磷氮系阻燃劑製備及其應用於木材防焰性能之研究

Application of Phosphorus-nitrogen Compound Fire-retardants onWood Flammability Performance

范姜士勳(Shih-Shiun Fan Jiang)

指導教授 ： 林曉洪

國立屏東科技大學/農學院/木材科學與設計系所/碩士(2012年)

https://doi.org/10.6346/NPUST.2012.00001

摘要

木材為生物性有機質材料，自古以來人類便取之作為建築與室內裝修用材。今日材料科技進步神速，建材種類日有新品，然無一能完全取代木材之優異性，故木材被稱為21世紀之「生態材料」。惟木材居住應用上，尚存在如燃燒性之不良性質，必需予以改善，以擴大其應用範圍。
本研究目的係以雙氰胺與磷酸為主阻燃劑，分別再與氨基磺酸胺、硼酸、硼砂、磷酸氫二銨及硫酸銨等單一阻燃劑進行合成，製備包含主阻燃劑等六種 複合型阻燃劑，以應用於國產針葉樹造林木三樹種（台灣杉、柳杉及杉木）之防焰性能之改善。首先將試材以10~20 %阻燃劑濃度含浸處理後，以氧氣指數試驗法（CNS 13590）評估阻燃劑處理對試材抑焰性效應，以尋求較佳阻燃劑配方與濃度；接著試材以15 %阻燃劑濃度含浸處理，利用熱重分析技術探討其熱降解反應之特性。最終試材以真空加壓注入法進行阻燃劑加壓注入處理，並以薄材料防焰性試驗法(CNS 7614)進行防焰性能試驗。各處理材也進行含水率(CNS 452)、密度(CNS 451)及吸濕性(CNS 6715)等物理性質試驗，以評估後續利用之可行性。
氧氣指數試驗結果顯示，各阻燃劑處理材均可改善抑焰效應，且抑焰效應以 複合型阻燃劑FR-A（雙氰胺－磷酸－氨基磺酸胺）處理材（1.62 % (kg/m3)-1）最佳，而FR-F（1.18 % (kg/m3)-1）者最差。次經熱重分析試驗後顯示，其殘炭量亦以 複合型阻燃劑FR-A處理材最高【空氣（27.17 %）及氮氣（38.91 %）】，而FR-F處理材最差【空氣（19.36 %）及氮氣（33.15 %）】。次藉SEM-EDXA技術得以觀測此六種 複合型阻燃劑於試材中分布情形，六種 複合型阻燃劑處理材之氧氣指數與熱重分析參數(殘炭重)兩者間呈一次直線迴歸顯著至極顯著相關。顯示，各阻燃劑之抑焰性效應與促進炭生成量兩者間存在密切之關係。其迴歸式如下所示：
空氣中：OI (v/v,%) =0.7891 x + 29.505 R2 = 0.8051*
氮氣中：OI (v/v,%) =1.149x + 6.4174 R2 = 0.7301 **
防焰試驗顯示，除 複合型阻燃劑FR-F（雙氰胺－磷酸－硫酸銨）處理材為防焰2級外，餘均能提升至防焰1級。另依CNS 11668 ”防焰合板”之防焰性能判定各處理材之炭化面積，均為合格(＜50 cm2)。
又，各處理材之物理性質（含水率、密度、吸濕量）顯示，含水率、密度及吸濕量，會因阻燃劑吸收量增加而提高之趨勢。依CNS 11668”防焰合板”試驗標準評估顯示，除 複合型阻燃劑FR-C（雙氰胺－磷酸－硼砂）者外，餘阻燃劑均能通過。 複合型阻燃劑FR-C（雙氰胺－磷酸－硼砂）處理材阻燃劑吸收量【83.18(kg/m3)】及密度為各阻燃劑處理材之冠(0.53 g/cm 3)。處理材之阻燃劑吸收量分別與含水率、密度及吸濕量呈一次直線迴歸之顯著相關。
綜合試驗結果顯示，本研究製備之六種阻燃阻燃劑中，有五種阻燃劑可通過國家標準，並可應用於實木建材之防焰處理。

【關鍵詞】針葉材、熱重分析、氧氣指數、防焰性能、阻燃劑

關鍵字

針葉材 ； 熱重分析 ； 氧氣指數 ； 防焰性能 ； 阻燃劑

並列摘要

Wood is a biological organic material, since ancient times human beings have to take it as architecture and interior decoration materials. Today, due to the material and technological progress rapidly, building a new type of day, and then no one can completely replace the superiority of wood,so wood is known as the 21st century timber "eco-materials." Except for timber live applications, such as the burning of surviving in adverse effect, must be improved in order to expand its scope of application.
The purpose of this study was using dicyandiamide and phosphoric acid as primary flame retardants mixed with single flame retardants such as sulfamic acid, boric acid, borax, diammonium phosphate and ammonium sulfate to prepare, contains primary flame retardants, six kinds of compound flame retardant,and to apply to domestic three wood species conifer plantation wood (Taiwania, Japanese cedar and China fir) of the flameproof performance improvement. First, all the test materials were impregnated to10 to 20% concentration of the flame retardant and then with oxygen index test method (CNS 13590) assess flame retardant material on the flame inhibition effects of test materials, in order to seek a better flame retardant formulation and concentration; meanwhile test material impregnation treatment with 15% concentration of flame retardant , using thermal gravimetric analysis technique to explore the characteristics of thermal degradation reactions. Finally,the flame retardant using vacuum pressure impregnation method into the wood specimens, and thin materials flameproof test method (CNS 7614) for flameproof performance tests assessment. The treated wood were also estimated the moisture content (CNS 452), density (CNS 451) , hygroscopic (CNS 6715) and other physical properties of the test, in order to assess the feasibility of subsequent use.
Oxygen index test results show that the flame retardant treated wood flame inhibition effect can be improved, and the inhibition effect of a compound flame retardant FR-A (DCD - phosphoric acid - amino acid amine) treated wood (1.62% (kg/m3) -1) best while FR-F (1.18% (kg/m3) -1) are the worst. Oxygen index test results show that the flame retardant treated wood flame inhibition effect can be improved, and the inhibition effect of a compound flame retardant FR-A (DCD - phosphoric acid - amino acid amine) treated wood (1.62% (kg/m3) -1) best while FR-F (1.18% (kg/m3) -1) are the worst. Then by TGA tests show that its carbon residue were also flame retardant FR-A compound material handling highest [in air (27.17%) and in nitrogen (38.91%)], while the FR-F treated wood worst [in air (19.36%) and in nitrogen (33.15%)]. Secondly,by SEM-EDXA technology can be observed that the six compound flame retardant materials in the distribution of the specimen, six kinds of compound flame retardant treated wood of oxygen index and thermal gravimetric analysis parameters (carbon residue weight) was once between extremely significant correlation significant linear regression. Shows that the flame retardant flame inhibition effects of carbon formation and promotion of the close relationship between the two. The regression formula is as follows:
Air: OI (v / v,%) = 0.7891 x + 29.505 R2 = 0.8051 *
Nitrogen: OI (v / v,%) = 1.149x + 6.4174 R2 = 0.7301 **
Flameproof test results show that in addition to the compound flame retardant FR-F (DCD - phosphoric acid - ammonium sulfate) treated wood is flameproof 2, the rest can upgrade to a flameproof 1. In addition, according to CNS 11668 "flameproof plywood" flameproof performance determination of the carbonized wood each treatment area are qualified (<50 cm2).
Also, the physical properties of the treated wood (moisture content, density, moisture absorption) showed that the moisture content, density and moisture absorption increased increasing with flame retardant . By CNS 11668 "flameproof plywood" test standard assessment shows that, in addition to the compound flame retardant FR-C (DCD - phosphoric acid - borax) above, the rest of flame retardants can pass. Compound flame retardant FR-C (DCD - phosphoric acid - borax) uptake retardant treated wood [83.18 (kg/m3)] and a density of each of the largest of flame retardant material (0.53 g / cm 3 ). The flame retardant treated wood moisture absorption with density and moisture content of the linear regression showed a significant correlation,respectively.

Keywords: Coniferous wood,Thermogravimrtry analysis,Oxygen index,Flameproof performance,Flame retardant

並列關鍵字

Coniferous wood ； Thermogravimetry analysis ； Oxygen index ； Flameproof performance ； Flame retardant

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