride in an amount of 70 wt% to 99 wt%, preferably 80 wt% to 95 wt% and acetic acid in an amount of 1 wt% to 30 wt%, more preferably 3 wt% to 15 wt%, wherein weight percentage (wt%) is compared to the total weight of the initial acetylation fluid.
It will be appreciated that as a result of the acetylation reaction, the composition of the acetylation fluid will change during the process as the acetylation reagent is consumed and reaction products, such as acetic acid, are formed. Typically, contacting the wood elements with an acetylation fluid comprises an impregnation step (e.g. with acetic anhydride).
In an interesting embodiment, the impregnation step comprises a Bethel type impregnation process. Wherein the wood elements to be impregnated are placed in a vacuum chamber and a vacuum is applied to evacuate air and/or other gases (e.g. N) from the wood2). An impregnating fluid (e.g., comprising acetic anhydride) is then added to the chamber under vacuum. After filling the chamber with liquid, a pressure typically up to 250 pounds per square inch (psi), preferably 150psi to 200psi, may be applied. The pressure is removed so that the wood is again subjected to atmospheric pressure. This type of process is generally preferred because it should generally produce a maximum impregnation load, which is believed to be directly related to the desired maximum acetyl level. The impregnation fluid is kept in contact with the wood elements under acetylation reaction conditions (typically in an autoclave) for a duration typically ranging from 1 hour to 10 hours, more preferably from 2 hours to 8 hours, even more preferably from 4 hours to 6 hours, most preferably about 5 hours.
However, in cases where maximum acetylation fluid uptake after impregnation is not a primary goal, more economical impregnation methods may also be used. Examples thereof known to the person skilled in the art of wood impregnation are the so-called Lowry and Rueping processes. These methods do not require an initial vacuum. Instead, the impregnation fluid is forced under pressure deep into the wood. Then, when the pressure is released, the compressed gas inside the wood expands, causing any excess preservative to be squeezed out of the wood.
In an interesting embodiment, the acetylation is performed according to any of the acetylation processes as described in WO2009/095687, WO2011/95824, WO2012/037481, WO2013/117641, WO2013/139937 or WO2016/008995, the disclosures of which are incorporated herein by reference. For example, a preferred method for obtaining high acetyl content is a three stage process as described in WO 2016/008995.
The acetylation reaction in the liquid phase is preferably carried out at a temperature of 120 ℃ to 200 ℃, more preferably 160 ℃ to 180 ℃. The skilled person will be able to optimize the time and temperature conditions selected for a given reactor equipment and depending on the wood species to be acetylated.
It should be noted that there are two different methods in the art in determining the degree of acetylation of wood. One based on WPG (weight percent gain). WPG compares samples (of extracted wood) before and after the acetylation treatment and as a result any substances added (and any residues still present in the wood) increase the value. WPG is interpreted as follows: WPG ═ MIncrease of/MSample before reaction) X 100%. Wherein M represents mass, and M representsIncrease of＝MReacted sample-MSample before reaction). Herein, it is to be understood that "reaction" refers to an acetylation reaction.
Another method is to actually measure the Acetyl Content (AC). This is expressed as AC ═ MAcetyl group/MReacted sample) X 100% is given. Generally, HPLC (high pressure liquid chromatography) can be used to quantify the acetate ion concentration resulting from saponification of acetyl groups from wood. Thus, the total mass of acetyl groups after acetylation can be considered as MAcetyl group. In this connection, it is understood that "post-reaction sample" refers to a sample obtained after the acetylation reaction but before the saponification reaction.
Determining MAcetyl groupThe preferred method is as follows. The wood sample was ground into wood particles. Residual traces of acetic acid and/or acetic anhydride were removed from these samples by washing with water and subsequent drying at 103 + -2 deg.C for 14 to 24 hours. After weighing these dried samples, acetyl groups in the form of acetate ions were released from the wood by saponification with sodium hydroxide solution at elevated temperature. The saponification reaction was run for 4 hours with stirring every 15 minutes. After calibrating the HPLC with a standard acetate solution and using sodium butyrate as an internal reference, acetate ions were quantified by High Pressure Liquid Chromatography (HPLC). Thus, M was obtainedAcetyl group。
It should be understood that,Mreacted sampleCan be determined by simply weighing the sample.
The different results of WPG and AC can be explained with reference to the following theoretical examples: a sample of e.g. 1g wood is acetylated and has a mass after reaction of 1.25 g. Thus, MAcetyl groupIt was 0.25 g. The WPG obtained was: (1.25-1.00)/1.00 × 100% ═ 25%. Calculated as acetyl content, AC ═ 1.25-1.00)/1.25 × 100% ═ 20%.
Therefore, care should be taken not to directly compare the degree of acetylation expressed in WPG with the degree of acetylation expressed in AC. In the present specification, AC values were chosen to identify the degree of acetylation.
In this connection, it is understood that the measurement of the acetyl content of the wood elements comprised in the board is performed by grinding at least a part of the board and using, for example, the above-described characterization by saponification and HPLC.
In another aspect, the present invention relates to a process for the manufacture of an acetylated rubberwood element according to the invention, wherein the process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are selected from the group consisting of fibers, chips, particles, slivers, and fiber bundles; preferably a fiber; and
b) contacting the wood elements with an acetylation agent;
wherein the acetylating agent is in the vapor phase.
In another aspect, the present invention relates to a process for the manufacture of an acetylated rubberwood element according to the invention, wherein the process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are selected from the group consisting of fibers, particles, slivers, and fiber bundles; preferably a fiber; and
b) contacting the wood elements with an acetylation agent to obtain acetylated rubber wood elements having an acetyl content of at least 17%, wherein preferably the acetylation agent is in the vapour phase.
In a preferred embodiment, the present invention relates to a process for the manufacture of acetylated rubberwood elements according to the invention, wherein said process comprises the following sequential steps:
a) providing wood elements from a rubber-wood, wherein the wood elements are chips; and
b) contacting the wood elements with an acetylation agent to obtain acetylated rubber wood elements having an acetyl content of at least 17%, wherein preferably the acetylation agent is in the vapour phase;
c) refining the acetylated shea elements to obtain fibers.
In another aspect, the invention relates to a method for manufacturing a panel according to the invention, wherein the method comprises the following sequential steps:
a) providing an acetylated wood element and an adhesive according to the invention; and
b) forming the plate.
In a preferred embodiment, in the process for manufacturing a board, preferably an MDF board, according to the invention, the acetylated wood elements have a moisture content of between 4 wt% and 8 wt% compared to the total weight of the acetylated wood elements. More preferably, the moisture content of the acetylated wood elements is between 5 and 7 wt%, even more preferably between 5.5 and 6.5 wt%. Most preferably, the moisture content of the acetylated wood elements is about 6 wt%. It should be understood that the moisture content refers to the moisture content immediately prior to the manufacture of the board.
The method of making medium density fiberboard according to the present invention is generally the same as that conventionally used to make conventional MDF. The composition of the MDF board of the invention is typically, in weight percent, 75% to 92% wood, 2% to 15% adhesive (glue), 0% to 2.5% additives, preferably 0.5% to 2.5% additives and 4% to 10% water.
The adhesive may generally be selected from the same types of adhesives used to make conventional MDF. Preferred adhesives are selected from phenol-formaldehyde resins, melamine urea-formaldehyde resins, or isocyanate-based adhesives, including methylene diphenyl diisocyanate (MDI) and polymeric methylene diphenyl diisocyanate (PMDI). Most preferably, MDI based adhesives are used.
The additives are optional. They are used in small amounts and for different purposes. The most widely used additive is a wax, preferably paraffin wax, which is added as a wax melt or in the form of an aqueous emulsion. Paraffin wax or other waxes are mainly added to improve the swelling properties of MDF.
In a preferred embodiment, the MDF board of the present invention is prepared in a process comprising the steps of:
a) providing acetylated rubberwood fibers as defined herein;
b) contacting the acetylated rubberwood fibers with a sizing agent and preferably an additive, preferably a wax;
c) drying;
d) casting the fibers onto a surface to form a mat;
e) cold pre-pressing;
f) hot pressing;
g) correcting and cutting to size;
h) and (6) polishing.
In commercial continuous processes, the surface on which the fibers are cast is typically a moving belt, with further steps including pressing by the moving belt, such as by a double belt press or calender. However, it is conceivable to arrange the mat on a continuously moving belt and to carry out the pressing in a multi-layer press.
MDF boards comprising acetylated wood fibres of the invention may be prepared according to the following general method for example:
(a) cutting solid rubber wood; acetylating the chips; refining the acetylated wood to form acetylated wood fibers; forming the fibers into an MDF board as described above; or
(b) Cutting solid rubber wood, and fine grinding to form wood fibers; acetylation of wood fibers; the fibers were made into MDF boards as described above.
Reference is provided for a background on particle-, oriented strand and fibre boards manufactured on the basis of acetylated wood, WO 2011/095824.
Preferably, the board of the invention, in particular MDF board, has at least0.8N/mm2Preferably at least 1.0N/mm2More preferably at least 1.2N/mm2Most preferably at least 1.5N/mm2Internal bond strength of (2).
It is to be understood that all embodiments as defined herein may be combined to describe other embodiments. When referred to herein as the "present invention" it is to be understood that reference is made to all embodiments of the invention.
Some embodiments are embodiments 1-15 listed below.
Embodiment 1: a panel comprising acetylated wood elements, wherein the acetylated wood elements are obtained from a rubber wood, and wherein the acetylated wood elements have an acetyl content of at least 17%.
Embodiment 2: a panel comprising acetylated wood elements, wherein the acetylated wood elements are obtained from a rubber wood, and wherein the acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting the wood elements with an acetylation agent;
wherein the acetylating agent is in the vapor phase.
Embodiment 3: a panel according to any one of the preceding embodiments, wherein the acetylated wood elements are present in an amount of at least 50 wt%, preferably at least 80 wt%, compared to the total weight of wood elements comprised in the panel.
Embodiment 4: a panel according to any one of the preceding embodiments, wherein the acetylated wood elements have an acetyl content of at most 35%.
Embodiment 5: the panel according to any of the preceding embodiments, wherein the panel is selected from the group consisting of medium density fiberboard, low density fiberboard, high density fiberboard, particleboard, and flakeboard; medium density fiberboard is preferred.
Embodiment 6: a panel according to any one of the preceding embodiments, wherein the acetylated wood elements are selected from the group consisting of fibres, chips, strands, particles, slivers and fibre tows; fibers are preferred.
Embodiment 7: a panel according to any of embodiments 2 to 6, wherein the acetylated wood elements have an acetyl content of at least 8%, preferably at least 17%.
Embodiment 8: acetylated wood elements, wherein the acetylated wood elements are rubber woods, wherein the acetylated wood elements are obtainable by a process comprising the following sequential steps:
a) providing wood elements from a rubber-wood material; and
b) contacting said wood elements with an acetylation agent, wherein said acetylation agent is in the vapor phase.
Embodiment 9: acetylated wood elements according to embodiment 8 wherein the acetylation agent is selected from the group consisting of acetic anhydride, acetic acid, ketene, acetyl chloride and combinations thereof.
Embodiment 10: acetylated wood element according to any of embodiments 8 and 9, wherein the acetylated wood element has an acetyl content of at least 8%, preferably at least 17%, and preferably at most 35%.
Embodiment 11: the acetylated wood element according to any of embodiments 8 to 10 wherein the wood element is a wood fibre.
Embodiment 12: the acetylated wood element according to any of embodiments 8 to 10 wherein the wood element is a wood chip.
Embodiment 13: acetylated wood elements, wherein the wood elements are fibers obtained by refining wood chips according to embodiment 12.
Embodiment 14: a method for manufacturing a panel according to any of embodiments 1 to 7, wherein the method comprises the following sequential steps:
a) providing an acetylated wood element according to any of embodiments 8 to 13 and a glue; and
b) forming the plate.
Embodiment 15: the method according to embodiment 14, wherein said acetylated wood elements have a moisture content of 4 to 8 wt% compared to the total weight of the acetylated wood fibres.
The invention will now be illustrated with reference to the following non-limiting examples.
Examples
Example 1: acetylation of wood elements made of rubber wood
Example 1.1 acetylation in the vapour phase at atmospheric pressure
The rubber wood chips were dried in an oven at 105 ℃ for 16 hours. The splits were then impregnated with an acetylation agent using the method according to Bethel. The acetylating reagent is a mixture of 10 vol% acetic acid and 90 vol% acetic anhydride, where vol% is compared to the total volume of the acetylating reagent. After impregnation, excess liquid was removed and the impregnated rubber wood chips were transferred to a reaction vessel. Acetylation is carried out at a temperature of 150 ℃ to 170 ℃ for 30 minutes to 120 minutes under atmospheric conditions. The fragments were then allowed to cool before analysis. Acetylated rubber wood chips with acetyl content of 17% to 20% were obtained in this way. The acetylated gum wood chips were refined to obtain acetylated gum wood fibers.
Example 1.2 acetylation in the vapor phase at elevated pressure
In another test, the rubber wood chips were dried in an oven at 105 ℃ for 16 hours and then subjected to Bethel type impregnation with an acetylation agent. The acetylating reagent is a mixture of 10 vol% acetic acid and 90 vol% acetic anhydride, where vol% is compared to the total volume of the acetylating reagent. After the impregnation process, the excess liquid was removed and the rubber wood chips were transferred to a reaction vessel. Remove air and use nitrogen (N)2) Instead. The splits were acetylated at 190 ℃ for 15 to 60 minutes at a pressure of 2 to 4 bar. The reaction vessel and its contents were then brought back to ambient conditions. The chemical recovery step is carried out at a temperature of 150 ℃ to 200 ℃ for 30 minutes to 60 minutes. The fragments were then allowed to cool before analysis. In this way acetylated rubber woods with acetyl content of 17 to 25%, mainly 20 to 25%, are obtainedThe wood chips. The acetylated gum wood chips were refined to obtain acetylated gum wood fibers.
Example 1.3 acetylation in liquid phase at elevated pressure
In another test, the rubber wood chips were dried in an oven at 105 ℃ for 16 hours. Transferring the rubber wood chips into a reaction vessel and applying nitrogen (N)2) Instead of air. The chips were then impregnated with an acetylating agent using the Bethel method. The acetylating reagent is a mixture of 10 vol% acetic acid and 90 vol% acetic anhydride, where vol% is compared to the total volume of the acetylating reagent. After the impregnation procedure, the chips are acetylated at a temperature of 150 ℃ to 190 ℃ for 15 minutes to 60 minutes at a pressure of 2 bar to 4 bar. Then, excess liquid is removed, and a chemical recovery step is performed at a temperature of 150 ℃ to 200 ℃ for 30 minutes to 60 minutes. The fragments were then brought to ambient conditions prior to analysis. Acetylated rubber wood chips with acetyl content of 17 to 25%, mainly 20 to 25%, were obtained in this way.
Example 2: preparation of MDF boards comprising acetylated Wood elements made of rubber Timber
Example 2.1
The acetylated rubberwood fibers obtained in example 1.1 or example 1.2 were mixed with MDI resin (6 wt%) and release wax (2 wt%) in a blow line after the refining step. The moisture content of the rubber wood fiber is controlled to 6 to 8 wt%. Hand-formed to dimensions 520x560x12mm3And pressed in a distance-adjusted down-stroke press. The prepressing pressure was 10 bar, the pressing temperature was 220 ℃ and the pressing factor was 10 s/mm. The density of the formed board was 740kg/m3. Reference MDF boards made from non-acetylated rubber wood fibers were prepared in the same manner.
Example 2.2
A panel was prepared according to example 2.1 from acetylated rubber wood fibres obtained according to example 1.2, the only difference being that 1 wt% of mould release wax was used instead of 2 wt% as mentioned in example 2.1. A reference MDF board made of non-acetylated rubberwood fibres was prepared in the same way as an MDF board made of acetylated rubberwood fibres.
Example 3: measurement of internal bond Strength of MDF boards
The internal bond strength of the prepared MDF boards was tested according to the procedure described in European Standard (European Norm) EN-319.
The acetylated rubber Wood MDF Board prepared by example 2.1 had an internal bond Strength of 1.92. + -. 0.2N/mm2. For the reference MDF board made of non-acetylated shea gum prepared as in example 2.1, the internal bond strength was 1.40. + -. 0.2N/mm2。
The acetylated rubber Wood MDF Board prepared by example 2.2 had an internal bond Strength of 1.84. + -. 0.2N/mm2. For the reference MDF board made of non-acetylated shea gum prepared as in example 2.2, the internal bond strength was 1.54. + -. 0.2N/mm2。