WO2015157944A1 - 一种利用石蜡-硅烷复合乳液改善高温热处理材性能的方法 - Google Patents

一种利用石蜡-硅烷复合乳液改善高温热处理材性能的方法 Download PDF

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WO2015157944A1
WO2015157944A1 PCT/CN2014/075512 CN2014075512W WO2015157944A1 WO 2015157944 A1 WO2015157944 A1 WO 2015157944A1 CN 2014075512 W CN2014075512 W CN 2014075512W WO 2015157944 A1 WO2015157944 A1 WO 2015157944A1
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wood
temperature heat
paraffin
heat treatment
composite emulsion
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PCT/CN2014/075512
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English (en)
French (fr)
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曹金珍
王望
朱愿
崔福通
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北京林业大学
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Priority to PCT/CN2014/075512 priority Critical patent/WO2015157944A1/zh
Publication of WO2015157944A1 publication Critical patent/WO2015157944A1/zh

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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
    • 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
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • 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

Definitions

  • the invention belongs to the field of wood processing, and particularly relates to a method for improving the performance of a high-temperature heat-treated material by using a paraffin-silane composite emulsion impregnation pretreatment. Background technique
  • Wood is a green material naturally grown by trees in nature. It is a huge biomass in forest ecosystems. As an industrial and domestic material, wood is closely related to national economic construction and human life, and has many excellent qualities, such as strong weight ratio, low processing energy consumption, less environmental pollution, recyclability and good environmental coordination.
  • the wood is mainly composed of cellulose, hemicellulose and lignin, so it contains a large amount of hydrophilic hydroxyl groups, which is easy to absorb water.
  • the moisture content of the wood causes some defects in the wood, such as dry shrinkage and wetness, and the size is not. Stable; Perishable, poor biological durability, etc., to some extent limit the use value and application range of wood.
  • High-temperature heat treatment technology is a technique commonly used to improve the performance of wood in recent years.
  • the method is to protect the wood under the conditions of high temperature steam (about 150 ⁇ 260 ° C) under the protection of superheated steam, inert gas or hot oil.
  • the heat treatment is carried out for a while.
  • the wood obtained by high-temperature heat treatment is called high-temperature heat-treated material, also called carbonized wood.
  • high-temperature heat-treated materials have many advantages, their water absorption and dimensional stability still cannot meet the requirements of contemporary industry.
  • CN101716790A discloses a method for producing rubber tree charcoal wood by resin pretreatment, which reduces the water absorption of the rubber tree charcoal wood and improves its dimensional stability and durability.
  • CN103240780A discloses a method for improving the properties of charred wood by using silica sol infusion pretreatment, which reduces the mass loss rate of carbonized wood, reduces the equilibrium moisture content, and improves dimensional stability and termite resistance.
  • concentration of silica sol used in this patent reaches 20-50%, resulting in excessive production costs, and too high a treatment concentration will affect the characteristics of the wood itself to some extent.
  • the present application provides a treatment method which is economical and environmentally friendly and can significantly improve the waterproof performance and dimensional stability of the high-temperature heat-treated material, thereby making the high-temperature heat-treated material more suitable. Used in outdoor environments.
  • a method for improving the performance of a high temperature heat treated material by using a paraffin-silane composite emulsion treatment comprising the following steps:
  • the wood is placed in an infusion tank for vacuum treatment, and then introduced into a paraffin-silane composite emulsion having a solid content of 1 to 6%, and the wood is taken out and air-dried, and then the kiln is dried to a moisture content of 12 to 18%. ;
  • the step 1) the paraffin-silane composite emulsion has a solid content of 2 to 4%.
  • the vacuum processing conditions of the step 1) are: a relative vacuum of -0.05 to -0.1 MPa, preferably -0.06 to -0.096 MPa, and a treatment time of 20 to 60 minutes.
  • the high-temperature heat treatment in the step 2) is to maintain the wood treated in the step 1) and dried at 180 220 ° C for 2 to 6 hours, and after cooling, a high-temperature heat-treated material is obtained.
  • step 2 The high temperature heat treatment described in step 2) is divided into three stages:
  • the above steps 2) are as follows: firstly, the wood is placed in a high-temperature heat treatment equipment, preheated at 55 ⁇ 65 °C for 1 ⁇ 3h, and then the temperature is raised to 120 ⁇ 140 °C within 14 ⁇ 24h. Maintain l ⁇ 4h, then continue to spray water vapor into the high temperature heat treatment equipment as protective gas, and gradually increase the temperature to 180 ⁇ 220 °C for 2 ⁇ 6h in the next 3 ⁇ 6h; then under the condition of water vapor protection, Gradually cool down to 110 ⁇ 130 °C within 3 ⁇ 6h, stop the steam supply, and naturally cool to remove the wood at room temperature.
  • the high temperature heat treatment equipment described in the present application is a device known to those skilled in the art for high temperature heat treatment of wood, such as XNH series wood high temperature heat treatment equipment (Jiangsu Xingnan Drying Equipment Co., Ltd.).
  • the paraffin-silane composite emulsion of the present invention is a technical solution disclosed by CN103341894A, An emulsion prepared by the following components and a ratio of raw materials: 1 to 2000 parts of a solid paraffin having a melting point of 48 to 64 ° C, and 1 to 2000 parts of an alkylalkalkoxysilane having a chain length of 1 to 18, 1 to 500 parts of nonionic surfactant, 1 to 200 parts of anionic surfactant, 1 to 200 parts of co-surfactant, 1 to 200 parts of fatty acid, and 10,000 parts of water.
  • the solid paraffin ⁇
  • melting point is 48-64 ° C
  • refined paraffin semi-refined paraffin, crude paraffin.
  • the alkylalkyltrialkoxysilane R ⁇ i OR 2 ) ⁇ wherein the substituent R 1 is a C1 to C18 alkyl group, and R 2 is a methyl group, an ethyl group, a propyl group or the like.
  • the nonionic surfactant sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether, polyoxyethylene sorbitan monolaurate, fatty alcohol polyoxyethylene ether, and the like.
  • the anionic surfactant sodium stearate, sodium alkyl sulfonate, succinate sulfonate, lignosulfonate, and the like.
  • the co-surfactant isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, and the like.
  • the fatty acid oleic acid, stearic acid, and the like.
  • the preparation method of the paraffin-silane composite emulsion placing the paraffin wax at 70 ° C ⁇ 100 ° C, preferably 80 ° C ⁇ 90 ° C, after the solid paraffin is completely dissolved, adding paraffin while stirring a trialkoxysilane, and sequentially adding a nonionic surfactant, an anionic surfactant, a co-surfactant, a fatty acid, and maintaining the entire system at 70 ° C to 100 ° C, preferably 80 ° C to 90
  • the mixture is heated and stirred at a speed of 2000 rpm to 10000 rpm, preferably 3000 rpm to 6000 rpm for 10 to 30 minutes, and water is added while stirring to prepare a preliminary emulsion.
  • the primary emulsion is subjected to high pressure homogenization through a high pressure homogenizer, and the homogenization pressure is 20 MPa to 80 MPa, preferably 40 MPa to 60 MPa, and the number of homogenization times is 1 to 2 times, preferably 2 times, to finally obtain a paraffin-silane composite emulsion.
  • the wood is pretreated by using a paraffin-silane composite emulsion, wherein the paraffin wax covers the surface of the wood cell to have a high hydrophobic coverage, and the silane chemically reacts with the hydroxyl group on the surface of the wood to jointly hinder the water absorption of the wood. , further improve the hydrophobicity and dimensional stability of the wood, and better adapt to the outdoor use environment. Moreover, silane has a certain bactericidal effect, which can improve the corrosion resistance of wood to a certain extent. On this basis, the high-temperature heat treatment conditions are optimized, and the wood hemicellulose is degraded in a large amount by heating at 180 ⁇ 220 °C.
  • paraffin-silane composite emulsion It is more evenly distributed in wood, and the degree of cross-linking reaction is obviously enhanced.
  • the combination of paraffin-silane composite emulsion and wood is strengthened. Under the solid content of 4%, good modification effect can be obtained, production cost can be reduced, and good synergy can be achieved. effect.
  • Fig. 1 is a water absorption ' & test result of the high temperature heat treated material of the present invention and a comparative example.
  • Fig. 2 is a graph showing the chord resistance expansion ratio of the wood of Example 4, Comparative Example 2 and Comparative Example 3 with respect to Comparative Example 1.
  • Fig. 3 is a SEM result of the chord section of Comparative Example 1.
  • Fig. 4 is a SEM result of the chord section of Comparative Example 2.
  • Fig. 5 is a SEM result of the chord section of Comparative Example 3.
  • Fig. 6 is a SEM result of the chord section of Example 4. detailed description
  • the wood used in the following examples is all southern pine, but not limited to southern pine, common softwood, such as European red pine, masson pine, etc., common hardwood, Such as Qingyang, Populus tomentosa, Birch, etc.
  • No. 54 semi-refined paraffin wax 100g, n-dodecyltrialkoxysilane 200g, sorbitan fatty acid ester span80 15g, polyoxyethylene sorbitan monolaurate tween80 35g, sodium stearate 20g, hard 20 g of fatty acid and 20 g of n-pentanol, 620 g of water.
  • a paraffin-silane composite emulsion was prepared according to the method described in CN103341894A.
  • the wood is pretreated by using the paraffin-silane composite emulsion prepared in the step 1), and the wood is placed in an infusion tank for vacuum treatment, the relative vacuum is -0.09 MPa, the treatment time is 30 min; and then the solid content is 4%.
  • the paraffin-silane composite emulsion was subjected to a pressure treatment, and the relative pressure of the pressure treatment was 1.5 MPa, and the treatment time was 40 minutes.
  • the wood was then taken out and air dried for 3 days, after which the kiln was dried to a moisture content of 18%.
  • the pretreated and dried wood is placed in a high temperature heat treatment apparatus and preheated at 60 ° C. Subsequently, the temperature was gradually increased to 130 ° C in 14 h and maintained for 1 h, and water vapor was continuously sprayed into the high-temperature heat treatment apparatus as a shielding gas. Then gradually increase the temperature to 180 ° C within 3 h for 3 h. Then, under the condition of water vapor protection, gradually reduce the temperature to 120 °C within 4 hours, stop the water vapor supply, naturally cool to normal temperature, take out the wood, and finally obtain the paraffin-silane composite emulsion pretreatment modified high temperature heat treatment material.
  • Example 2
  • No. 58 semi-refined paraffin 120g, n-butyltriethoxysilane 240g, sorbitan fatty acid ester span20 10g, polyoxyethylene sorbitan monolaurate tween80 20g, sodium dioctylsulfosuccinate 10g 5 g of lauric acid and 5 g of isoamyl alcohol, 670 g of water.
  • a paraffin-silane composite emulsion was prepared according to the method described in CN103341894A.
  • the prepared paraffin-silane composite emulsion was used to pretreat the wood, and the wood was placed in an infusion tank for vacuum treatment.
  • the relative vacuum was -0.06 MPa and the treatment time was 60 min.
  • the paraffin-silane with a solid content of 3% was introduced.
  • the composite emulsion was subjected to a pressure treatment, and the relative pressure of the press treatment was 1.5 MPa, and the treatment time was 90 minutes.
  • the wood was then taken out and air dried for 5 days, after which the kiln was dried to a moisture content of 16%.
  • the pretreated and dried wood is placed in a high-temperature heat treatment equipment, preheated at 60 ° C, and then gradually raised to 130 ° C and maintained for 2 h within 20 h, and the water vapor is continuously sprayed into the high temperature heat treatment equipment as Protective gas. Then gradually increase the temperature to 190 ° C within 4 h for 4 h. Then, under the condition of water vapor protection, gradually reduce the temperature to 120 °C within 3 hours, stop the water vapor supply, naturally cool to normal temperature, take out the wood, and finally obtain the paraffin-silane composite emulsion pretreatment modified high temperature heat treatment material.
  • a paraffin-silane composite emulsion was prepared according to the method described in CN103341894A.
  • the prepared paraffin-silane composite emulsion was used to pretreat the wood, and the wood was placed in an infusion tank for vacuum treatment.
  • the relative vacuum was -0.08 MPa, the treatment time was 50 min; then the solid content was 4%.
  • the paraffin-silane composite emulsion was subjected to a pressure treatment, and the relative pressure of the pressure treatment was 2.5 MPa, and the treatment time was 60 minutes.
  • the wood was then taken out and air dried for 7 days, after which the kiln was dried to a moisture content of 17%.
  • the pretreated and dried wood is placed in a high-temperature heat treatment equipment, preheated at 60 ° C, and then gradually raised to 130 ° C and maintained for 2 h in 16 h, and the water vapor is continuously sprayed into the high-temperature heat treatment equipment as Protective gas. Then gradually increase the temperature to 200 ° C in 4 h for 6 h. Then, under the condition of water vapor protection, gradually reduce the temperature to 120 °C within 5 hours, stop the water vapor supply, naturally cool to normal temperature, take out the wood, and finally obtain the paraffin-silane composite emulsion pretreatment modified high temperature heat treatment material.
  • a paraffin-silane composite emulsion was prepared according to the method described in CN103341894A.
  • the prepared paraffin-silane composite emulsion was used to pretreat the wood, and the wood was placed in an infusion tank for vacuum treatment.
  • the relative vacuum was -0.09 MPa and the treatment time was 60 min.
  • the paraffin-silane with a solid content of 2% was introduced.
  • the composite emulsion was subjected to a pressure treatment, and the relative pressure of the pressure treatment was 2.0 MPa, and the treatment time was 120 minutes.
  • the wood was then taken out and air dried for 10 days, after which the kiln was dried to a moisture content of 12%.
  • the pretreated and dried wood is placed in a high-temperature heat treatment equipment, preheated at 60 ° C, and then gradually increased to 130 ° C for 24 h within 24 h, and the water vapor is continuously sprayed into the high-temperature heat treatment equipment.
  • Protective gas Then gradually increase the temperature to 220 ° C within 6 h for 4 h.
  • under the condition of water vapor protection gradually reduce the temperature to 120 °C within 5 hours, stop the water vapor supply, naturally cool to normal temperature, take out the wood, and finally obtain the paraffin-silane composite emulsion pretreatment modified high temperature heat treatment material.
  • Comparative example 1 Comparative example 1
  • the southern pine was not treated, and the kiln was dried to a moisture content of 12%.
  • the paraffin-silane composite emulsion ratio is: 54# semi-refined paraffin wax 100g, n-dodecyl trialkoxysilane 200g, sorbitan fatty acid ester span80 15g, polyoxyethylene sorbitan monolaurate tween80 35 g, sodium stearate 20 g, stearic acid 20 g, and n-pentanol 20 g, water 620 g.
  • a paraffin-silane composite emulsion was prepared according to the method described in CN103341894A.
  • the untreated southern pine kiln was dried to a moisture content of 12%, and the wood was placed in an infusion tank for vacuum treatment.
  • the relative vacuum was -0.09 MPa and the treatment time was 60 min.
  • the paraffin wax with a solid content of 2% was introduced.
  • the silane composite emulsion was subjected to a pressure treatment, and the relative pressure of the pressure treatment was 20 MPa, and the treatment time was 120 minutes.
  • the wood was then taken out and air dried for 10 days, after which the kiln was dried to a moisture content of 12%.
  • Example 4 The wood of Example 4 and Comparative Example 1-3 was selected, and the surface of the sample was observed using a S-3000N scanning electron microscope (SEM) manufactured by Hitachi. The results are shown in Fig. 3.
  • Figures 3, 4, 5 and 6 are SEM results of the chord cuts of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 4, respectively.
  • the invention provides a method for improving the performance of a high-temperature heat-treated material by using a paraffin-silane composite emulsion treatment.
  • Method pretreatment of wood with paraffin-silane composite emulsion, on the basis of which, high temperature heat treatment conditions are optimized, and wood hemicellulose is degraded by heating at 180-220 temperature.
  • the components in paraffin-silane composite emulsion are distributed in wood. More uniform, the degree of cross-linking reaction is obviously enhanced, and the combination of paraffin-silane composite emulsion and wood is strengthened, and a good modification effect can be obtained under the solid content of 4% or less, and the production cost is lowered.
  • the wood prepared in this case can be widely used in interior decoration, exterior decoration, floor, fence, indoor and outdoor furniture, etc. Compared with the prior art, this solution is more suitable for outdoor high humidity environment. Using this technology, the problem of dimensional stability of wood can be better solved under the premise of the existing foundation, which will greatly promote the use of wood of plantation forest and excavate a greater potential market opportunity for plantation timber.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

本发明涉及一种利用石蜡-硅烷复合乳液处理改善高温热处理材性能的方法，包括如下步骤：1）石蜡-硅烷复合乳液预处理；2）高温热处理。本发明中利用石蜡-硅烷复合乳液对木材进行预处理，其中石蜡覆盖在木材细胞比表面起到高疏水性覆盖作用，硅烷与木材表面羟基发生化学反应，共同起到阻碍降低木材吸水性的作用，进一步提高了高温热处理材的疏水性和尺寸稳定性；同时，高温热处理过程中，复合乳液有效成分在木材中重新分布，更好的发挥了防水的作用。如此得到的改性木材可以更好地适应室外使用环境。

Description

一种利用石蜡-硅烷复合乳液改善高温热处理材性能的方法 技术领域
本发明属于木材加工领域， 具体涉及一种利用石蜡-硅烷复合乳液浸渍预 处理改善高温热处理材性能的方法。 背景技术
木材是树木在自然界中天然生长形成的一种绿色材料， 是森林生态系统 中储量巨大的生物质。 木材作为工业和生活用材， 与国民经济建设和人类生 活息息相关， 并拥有诸多优良品质， 如强重比大、 加工能耗少、 环境污染少、 可回收利用以及良好的环境协调性等。 木材主要由纤维素、 半纤维素和木质 素组成， 因此其中含有大量亲水性的羟基， 易吸水， 在使用过程中木材含水 率的变化导致木材存在一些缺陷， 如干缩湿涨、 尺寸不稳定； 易腐、 生物耐 久性差等， 在一定程度上限制了木材的使用价值和应用范围。
高温热处理技术是一种近些年来常用的改善木材性能的技术， 该方法将 木材在有过热蒸汽、 惰性气体或热油等保护的条件下， 在高温 （约为 150 ~ 260°C )的环境下进行一段时间的热处理。 经过高温热处理得到的木材被称为 高温热处理材， 也称炭化木。 虽然高温热处理材具有诸多优点， 但其吸水性 和尺寸稳定性仍然无法满足当代工业要求。 针对这一缺陷， CN101716790A 公开了一种使用树脂预处理生产橡胶树炭化木的方法， 降低了橡胶树炭化木 的吸水性， 提高了其尺寸稳定性和耐久性。 但是该专利中所使用的酚醛树脂 与脲醛树脂等树脂改性剂均在一定程度上存在甲醛释放的隐患， 破坏了高温 热处理材原有的环保特性。 CN103240780A公开了一种使用硅溶胶浸注预处理 改善炭化木性能的方法， 减少了炭化木的质量损失率， 降低了平衡含水率， 提高了尺寸稳定性和防白蚁性。但是该专利中使用的硅溶胶浓度达到 20-50%， 导致生产成本过高，且过高的处理浓度会在一定程度上影响木材自身的特性。 发明内容
针对上述现有技术存在的缺陷， 本申请提供一种经济环保且能显著提高 高温热处理材防水性能和尺寸稳定性的处理方法， 从而使高温热处理材更适 用于户外环境。
为了实现上述目的， 本发明采用如下技术方案：
一种利用石蜡-硅烷复合乳液处理改善高温热处理材性能的方法， 包括如 下步骤：
1 ) 石蜡-硅烷复合乳液预处理
将木材置于浸注罐内先进行真空处理，再导入固含量为 1~6%的石蜡 -硅烷 复合乳液加压处理， 再将木材取出气干， 随后窑干至含水率为 12~18%；
2 ) 高温热处理。
在上述方法中， 步骤 1 )所述石蜡-硅烷复合乳液固含量为 2~4%。
在上述方法中，步骤 1 )所述真空处理条件：相对真空度为 -0.05~ -O.lMPa, 优选为 -0.06~ -0.096MPa, 处理时间为 20~60min。
在上述方法中， 步骤 1 ) 所述加压处理条件： 加压处理的相对压力为 0.5~4.0Mpa, 优选为 1.5~2.5Mpa， 处理时间为 30〜： I20min。
步骤 2 ) 中所述高温热处理是将步骤 1 ) 处理并干燥好的木材在 180 220 °C条件下保持 2~6h， 冷却后得到高温热处理材。
步骤 2 ) 中所述高温热处理分为三个阶段：
1 )在 55~65°C条件下预热 l~3h;
2 )在 14~24h内均速将温度提高到 120~140°C并维持 l~4h;
3 )在 3~6h内逐步升温至 180~220°C， 保持 2~6h。
上述步骤 2 ) 具体步骤为： 先将木材置于高温热处理设备中， 在 55~65°C 条件下预热 l~3h，再在 14~24h内均速将温度提高到 120~140°C并维持 l~4h， 然 后持续向高温热处理设备中喷入水蒸气作为保护气体， 并在随后的 3~6h内逐 步升温至 180~220°C， 保持 2~6h; 再在水蒸气保护的条件下， 在 3~6h内逐步降 温至 110~130°C， 停止水蒸气供应， 自然冷却到常温取出木材。
本申请所述高温热处理设备为本领域技术人员所了解的专用于木材高温 热处理的设备， 如 XNH系列木材高温热处理设备（江苏星楠干燥设备有限公 司 )。
本发明所述的石蜡-硅烷复合乳液为 CN103341894A公开的技术方案， 包 括如下组分及配比原料制成的乳液： 熔点为 48~64°C的固体石蜡 1~2000份，链 烷基长度为 1~18的链烷基三烷氧基硅烷 1~2000份，非离子型表面活性剂 1~500 份， 阴离子型表面活性剂 1~200份， 助表面活性剂 1~200份， 脂肪酸 1~200份， 水 1 10000份。 优选的为： 熔点为 54~58°C的固体石蜡 500 750份， 链烷基长度 为 12的链烷基三烷氧基硅烷 1000 1500份， 非离子型表面活性剂 100 200份， 阴离子型表面活性剂以 40~50份， 助表面活性剂 40~50份， 脂肪酸 40~50份， 水 1~8000份。
其中， 所述固体石蜡： 巿购， 熔点为 48~64°C， 精炼石蜡、 半精炼石蜡、 粗石蜡。 所述链烷基三烷氧基硅烷： R^i OR2)^ 其中取代基 R1为 C1~C18链 烷基， R2为甲基、 乙基、 丙基等。 所述非离子表面活性剂： 失水山梨醇脂肪 酸酯、 聚乙二醇辛基苯基醚类、 聚氧乙烯去水山梨醇单月桂酸酯、 脂肪醇聚 氧乙烯醚等。 所述阴离子表面活性剂： 硬脂酸钠、 烷基磺酸钠、 琥珀酸酯磺 酸盐、 木质素磺酸盐等。 所述助表面活性剂： 异丙醇、 正丁醇、 异丁醇、 正 戊醇、 异戊醇、 1-己醇、 2-己醇等。 所述脂肪酸： 油酸、 硬脂酸等。
所述石蜡-硅烷复合乳液的制备方法： 将固体石蜡置于 70°C~100°C的条件 下， 优选为 80°C~90°C， 待固体石蜡完全溶解后， 边搅拌边加入链烷基三烷氧 基硅烷， 并依次加入非离子表面活性剂、 阴离子表面活性剂、 助表面活性剂、 脂肪酸， 使整个体系保持在 70°C~100°C条件下， 优选为 80°C~90°C加热并以 2000rpm~10000rpm的速度， 优选为 3000rpm~6000rpm搅拌 10~30min， 边搅拌 边加入水， 制备完成初乳液。 将初乳液经过高压均质机进行高压均质， 均质 压力为 20MPa~80MPa， 优选为 40MPa~60MPa， 均质次数为 1~2次， 优选为 2 次， 最终制得石蜡-硅烷复合乳液。
本发明中利用石蜡-硅烷复合乳液对木材进行预处理， 其中石蜡覆盖在木 材细胞比表面起到高疏水性覆盖作用， 硅烷与木材表面羟基发生化学反应， 共同起到阻碍降低木材吸水性的作用， 进一步提高了木材的疏水性和尺寸稳 定性， 更好地适应室外使用环境。 而且硅烷具有一定的杀菌作用， 可以在一 定程度上提高木材的耐腐性能。 在此基础上， 优化高温热处理条件， 在 180~220°C温度内加热使木材半纤维素大量降解， 石蜡-硅烷复合乳液中成分 在木材中分布更均匀， 交联反应程度明显增强， 强化了石蜡-硅烷复合乳液与 木材的结合， 在固含量 4%以下即可取得良好的改性效果， 降低生产成本， 体 现出良好的协同作用。 附图说明
图 1为本发明高温热处理材与对照例的吸水' &测试结果。
图 2为实施例 4、 对照例 2与对照例 3相对于对照例 1的木材弦向抗膨胀率。 图 3为对照例 1的弦切面 SEM结果。
图 4为对照例 2的弦切面 SEM结果。
图 5为对照例 3的弦切面 SEM结果。
图 6为实施例 4的弦切面 SEM结果。 具体实施方式
为了对比各不同实施例与对照例处理材的性能， 以下实施例所用木材均 为美国南方松， 但不限制为南方松， 常见针叶材， 如欧洲赤松、 马尾松等， 常见阔叶材， 如青杨、 毛白杨、 桦木等均可。
实施例 1
( 1 ) 石蜡-硅烷复合乳液原料配比
54号半精炼石蜡 100g， 正十二烷基三烷氧基硅烷 200g， 失水山梨醇脂肪 酸酯 span80 15g、聚氧乙烯去水山梨醇单月桂酸酯 tween80 35g、硬脂酸钠 20g、 硬脂酸 20g和正戊醇 20g， 水 620g。
按照 CN103341894A所述方法制备得到石蜡-硅烷复合乳液。
( 2 ) 制备高温热处理材
使用步骤 1 ) 制得的石蜡-硅烷复合乳液预处理木材， 将木材置于浸注罐 内先进行真空处理， 相对真空度为 -0.09MPa， 处理时间为 30min; 之后导入固 含量为 4%的石蜡-硅烷复合乳液， 进行加压处理， 加压处理的相对压力为 1.5MPa, 处理时间为 40min。 之后将木材取出气干 3天， 随后窑干至含水率为 18%。
将预处理并干燥好的木材置于高温热处理设备中， 使用 60°C进行预热， 随后在 14h内逐步将温度提高到 130°C并维持 lh， 开始持续向高温热处理设备 中喷入水蒸气作为保护气体。 随后在 3h内逐步升温至 180°C， 保持 3h。 随后在 水蒸气保护的条件下， 在 4h内逐步降温至 120°C， 停止水蒸气供应， 自然冷却 到常温， 取出木材， 最终制得石蜡-硅烷复合乳液预处理改性高温热处理材。 实施例 2
( 1 ) 石蜡 -硅烷复合乳液配比
58号半精炼石蜡 120g， 正丁基三乙氧基硅烷 240g， 失水山梨醇脂肪酸酯 span20 10g、 聚氧乙烯去水山梨醇单月桂酸酯 tween80 20g, 二辛基磺基琥珀 酸钠 10g， 月桂酸 5g和异戊醇 5g， 水 670g。
按照 CN103341894A所述方法制备得到石蜡-硅烷复合乳液。
( 2 ) 制备高温热处理材
使用制得的石蜡-硅烷复合乳液预处理木材， 将木材置于浸注罐内先进行 真空处理，相对真空度为 -0.06MPa， 处理时间为 60min; 之后导入固含量为 3% 的石蜡-硅烷复合乳液， 进行加压处理， 加压处理的相对压力为 1.5MPa， 处理 时间为 90min。 之后将木材取出气干 5天， 随后窑干至含水率为 16%。
将预处理并干燥好的木材置于高温热处理设备中， 使用 60°C进行预热， 随后在 20h内逐步将温度提高到 130°C并维持 2h， 开始持续向高温热处理设备 中喷入水蒸气作为保护气体。 随后在 4h内逐步升温至 190°C， 保持 4h。 随后在 水蒸气保护的条件下， 在 3h内逐步降温至 120°C， 停止水蒸气供应， 自然冷却 到常温， 取出木材， 最终制得石蜡-硅烷复合乳液预处理改性高温热处理材。 实施例 3
( 1 ) 石蜡 -硅烷复合乳液配比
52号半精炼石蜡 105g， 正丁基三乙氧基硅烷 230g， 聚氧乙烯脂肪酸酯 A-1055 10g, 二辛基磺基琥珀酸钠 10g、 月桂酸 5g和正己醇 5g， 水 745g。
按照 CN103341894A所述方法制备得到石蜡-硅烷复合乳液。
( 2 ) 制备高温热处理材
使用制得的石蜡-硅烷复合乳液预处理木材， 将木材置于浸注罐内先进行 真空处理，相对真空度为 -0.08MPa， 处理时间为 50min; 之后导入固含量为 4% 的石蜡-硅烷复合乳液， 进行加压处理， 加压处理的相对压力为 2.5Mpa， 处理 时间为 60min。 之后将木材取出气干 7天， 随后窑干至含水率为 17%。
将预处理并干燥好的木材置于高温热处理设备中， 使用 60°C进行预热， 随后在 16h内逐步将温度提高到 130°C并维持 2h， 开始持续向高温热处理设备 中喷入水蒸气作为保护气体。 随后在 4h内逐步升温至 200°C， 保持 6h。 随后在 水蒸气保护的条件下， 在 5h内逐步降温至 120°C， 停止水蒸气供应， 自然冷却 到常温， 取出木材， 最终制得石蜡-硅烷复合乳液预处理改性高温热处理材。 实施例 4
( 1 ) 制备石蜡-硅烷复合乳液
56号半精炼石蜡 105g， 正丁基三乙氧基硅烷 210g， 脂肪醇聚氧乙烯醚 AE05 5g、 脂肪醇聚氧乙烯醚 AE09 25g、 十二烷基磺酸钠 8g、 油酸 8g和正丁 醇 8g， 水 666g。
按照 CN103341894A所述方法制备得到石蜡-硅烷复合乳液。
( 2 ) 制备高温热处理材
使用制得的石蜡-硅烷复合乳液预处理木材， 将木材置于浸注罐内先进行 真空处理，相对真空度为 -0.09MPa， 处理时间为 60min; 之后导入固含量为 2% 的石蜡-硅烷复合乳液， 进行加压处理， 加压处理的相对压力为 2.0MPa， 处理 时间为 120min。 之后将木材取出气干 10天， 随后窑干至含水率为 12%。
将预处理并干燥好的木材置于高温热处理设备中， 使用 60°C进行预热， 随后在 24h内逐步将温度提高到 130°C并维持 4h， 开始持续向高温热处理设备 中喷入水蒸气作为保护气体。 随后在 6h内逐步升温至 220°C， 保持 4h。 随后在 水蒸气保护的条件下， 在 5h内逐步降温至 120°C， 停止水蒸气供应， 自然冷却 到常温， 取出木材， 最终制得石蜡-硅烷复合乳液预处理改性高温热处理材。 对照例 1
未处理南方松， 窑干干燥到含水率 12%。
对照例 2
将未处理南方松窑干干燥到含水率 12%， 随后置于高温热处理设备中， 使用 60°C进行预热， 随后在 24h内逐步将温度提高到 130°C并维持 4h， 开始持 续向高温热处理设备中喷入水蒸气作为保护气体。随后在 6h内逐步升温至 180 °C， 保持 4h。 随后在水蒸气保护的条件下， 在 5h内逐步降温至 120°C， 停止水 蒸气供应， 自然冷却到常温， 取出木材， 最终制得未经预处理的高温热处理 对照例 3
石蜡-硅烷复合乳液配比为： 54号半精炼石蜡 100g， 正十二烷基三烷氧基 硅烷 200g， 失水山梨醇脂肪酸酯 span80 15g、聚氧乙烯去水山梨醇单月桂酸酯 tween80 35g、 硬脂酸钠 20g、 硬脂酸 20g和正戊醇 20g， 水 620g。 按照 CN103341894A所述方法制备得到石蜡-硅烷复合乳液。
将未处理南方松窑干干燥到含水率 12%， 将木材置于浸注罐内先进行真 空处理， 相对真空度为 -0.09MPa， 处理时间为 60min; 之后导入固含量为 2% 的石蜡-硅烷复合乳液， 进行加压处理， 加压处理的相对压力为 20MPa， 处理 时间为 120min。 之后将木材取出气干 10天， 随后窑干至含水率为 12%。
实验例 1 平衡含水率与接触角
参照 GB 1931-91《木材含水率测定方法》测定实施例 1-4与对照例 1-3在 20
°C， 65%相对湿度条件下的平衡含水率。 使用接触角测量仪测量实施例 1-4与 对照例 1-3木材表面的水接触角， 结 如表 1所示：
Figure imgf000009_0001
组别 平衡含水率 （％) 接触角 （° )
对照例 1 10.23 ( 0.17 ) 40.24 ( 2.45 )
对照例 2 9.77 ( 0.03 ) 82.54 ( 1.48 )
对照例 3 9.21 ( 0.12 ) 110.14 ( 2.98 )
实施例 1 8.36 ( 0.04 ) 115.95 ( 3.81 )
实施例 2 7.15 ( 0.11 ) 122.51 ( 1.58 )
实施例 3 6.06 ( 0.08 ) 130.22 ( 3.69 )
实施例 4 5.31 ( 0.13 ) 136.99 ( 2.87 )
结果表明， 石蜡-硅烷复合乳液浸渍与高温热处理技术相结合使木材的平 衡含水率明显降低， 表面接触角明显提高， 高于二者单独使用的效果， 表明 两种处理可以协同降低木材的吸湿性， 提高木材的表面疏水性。
实验例 2 吸水性
参照 GB/T 1934.1-2009《木材吸水性测定方法》， 测量木材的吸水性， 结 果如图 1所示。
结果表明， 石蜡-硅烷复合乳液和高温热处理均可以有效地降低木材的吸 水性， 而二者联合使用后效果大大优于单独使用的效果， 表明石蜡-硅烷复合 乳液浸渍预处理和高温热处理可以协同降低木材的吸水性。
实验例 3 尺寸稳定性
参照 ASTM D4446"Standard Test Method for Anti-Swelling Effectiveness of Water-Repellent Formulations and Differential Swelling of Untreated Wood When Exposed to Liquid Water Environments"测量实施例 4、 对照例 2与对照例 3相对 于对照例 1的木材弦向抗膨胀率 （ASE )。 结果如图 2所示。
结果表明， 单独使用高温热处理技术的木材， 其 ASE提高有限， 不高于 30%; 而单独使用石蜡-硅烷复合乳液， 尽管有较高的初始 ASE， 但是随着时 间的延长， ASE下降极快。 而将两种方法联合使用， 可以获得一种具有稳定 的高 ASE的木材， 体现了两种方法优良的协同作用。
实验例 4 扫描电镜分析
选择实施例 4和对照例 1-3的木材，使用 Hitachi公司生产的 S-3000N型扫描 电子显微镜 （SEM ) 对试样表面进行观测， 结果如图 3所示。 图 3、 4、 5和 6 分别为对照例 1、 对照例 2、 对照例 3和实施例 4的弦切面 SEM结果。
结果表明， 高温热处理会在木材细胞表面产生新的孔隙和裂缝， 对木材 的性能产生不良的影响， 而石蜡-硅烷乳液中的主要成分可以有效地填充这些 孔隙和裂缝； 同时， 在热的作用下， 石蜡-硅烷乳液中的主要成分会在木材细 胞壁表面重新分布， 使分布变得更加均匀。 除此之外， 热作用有利于硅烷和 木材之间发生交联反应。 以上的原因可以用来解释石蜡-硅烷乳液浸渍预处理 和高温热处理之间存在的协同作用。 工业实用性
本发明提出一种利用石蜡-硅烷复合乳液处理改善高温热处理材性能的 方法， 利用石蜡-硅烷复合乳液对木材进行预处理， 在此基础上， 优化高温热 处理条件，在 180-220 温度内加热使木材半纤维素大量降解， 石蜡-硅烷复合 乳液中成分在木材中分布更均匀， 交联反应程度明显增强， 强化了石蜡 -硅烷 复合乳液与木材的结合， 在固含量 4%以下即可取得良好的改性效果， 降低生 产成本。 本案所制备的木材可以广泛的用于建筑内装修、 外装修、 地板、 栅 栏、 室内外家具等方面， 与以往技术相比， 此方案更加适用于室外的高湿环 境。 使用该技术， 可以在现有基础的前提下， 更好的解决木材的尺寸稳定性 问题， 将极大地促进人工林木材的使用范围， 为人工林木材发掘出更大的潜 在巿场机会。

Claims

权 利 要 求 书
1、 一种利用石蜡-硅烷复合乳液处理改善高温热处理材性能的方法， 其 特征在于， 包括如下步骤：
1 ) 石蜡-硅烷复合乳液预处理
将木材置于浸注罐内先进行真空处理，再导入固含量为 1~6%的石蜡 -硅烷 复合乳液加压处理， 再将木材取出气干， 随后窑干至含水率为 12~18%；
2 ) 高温热处理。
2、 根据权利要求 1所述的方法， 其特征在于， 步骤 1 )所述石蜡-硅烷复 合乳液固含量为 2~4%。
3、根据权利要求 1所述的方法， 其特征在于， 步骤 1 )所述真空处理条件: 相对真空度为 -0.05〜 - O.lMPa, 处理时间为 20~60min。
4、 根据权利要求 3所述的方法， 其特征在于， 所述相对真空度为 -0.06~ -0.096MPa。
5、根据权利要求 1所述的方法， 其特征在于， 步骤 1 )所述加压处理条件: 加压处理的相对压力为 0.5 4.0 MPa， 处理时间为 30~120min。
6、根据权利要求 5所述的方法，其特征在于，所述相对压力为 0.5 4.0 MPa, 优选为 1.5 2.5 MPa。
7、 根据权利要求 1所述的方法， 其特征在于， 步骤 2 ) 中所述高温热处理 是将步骤 1 ) 处理并干燥好的木材在 180~220°C条件下保持 2~6h， 冷却后得到 高温热处理材。
8、 根据权利要求 7所述的方法， 其特征在于， 所述高温热处理分为三个
1 )在 55~65 °C条件下预热 l~3h;
2 )在 14~24h内均速将温度提高到 120~140°C并维持 l~4h;
3 )在 3~6h内逐步升温至 180~220°C， 保持 2~6h。
9、 根据权利要求 8所述的方法， 其特征在于， 步骤 2 )具体步骤为： 先将 木材置于高温热处理设备中， 在 55-65 °C条件下预热 l-3h， 再在 14-24h内均速 将温度提高到 120~140°C并维持 l~4h，然后持续向高温热处理设备中喷入水蒸 气作为保护气体， 并在随后的 3~6h内逐步升温至 180~220°C， 保持 2~6h; 再在 水蒸气保护的条件下， 在 3~6h内逐步降温至 110~130°C， 停止水蒸气供应， 自 然冷却到常温取出木材。
10、 权利要求 1 -9任一所述方法制备得到的高温热处理材。
PCT/CN2014/075512 2014-04-16 2014-04-16 一种利用石蜡-硅烷复合乳液改善高温热处理材性能的方法 WO2015157944A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ309803B6 (cs) * 2021-09-21 2023-10-25 Univerzita Pardubice Přípravky pro zvýšení kluznosti povrchů polymerních materiálů a kompozitů

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101069972A (zh) * 2007-05-28 2007-11-14 浙江林学院 一种热处理炭化木材的生产方法
WO2009087262A1 (en) * 2008-01-09 2009-07-16 Borenova Oy Method for pressure impregnating wood or wood products with wood preservative containing water glass and impregnated wood or wood product
CN103341894A (zh) * 2013-07-22 2013-10-09 北京林业大学 一种石蜡-硅烷复合防水剂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101069972A (zh) * 2007-05-28 2007-11-14 浙江林学院 一种热处理炭化木材的生产方法
WO2009087262A1 (en) * 2008-01-09 2009-07-16 Borenova Oy Method for pressure impregnating wood or wood products with wood preservative containing water glass and impregnated wood or wood product
CN103341894A (zh) * 2013-07-22 2013-10-09 北京林业大学 一种石蜡-硅烷复合防水剂及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ309803B6 (cs) * 2021-09-21 2023-10-25 Univerzita Pardubice Přípravky pro zvýšení kluznosti povrchů polymerních materiálů a kompozitů

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