CN112250576B - Bifunctional reactive rosin resin, preparation method thereof and application thereof in improving performance of fast-growing wood - Google Patents
Bifunctional reactive rosin resin, preparation method thereof and application thereof in improving performance of fast-growing wood Download PDFInfo
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- CN112250576B CN112250576B CN202011134516.7A CN202011134516A CN112250576B CN 112250576 B CN112250576 B CN 112250576B CN 202011134516 A CN202011134516 A CN 202011134516A CN 112250576 B CN112250576 B CN 112250576B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- 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
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
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- 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
- B27K3/156—Combined with grafting onto wood fibres
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- 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
- B27K5/04—Combined bleaching or impregnating and drying of wood
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- 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
- B27K2240/00—Purpose of the treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a bifunctional reactive rosin resin, a preparation method thereof and application thereof in improving the performance of fast-growing wood. The invention takes hydrogenated rosin and maleic anhydride as main raw materials, and prepares bifunctional reactive rosin resin REMG by methods such as epoxy ring opening, esterification and the like. Dissolving REMG in absolute ethyl alcohol, and adding an initiator to prepare a steeping fluid; and (3) putting the fast-growing wood into the impregnation liquid, and impregnating, drying and curing to obtain the modified fast-growing wood. The REMG prepared by the invention has the advantages that the soft chain segment contains two double bonds, so that the crosslinking degree of the REMG is improved, the bonding strength of the REMG and wood is improved, and the modified fast growing wood with excellent performance is prepared. The method provided by the invention is simple, low in production cost and has an industrial application prospect; in addition, the rosin is a green renewable resource, a new way is explored for high-value utilization of the rosin, the additional value of the rosin is greatly improved, and the rosin is environment-friendly.
Description
Technical Field
The invention belongs to the field of wood modification, and particularly relates to bifunctional reactive rosin resin, a preparation method thereof, and application thereof in improving the performance of fast-growing wood.
Background
Since ancient times, wood is widely applied to various fields such as pulping and papermaking, building design, interior decoration, furniture manufacturing and the like due to the unique characteristics of easy processing, high strength-weight ratio, environmental friendliness and beautiful texture. However, the supply of high-quality wood cannot meet the increasing market demand due to the long growth cycle of high-quality wood, and the contradiction between the supply and demand of wood is particularly prominent. The demand of China for wood is huge and increases year by year, however, the current situation of China for wood resources is that available resources are few, high-quality wood and large-diameter wood are lack, the external dependence is high, and the safety situation of wood is severe. To alleviate this contradiction, China vigorously develops artificial forests. The fast-growing poplar is one of three kinds of fast-growing artificial forest in China due to its advantages of short growth period, strong adaptability, high yield and the like. However, the fast-growing poplar has the disadvantages of poor dimensional stability, high hygroscopicity, poor mechanical strength and the like, so that the high-value utilization of the fast-growing poplar is greatly limited. Therefore, modification of fast-growing wood becomes necessary.
The chemical modifier for modifying the fast-growing wood comprises the following components: thermosetting resin, organic monomer, paraffin, acetylation reagent, furfuryl alcohol resin and N-hydroxymethyl amide compound. However, the water resistance and the mechanical property of the fast-growing wood are improved, and the problems of high treatment temperature, easy loss, slow release of harmful substances and the like of the modifier still exist. The mechanical strength of the wood is reduced due to the structural damage of the wood and the thermal degradation reaction of cellulose, hemicellulose and lignin in the processes of compaction treatment, high-temperature heat treatment and the like. Therefore, the method for modifying the carbon fiber has great practical significance and is environment-friendly and can be used in a medium-low temperature range.
Rosin is an important terpenoid forest secondary metabolite, and has a unique tricyclic diterpene rigid structure, so that the rosin has the characteristics of good hydrophobicity, high hardness and the like. The main component of rosin is resin acid, namely monocarboxylic acid which takes a three-membered phenanthrene ring structure as a framework and contains two double bonds. Based on the conjugated double bond and carboxyl, Diels-Alder addition, hydrogenation, polymerization, esterification, isomerization and other reactions can occur. The method is widely applied to the production of paper making, printing ink, adhesives, coatings, soaps, medicines, pesticides and the like. The rosin with high hardness and good hydrophobicity is applied to the field of wood modification, and the wood with certain hydrophobicity and mechanical properties has great research significance. However, although natural rosin has certain rigidity and hydrophobicity, its binding ability with wood is insufficient, so that its application in the wood field is limited.
Disclosure of Invention
The invention aims to provide a bifunctional reactive rosin resin, a preparation method thereof and application thereof in improving the performance of fast-growing wood, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a difunctional reactive rosin Resin (REMG) having the following molecular structure:
the preparation method of the bifunctional reaction type rosin Resin (REMG) comprises the following steps:
s1, under the action of a catalyst, carrying out esterification reaction on hydrogenated rosin and epoxy chloropropane to obtain an intermediate product I;
s2, adding maleic anhydride into the intermediate product I, adding a polymerization inhibitor and a catalyst at the same time, and carrying out esterification reaction on the intermediate product I and the maleic anhydride to obtain an intermediate product II;
s3, adding glycidyl methacrylate into the intermediate product II, adding the polymerization inhibitor and the catalyst again, and carrying out esterification reaction on the intermediate product II and the glycidyl methacrylate to obtain a final product, namely REMG.
As a preferable technical scheme, the catalyst is 2, 3-epoxypropyl trimethyl ammonium chloride, and the polymerization inhibitor is p-hydroxyanisole.
Another object of the present invention is to provide the use of the above difunctional reactive rosin resin for improving the properties of fast-growing wood, comprising the following steps:
(1) dissolving bifunctional reactive rosin resin in absolute ethyl alcohol, and adding an initiator to prepare an impregnation solution; preferably, the mass concentration of the bifunctional reaction type rosin resin in the impregnation liquid is 20-60%; the initiator is BPO, and the mass of the initiator is 1-5% of that of the bifunctional reactive rosin resin; specifically, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% may be selected.
(2) Putting the fast-growing wood into a steeping fluid, and taking out the fast-growing wood after steeping, wherein the purpose of steeping is to enable the REMG to enter cells of the fast-growing wood; preferably, the impregnation sequentially comprises vacuum impregnation and room-temperature normal-pressure impregnation; the vacuum degree of the vacuum impregnation is 0.08-0.1 Mpa, and the time is 20-60 min; the room-temperature normal-pressure impregnation time is 20-28 h, and the temperature is 20-27 ℃. Further preferably, the vacuum degree of vacuum impregnation can be 0.08MPa, 0.09MPa or 0.1MPa, and the impregnation time can be 20min, 30min, 40min, 50min or 60 min; the soaking time at room temperature and normal pressure can be 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h or 28 h.
(3) And (3) putting the fast-growing wood taken out in the step (2) into an oven, firstly, drying to volatilize the absolute ethyl alcohol soaked in the fast-growing wood, and then, curing to finish the modification of the fast-growing wood to obtain the modified fast-growing wood. Preferably, the temperature of the drying treatment is 30-50 ℃; the curing treatment temperature is 110-120 ℃, and the curing treatment time is 10-14 h. Further preferably, the temperature of the drying treatment can be 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, and the time can be 1h, 1.5h or 2 h; the curing treatment temperature can be 110 deg.C, 111 deg.C, 112 deg.C, 113 deg.C, 114 deg.C, 115 deg.C, 116 deg.C, 117 deg.C, 118 deg.C, 119 deg.C or 120 deg.C, and the curing time can be 10h, 11h, 12h, 13h or 14 h.
The invention obtains the following technical effects:
(1) the invention takes hydrogenated rosin and maleic anhydride as main raw materials, and prepares bifunctional reactive rosin resin REMG by methods such as epoxy ring opening, esterification and the like. Because the soft chain segment of the REMG contains two double bonds, after the REMG enters the interior of the wood through impregnation, a double crosslinking reaction is carried out under the action of an initiator in the curing treatment, and the formed high molecular polymer is deposited on the cell cavity, the cell gap and the cell wall of the wood, so that the functions of strengthening the cell wall, sharing load and reducing wood deformation are achieved, and the mechanical property of the wood is further improved. Namely, the invention increases the crosslinking degree of the REMG and improves the bonding strength of the REMG and the wood by increasing the number of functional groups in the REMG.
(2) The modified fast-growing wood is obtained through simple dipping, drying and curing treatment, the preparation method is simple, the production cost is low, and the modified fast-growing wood has an industrial application prospect; the rosin is a green renewable resource, and the invention explores a new way for high-value utilization of the rosin, greatly improves the added value of the rosin and has environmental friendliness.
(3) Through the immersion modification treatment of the REMG, the density and the weight gain rate of the fast-growing wood are obviously increased, the mass loss rate is 2-6%, the contact angle is increased by 38-64 degrees, the water absorption is reduced by 50-59%, the static bending strength, the elastic modulus and the compressive strength are respectively increased by 42.9%, 39.9% and 97.9%, and the prepared REMG modified material has good water resistance and good mechanical properties, so that the fast-growing wood is limited and weakened in application.
Drawings
Fig. 1 is a water absorption graph of modified fast-growing woods manufactured in examples and comparative examples.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The fast-growing wood selected in the following embodiments is fast-growing poplar, and other fast-growing woods in the art, such as eucalyptus and pine, are also applicable to the following test method, and are not listed here.
Example 1
Preparation of difunctional reactive rosin resin REMG: 320g of hydrogenated rosin, 89.6g of epichlorohydrin and 0.8192 g of 2, 3-epoxypropyltrimethylammonium chloride were weighed out accurately into a 1000 mL four-neck flask, and a reflux and mechanical stirring device was connected. Setting the reaction temperature at 110 ℃, and reacting until the acid value is less than 1mg/g to obtain an intermediate product I; cooling to 80 ℃, adding 94.97g of maleic anhydride, adding 0.4749 g of p-hydroxyanisole serving as a polymerization inhibitor, supplementing 0.1899 g of 2, 3-epoxypropyltrimethylammonium chloride, and reacting for 3 hours to obtain an intermediate product II; finally, 137.66g of glycidyl methacrylate is added, 0.6883 g of p-hydroxyanisole and 0.2753 g of 2, 3-epoxypropyl trimethyl ammonium chloride are added, the acid value is less than 5mg/g, the reaction is stopped, and discharging is carried out to obtain the REMG, wherein the molecular structural formula is as follows:
example 2
Randomly selecting 20 × 20 × 20mm without damage 3 The fast-growing poplar wood block is dried to constant weight at 105 ℃, and the weight and the size of the wood block are measured. Weighing bifunctional reactive rosin resin REMG, dissolving in absolute ethanol to prepare REMG ethanol solutions with mass concentrations of 30% and 50%, and adding initiator BPO (2% of RMEG mass) to prepare an impregnation solution. And (2) placing the fast-growing wood in the impregnation liquid at a vacuum degree of 0.095MPa for 30min, impregnating at room temperature (25 ℃) for 24h under normal pressure, filtering, drying in an oven at 40 ℃ for 1h to volatilize ethanol, and then raising the temperature to 120 ℃ for curing for 12h to obtain the RMEG modified material. The mass and size thereof were measured. The weight gain of the modified REMG material obtained through modification is 55.86%, which indicates that RMEG is successfully cured and filled in wood.
Comparative example 1
Preparation of monofunctional reactive rosin resin RESG: 320g of hydrogenated rosin, 89.6g of epichlorohydrin and 0.8192 g of 2, 3-epoxypropyltrimethylammonium chloride were weighed out accurately into a 1000 mL four-neck flask, and a reflux and mechanical stirring device was connected. Setting the reaction temperature at 110 ℃, and reacting until the acid value is less than 1mg/g to obtain an intermediate product I; cooling to 80 ℃, adding 96.91g of succinic anhydride, adding 0.4846 g of p-hydroxyanisole serving as a polymerization inhibitor, supplementing 0.1940 g of 2, 3-epoxypropyltrimethylammonium chloride, and reacting for 3 hours to obtain an intermediate product II; finally, 137.66g of glycidyl methacrylate is added, 0.6883 g of p-hydroxyanisole and 0.2753 g of 2, 3-epoxypropyl trimethyl ammonium chloride are added, the acid value is less than 5mg/g, the reaction is stopped, and discharging is carried out to obtain RESG, wherein the molecular structural formula is as follows:
comparative example 2
The same procedure as in example 2 was followed, except that an equal amount of the ethanol solution of REMG was used as the impregnation solution instead of the ethanol solution of REMG. The prepared wood sample was designated as a blank wood.
Comparative example 3
The same procedure as in example 2 was conducted, except that RESG ethanol solutions having 30% and 50% by mass concentrations were used as the impregnation solution instead of the REMG ethanol solution. The prepared wood sample is marked as RESG modified wood.
Detection and analysis
To investigate the water resistance of the REMG modifier, the wood samples prepared in example 2 and comparative examples 2 to 3 were immersed in deionized water at room temperature, and the mass of the wood samples was measured after different time intervals. WU (water absorption) was calculated according to the following formula, wherein: w 1 Weight of wood sample before impregnation, W 2 Is the total weight of the wood sample after immersion in deionized water for various time intervals.
WU＝(W 2 -W 1 )/W 1 ×100
The water absorption data of the wood samples are shown in fig. 1, and it can be seen from fig. 1 that the water absorption of both the REMG modified wood and the RESG wood is significantly reduced compared to the blank control wood. All wood water absorption rates are increased and then tend to be constant. After 12 days of impregnation, the water absorption of the blank control wood is as high as 176.2%; the water absorption of the 30% regg modified material was 87.3%, and the water absorption of the 50% regg modified material was 71.7%; the water absorption of the control 30% RESG wood was 92.5%, and the water absorption of the 50% RESG wood was 75.7%. The water absorption of the reg modified material with the same concentration is lower than that of the RESG modified material, i.e., the reg modification effect is better. The reason why the REMG modified material has better water resistance is that REMG is a monomer with bifunctionality, and under the condition of heating and the existence of an initiator, two double bonds on a long chain can generate a co-crosslinking reaction, so that the formed polymer has better hydrophobic property.
To study the mechanical properties of the REMG, MOR, MOE and CS were examined for all wood samples according to GB/T1936.1-2009, GB/T1936.2-2009 and GB/T1939-2009. The results are shown in table 1:
TABLE 1 mechanical Properties of the Wood samples
As can be seen from Table 1, the mechanical properties of the REMG modified material are obviously improved, and compared with a blank Control (CW), the increase rates of MOR, MOE and CS of the 30 percent REMG modified material are respectively 34.3 percent, 37.9 percent and 48.8 percent; MOR, MOE and CS of the 50% REMG modifier were 42.9%, 39.9% and 97.9%, respectively. Compared with RESG wood of a control group with the same concentration, the mechanical properties of the REMG modified material are improved more obviously. The mechanical property of the modified wood is improved because the REMG modifier immersed in the wood performs double cross-linking reaction, and the formed high molecular polymer is deposited on the cell cavity, the intercellular spaces and the cell walls of the wood, so that the effects of enhancing the cell walls, sharing loads and reducing the deformation of the wood are achieved, and the mechanical property of the wood is improved. The REMG modification effect is better than that of the RESG modification effect in the control group, probably because REMG is a bifunctional modifier, and the mechanical strength of the polymer generated by the double cross-linking reaction is stronger than that of the polymer formed after RESG cross-linking. The REMG effectively strengthens the wooden framework by the methods of vacuum impregnation and heating solidification, and improves the mechanical property of the fast-growing poplar.
Claims (7)
1. A bifunctional reactive rosin resin characterized by: the molecular structural formula is as follows:
2. the method of claim 1 wherein the difunctional reactive rosin resin is prepared by: the method comprises the following steps:
s1, carrying out esterification reaction on hydrogenated rosin and epoxy chloropropane under the action of a catalyst to obtain an intermediate product I;
s2, adding maleic anhydride into the intermediate product I, adding a polymerization inhibitor and a catalyst at the same time, and carrying out esterification reaction on the intermediate product I and the maleic anhydride to obtain an intermediate product II;
s3, adding glycidyl methacrylate into the intermediate product II, adding the polymerization inhibitor and the catalyst again, and carrying out esterification reaction on the intermediate product II and the glycidyl methacrylate to obtain a final product, namely the bifunctional reactive rosin resin.
3. The method of claim 2, wherein: the catalyst is 2, 3-epoxypropyl trimethyl ammonium chloride, and the polymerization inhibitor is p-hydroxyanisole.
4. The use of a difunctional reactive rosin resin according to claim 1 for improving fast-growing wood properties, wherein: the method comprises the following steps:
(1) dissolving bifunctional reactive rosin resin in absolute ethyl alcohol, and adding an initiator to prepare an impregnation solution;
(2) putting the fast-growing wood into a steeping fluid, and taking out after steeping;
(3) and (3) putting the fast-growing wood taken out in the step (2) into an oven, firstly, drying to volatilize the absolute ethyl alcohol soaked in the fast-growing wood, and then, curing to finish the modification of the fast-growing wood to obtain the modified fast-growing wood.
5. Use according to claim 4, characterized in that: in the step (1), the mass concentration of the bifunctional reaction type rosin resin in the impregnation liquid is 20-60%; the initiator is BPO, and the mass of the initiator is 1-5% of that of the bifunctional reactive rosin resin.
6. Use according to claim 4, characterized in that: in the step (2), the impregnation sequentially comprises vacuum impregnation and room-temperature normal-pressure impregnation; the vacuum degree of the vacuum impregnation is 0.08-0.1 Mpa, and the time is 20-60 min; and the room-temperature normal-pressure impregnation time is 20-28 h.
7. Use according to claim 4, characterized in that: in the step (3), the temperature of the drying treatment is 30-50 ℃; the curing treatment temperature is 110-120 ℃, and the curing treatment time is 10-14 h.
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| CN101215445A (en) * | 2007-12-28 | 2008-07-09 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| CN108058250A (en) * | 2017-12-21 | 2018-05-22 | 安徽明豪实木家俱有限公司 | A kind of method of modifying for cotton wood |
| CN109705261A (en) * | 2017-10-26 | 2019-05-03 | 中国林业科学研究院木材工业研究所 | A kind of environment-friendly type Wood modifier and its application and Wooden modifying processing method |
| CN110577799A (en) * | 2019-09-24 | 2019-12-17 | 广东科茂林产化工股份有限公司 | Epoxy compound modified rosin resin and preparation method and application thereof |
| AU2019101692A4 (en) * | 2019-12-24 | 2020-02-06 | Institute of Chemical Industry of Forest Products Chinese Academy of Forestry | Method for Modification of Fast Growing Wood Using Rosin-based Unsaturated Resin |
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- 2020-10-21 CN CN202011134516.7A patent/CN112250576B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101215445A (en) * | 2007-12-28 | 2008-07-09 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| CN109705261A (en) * | 2017-10-26 | 2019-05-03 | 中国林业科学研究院木材工业研究所 | A kind of environment-friendly type Wood modifier and its application and Wooden modifying processing method |
| CN108058250A (en) * | 2017-12-21 | 2018-05-22 | 安徽明豪实木家俱有限公司 | A kind of method of modifying for cotton wood |
| CN110577799A (en) * | 2019-09-24 | 2019-12-17 | 广东科茂林产化工股份有限公司 | Epoxy compound modified rosin resin and preparation method and application thereof |
| AU2019101692A4 (en) * | 2019-12-24 | 2020-02-06 | Institute of Chemical Industry of Forest Products Chinese Academy of Forestry | Method for Modification of Fast Growing Wood Using Rosin-based Unsaturated Resin |
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