TW202045700A - Flame-retardant composite and its method - Google Patents
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本發明有關於一種複合材料,特別是指一種阻燃高分子複合材料及其方法。The invention relates to a composite material, in particular to a flame-retardant polymer composite material and its method.
近來隨著公共安全意識提升,阻燃劑(Flame Retardant)的消費量不斷成長,估計全球阻燃劑的用量已超過210萬噸,是僅次於可塑劑的使用量第二大塑膠添加劑品項。常見的許多熱塑性高分子聚合物,如:PP、PE、ABS、PC 等都因為其具有易燃的特性而必須在生產的過程中添加阻燃劑,估計阻燃劑占整體塑膠添加劑市場比重的17%。而過去最常被使用的鹵系阻燃劑雖然其阻燃效果卓越,但在燃燒後鹵系阻燃劑卻會造成大量濃煙及有毒性氣體,因應歐盟法規 ROHS 限令,目前常用之鹵素耐燃劑已逐漸被禁用,發展無鹵系阻燃材料已成為全球焦點。With the recent increase in public safety awareness, the consumption of flame retardants has continued to grow. It is estimated that the global use of flame retardants has exceeded 2.1 million tons, making it the second largest plastic additive item after plasticizers. . Many common thermoplastic polymers, such as PP, PE, ABS, PC, etc., must be added with flame retardants in the production process because of their flammable characteristics. It is estimated that flame retardants account for the proportion of the overall plastic additive market 17%. Although the halogen-based flame retardants most frequently used in the past have excellent flame retardant effects, they will cause a lot of dense smoke and toxic gases after burning. In response to the ROHS restrictions of EU regulations, the currently commonly used halogens are flame-resistant Agents have been gradually banned, and the development of halogen-free flame retardant materials has become a global focus.
一般依據非鹵阻燃劑之化學組成,可將非鹵阻燃劑作以下分類:Generally based on the chemical composition of non-halogen flame retardants, non-halogen flame retardants can be classified as follows:
(1)磷系化合物為目前全球無鹵阻燃劑中,最具前景的阻燃劑。此類阻燃劑在塑膠受熱後會在塑膠表面形成阻燃的碳化層,碳化層阻擋了可燃性氣體與因燃燒所產生的熱輻射兩者之流通,達到阻燃的目的。然而磷系阻燃劑材料卻容易水解、價格較含鹵阻燃劑貴且用量較含鹵阻燃劑高約20%,且材料物性顯著降低,這些缺點為目前磷系阻燃劑使用較受到限制之處。(1) Phosphorus compounds are currently the most promising flame retardants among halogen-free flame retardants in the world. Such flame retardants will form a flame-retardant carbonized layer on the surface of the plastic after the plastic is heated. The carbonized layer blocks the flow of combustible gas and heat radiation generated by combustion to achieve the purpose of flame retardancy. However, phosphorus-based flame retardants are easily hydrolyzed, are more expensive than halogen-containing flame retardants, and the amount is about 20% higher than halogen-containing flame retardants, and the material properties are significantly reduced. These shortcomings are that the current use of phosphorus-based flame retardants is more affected Limitations.
(2)氮系化合物阻燃劑如三聚氰胺系列化合物,在受熱後會產生不燃性的氮氣,稀釋空氣中可燃性氣體的濃度以達成樹脂的阻燃效果。(2) Nitrogen-based compound flame retardants, such as melamine-based compounds, will produce incombustible nitrogen after being heated, which dilutes the concentration of flammable gas in the air to achieve the flame retardant effect of the resin.
(3)磷氮(P/N)系化合物阻燃劑結合了磷系阻燃劑產生焦炭以及氮系阻燃劑產生非燃性氣體的特性,在受熱時會產生膨脹的碳化層,該碳化層可以大幅提升樹脂材料的阻燃性。此類型的阻燃劑具備了用量少、無毒的優點。聚磷酸銨與美耐米磷酸鹽類為常見的此類型阻燃劑。(3) Phosphorus-nitrogen (P/N)-based compound flame retardants combine the characteristics of phosphorus-based flame retardants to produce coke and nitrogen-based flame retardants to produce non-combustible gas. When heated, they will produce an expanded carbonized layer. This carbonization The layer can greatly improve the flame retardancy of the resin material. This type of flame retardant has the advantages of low dosage and non-toxicity. Ammonium polyphosphate and Melamine phosphates are common flame retardants of this type.
(4)反應性阻燃劑分子結構具備與樹脂材料上之官能基形成化學鍵結的能力,因為化學鍵結形成之故,較不會有相容性的問題產生。DOPO系列為此類阻燃劑(反應性阻燃劑)中最具代表性的一支。用量不多為此類阻燃劑的另一個優點。然而無法與多種樹脂材料鍵結且價格較貴,導致此類型的阻燃劑目前只能應用至少數領域如環氧樹脂。(4) The molecular structure of the reactive flame retardant has the ability to form a chemical bond with the functional group on the resin material. Because of the formation of the chemical bond, there will be less compatibility problems. The DOPO series is the most representative of such flame retardants (reactive flame retardants). The small amount is another advantage of this type of flame retardant. However, it cannot be bonded with a variety of resin materials and is relatively expensive. As a result, this type of flame retardant can only be used in at least a few fields such as epoxy resin.
(5)金屬氫氧化物如氫氧化鋁與氫氧化鎂主要是藉其分子結構中所含的結晶水進行阻燃。結晶水可以在塑膠受熱時,降低塑膠的溫度,達到阻燃的目的。其優點為便宜、無毒、不易揮發且熱安定性良好,然而其阻燃效果有限,需添加大量添加劑才有較佳的阻燃效果,但大量添加於塑膠中時,也影響塑膠其他物性。(5) Metal hydroxides such as aluminum hydroxide and magnesium hydroxide are mainly flame-retardant by the crystal water contained in their molecular structure. Crystal water can reduce the temperature of the plastic when the plastic is heated to achieve the purpose of flame retardancy. Its advantages are cheap, non-toxic, non-volatile and good thermal stability. However, its flame-retardant effect is limited, and a large amount of additives need to be added to have a better flame-retardant effect. However, when a large amount is added to the plastic, it also affects other physical properties of the plastic.
(6)矽系阻燃劑主要分為矽高分子(Silicone polymer)粉末以及二氧化矽(Silica)兩大塊,由於含矽之化合物本身就具備阻燃的特性,將之添加於樹脂材料內可以改善樹脂材料之阻燃性。然而矽高分子價格較貴,為此類阻燃劑之最大缺點。而二氧化矽本身添加至樹脂材料中並沒有很好的阻燃效果,主要是作為與磷系阻燃劑搭配之協同劑,售價低廉為二氧化矽之最大優勢。(6) Silicon-based flame retardants are mainly divided into silicon polymer powder and silicon dioxide (Silica). Since silicon-containing compounds are inherently flame-retardant, they are added to resin materials Can improve the flame retardancy of resin materials. However, silicon polymer is more expensive, which is the biggest disadvantage of this type of flame retardant. The addition of silica itself to resin materials does not have a good flame retardant effect. It is mainly used as a synergist with phosphorus-based flame retardants. Low price is the biggest advantage of silica.
值得注意的是,上述各項無鹵阻燃劑應用於樹脂材料中,雖然可以達到阻燃等級,但樹脂材料成本提高與其它物性如熱性質、電氣性質或機械性質降低則成為衍生的問題,有待進一步改善。It is worth noting that the above-mentioned halogen-free flame retardants are used in resin materials. Although they can reach the flame retardant level, the increase in the cost of resin materials and the reduction of other physical properties such as thermal, electrical or mechanical properties have become derivative problems. Needs to be further improved.
為克服上述技術問題,本發明之目的在於提供一種阻燃高分子複合材料及其方法,透過在聚烯烴高分子材料中添加經表面熱處理及化學改質之改質矽藻土,增加聚烯烴高分子材料與矽藻土之親和性,以減少無鹵阻燃劑添加量並維持聚烯烴高分子的物性,克服添加無鹵阻燃劑之高成本及導致性能下降的問題,進而製備成兼具低成本及無鹵阻燃特性之複合材料。In order to overcome the above technical problems, the purpose of the present invention is to provide a flame-retardant polymer composite material and a method thereof. By adding modified diatomaceous earth that has undergone surface heat treatment and chemical modification to the polyolefin polymer material, the content of polyolefin is increased. The affinity between molecular materials and diatomaceous earth can reduce the amount of halogen-free flame retardants added and maintain the physical properties of polyolefin polymers, overcome the high cost of adding halogen-free flame retardants and the problem of performance degradation, and then prepare both Low cost and halogen-free flame retardant composite material.
為達上述目的,本發明所提供一種阻燃高分子複合材料,包括:聚烯烴高分子材料,佔該阻燃高分子複合材料重量百分比的64%至69%;改質矽藻土,佔該阻燃高分子複合材料重量百分比的6%至10%,該改質矽藻土係由矽藻土原料經表面熱處理及化學改質後形成;聚磷酸胺,佔該阻燃高分子複合材料重量百分比的6%至14%;膨脹石墨,佔該阻燃高分子複合材料重量百分比的8%至12%;以及,木粉,佔該阻燃高分子複合材料重量百分比的5%至15%。To achieve the above objective, the present invention provides a flame-retardant polymer composite material, including: polyolefin polymer material, accounting for 64% to 69% by weight of the flame-retardant polymer composite material; modified diatomaceous earth, accounting for 6% to 10% by weight of the flame-retardant polymer composite material, the modified diatomaceous earth is formed by surface heat treatment and chemical modification of the diatomite raw material; polyphosphate amine accounts for the weight of the flame-retardant polymer composite material 6% to 14% of the percentage; expanded graphite, accounting for 8% to 12% of the flame-retardant polymer composite material; and wood flour, accounting for 5% to 15% of the flame-retardant polymer composite material.
進一步地,本發明阻燃高分子複合材料的該聚烯烴高分子材料係選自高密度聚乙烯(HDPE)或廢棄聚乙烯。Further, the polyolefin polymer material of the flame-retardant polymer composite material of the present invention is selected from high-density polyethylene (HDPE) or waste polyethylene.
進一步地,本發明阻燃高分子複合材料的該改質矽藻土的矽藻土原料選自矽藻土新料或生產過程產生之廢棄矽藻土。Further, the diatomaceous earth raw material of the modified diatomaceous earth of the flame-retardant polymer composite material of the present invention is selected from new diatomaceous earth materials or waste diatomaceous earth produced during the production process.
進一步地,本發明阻燃高分子複合材料的該改質矽藻土的矽藻土原料係於200至600℃的溫度條件下進行2至4小時的熱處理;熱處理後的矽藻土原料係透過噴灑溶於揮發性溶劑的改質劑進行化學改質;該揮發性溶劑選自甲醇、乙醇、丙酮或二氯甲烷中的一種,該改質劑選自丙三甲氧矽烷、乙烯基三乙氧矽烷、丙三乙氧矽烷或3-氨丙基三乙氧基矽烷中的一種。Further, the diatomaceous earth material of the modified diatomaceous earth of the flame-retardant polymer composite material of the present invention is heat-treated for 2 to 4 hours at a temperature of 200 to 600°C; the heat-treated diatomaceous earth material is transparent Spray a modifier dissolved in a volatile solvent for chemical modification; the volatile solvent is selected from one of methanol, ethanol, acetone or dichloromethane, and the modifier is selected from glycerol and vinyltriethoxy One of silane, triethoxysilane, or 3-aminopropyl triethoxysilane.
進一步地,本發明阻燃高分子複合材料中,該揮發性溶劑為丙酮溶液,該改質劑為丙三甲氧矽烷;該矽藻土原料係透過噴灑溶於丙酮溶液的丙三甲氧矽烷進行化學改質。Further, in the flame-retardant polymer composite material of the present invention, the volatile solvent is an acetone solution, and the modifier is glycerol; the raw material of diatomaceous earth is chemically sprayed with glycerol dissolved in acetone. Modified.
此外,本發明另提供一種阻燃高分子複合材料製備方法,該方法的步驟包括:In addition, the present invention also provides a method for preparing a flame-retardant polymer composite material. The steps of the method include:
材料提供步驟:提供聚烯烴高分子材料、改質矽藻土、聚磷酸胺以及膨脹石墨;Material supply steps: provide polyolefin polymer materials, modified diatomaceous earth, amine polyphosphate and expanded graphite;
聚烯烴高分子材料前處理步驟:將該聚烯烴高分子材料加熱至軟化;Pre-treatment steps of polyolefin polymer material: heating the polyolefin polymer material to soften;
矽藻土熱處理步驟:將該改質矽藻土的矽藻土原料放入烘箱內熱處理,處理溫度為200至600℃、處理時間為2至4小時;Diatomite heat treatment step: put the diatomite material of modified diatomite into an oven for heat treatment, the treatment temperature is 200 to 600°C, and the treatment time is 2 to 4 hours;
矽藻土改質步驟:提供改質劑及揮發性溶劑,將該改質劑溶入該揮發性溶劑後均勻噴灑於該矽藻土原料上,待揮發性溶劑揮發後製得該改質矽藻土;Diatomite modification step: provide a modifier and a volatile solvent, dissolve the modifier into the volatile solvent and spray it evenly on the diatomaceous earth raw material, and prepare the modified diatom after the volatile solvent volatilizes earth;
混合步驟:將佔該阻燃高分子複合材料重量百分比為64%至69%的聚烯烴高分子材料、6%至10%的改質矽藻土、6%至14%的聚磷酸胺、8%至12%的膨脹石墨以及5%至15%的木粉混合,製得該阻燃高分子複合材料。Mixing step: the weight percentage of the flame-retardant polymer composite material is 64% to 69% polyolefin polymer material, 6% to 10% modified diatomaceous earth, 6% to 14% polyamine polyphosphate, 8% % To 12% of expanded graphite and 5% to 15% of wood powder are mixed to prepare the flame-retardant polymer composite material.
進一步地,該阻燃高分子複合材料製備方法中,該矽藻土改質步驟的改質劑較佳為丙三甲氧矽烷,該揮發性溶劑較佳為丙酮溶液。Furthermore, in the preparation method of the flame-retardant polymer composite material, the modifier of the diatomite modification step is preferably glycerol, and the volatile solvent is preferably an acetone solution.
更進一步地,該矽藻土改質步驟中,該丙三甲氧矽烷與該丙酮溶液的體積比例為1:1,該丙三甲氧矽烷與該矽藻土原料的體積比例為1:1。Furthermore, in the diatomite modification step, the volume ratio of the glycerol and the acetone solution is 1:1, and the volume ratio of the glycerol and the diatomaceous earth raw material is 1:1.
進一步地,該阻燃高分子複合材料製備方法中,該聚烯烴高分子材料、該改質矽藻土、該聚磷酸胺、該膨脹石墨的混合環境溫度為150至180℃。Further, in the preparation method of the flame-retardant polymer composite material, the temperature of the mixed environment of the polyolefin polymer material, the modified diatomaceous earth, the polyphosphate amine, and the expanded graphite is 150 to 180°C.
進一步地,該阻燃高分子複合材料製備方法中,該混合步驟更包含進行一攪拌動作,該攪拌動作的攪拌速率為50至80轉/每分鐘。Further, in the preparation method of the flame-retardant polymer composite material, the mixing step further includes performing a stirring action, and the stirring rate of the stirring action is 50 to 80 revolutions per minute.
本發明由於使用了以上技術方案,於聚烯烴高分子材料中添加熱處理及化學改質後之矽藻土可有效降低阻燃劑的添加量,符合目前環保趨勢及廢棄物再利用,使本發明的阻燃高分子複合材料能夠以較少的無鹵阻燃劑添加量達到阻燃效果並維持高分子材料的物性、機械強度等,從而形成兼具低成本及無鹵阻燃特性之複合材料。此外,本發明的阻燃高分子複合材料合乎國際環保需求,具備環保、耐燃、循環再利用等優勢,使其較市場產品更具競爭力,能夠應用於建築裝修、家居用品、塑木材料等領域,有效起到阻燃作用。Due to the use of the above technical solutions in the present invention, adding heat-treated and chemically modified diatomaceous earth to polyolefin polymer materials can effectively reduce the amount of flame retardant added, which conforms to the current environmental protection trend and waste recycling, so that the present invention The flame-retardant polymer composite material can achieve the flame-retardant effect with a small amount of halogen-free flame retardant and maintain the physical properties and mechanical strength of the polymer material, thereby forming a composite material with both low cost and halogen-free flame retardant properties . In addition, the flame-retardant polymer composite material of the present invention meets the international environmental protection needs, has the advantages of environmental protection, flame resistance, recycling, etc., making it more competitive than market products, and can be used in building decoration, household products, plastic wood materials, etc. Field, effectively play a flame retardant effect.
有關於本發明為達成上述目的,所採用之技術、手段及其他功效,茲舉一較佳可行實施例並配合表格詳細說明如後。Regarding the technology, means and other effects used by the present invention to achieve the above-mentioned objects, a preferred and feasible embodiment is described in detail in conjunction with the table below.
為利於對本發明的瞭解,以下結合實施例進行說明。In order to facilitate the understanding of the present invention, the following description will be given in conjunction with the embodiments.
本發明特徵與優點的一些實施例將在以下說明中詳細敘述。應理解的是本發明能夠在不同的態樣上具有各種的變化,然其皆不脫離本發明的範圍,且其中的說明及圖式在本質上係當作說明之用,而非用於限制本發明。Some embodiments of the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different aspects, but they do not depart from the scope of the present invention, and the descriptions and drawings therein are essentially for illustrative purposes rather than limiting this invention.
本發明提供一種阻燃高分子複合材料及其方法,該阻燃高分子複合材料的重量百分比組成包括64%至69%的聚烯烴高分子材料、6%至10%的改質矽藻土、6%至14%的聚磷酸胺、8%至12%的膨脹石墨以及木粉的5%至15%;其中,該改質矽藻土係由矽藻土原料經表面熱處理及化學改質後形成。The present invention provides a flame-retardant polymer composite material and a method thereof. The weight percentage composition of the flame-retardant polymer composite material includes 64% to 69% polyolefin polymer material, 6% to 10% modified diatomaceous earth, 6% to 14% of amine polyphosphate, 8% to 12% of expanded graphite and 5% to 15% of wood powder; among them, the modified diatomaceous earth is made of diatomaceous earth raw materials after surface heat treatment and chemical modification form.
以下請配合參閱表一至表四,說明阻燃高分子複合材料的組成、其製法及其功效試驗。Please refer to Table 1 to Table 4 below to explain the composition of the flame-retardant polymer composite material, its preparation method and its efficacy test.
本發明提供的阻燃高分子複合材料製備方法,其步驟包括:材料提供步驟、聚烯烴高分子材料前處理步驟、矽藻土熱處理步驟、矽藻土改質步驟以及混合步驟。其中:The preparation method of the flame-retardant polymer composite material provided by the present invention includes the steps of: material providing step, polyolefin polymer material pretreatment step, diatomite heat treatment step, diatomite modification step, and mixing step. among them:
該材料提供步驟:提供聚烯烴高分子材料、改質矽藻土、聚磷酸胺以及膨脹石墨。The material supply steps: provide polyolefin polymer material, modified diatomaceous earth, polyphosphate amine and expanded graphite.
該聚烯烴高分子材料前處理步驟:將該聚烯烴高分子材料加熱至軟化。The pretreatment step of the polyolefin polymer material: heating the polyolefin polymer material to soften.
該矽藻土熱處理步驟:將該改質矽藻土的矽藻土原料放入烘箱內熱處理,處理溫度為200至600℃、處理時間為2至4小時。The heat treatment step of the diatomite: putting the diatomite raw material of the modified diatomite into an oven for heat treatment, the treatment temperature is 200 to 600° C., and the treatment time is 2 to 4 hours.
該矽藻土改質步驟:提供改質劑及揮發性溶劑,將該改質劑溶入該揮發性溶劑後均勻噴灑於該矽藻土原料上,待揮發性溶劑揮發後製得該改質矽藻土。The diatomite modification step: provide a modifier and a volatile solvent, dissolve the modifier into the volatile solvent, and spray the modifier evenly on the diatomite raw material. After the volatile solvent evaporates, the modified silica is obtained Algae earth.
該混合步驟:將佔該阻燃高分子複合材料重量百分比為64%至69%的聚烯烴高分子材料、6%至10%的改質矽藻土、6%至14%的聚磷酸胺、8%至12%的膨脹石墨以及5%至15%的木粉混合,製得該阻燃高分子複合材料。The mixing step: the weight percentage of the flame-retardant polymer composite material is 64% to 69% polyolefin polymer material, 6% to 10% modified diatomaceous earth, 6% to 14% polyamine polyphosphate, 8% to 12% of expanded graphite and 5% to 15% of wood powder are mixed to prepare the flame-retardant polymer composite material.
於本發明實施例中,該聚烯烴高分子材料係選自高密度聚乙烯(HDPE)或廢棄聚乙烯。該高密度聚乙烯是指市售可取得的純高密度聚乙烯;該廢棄聚乙烯可取自牛奶瓶或塑膠桶,但不限於此。In the embodiment of the present invention, the polyolefin polymer material is selected from high density polyethylene (HDPE) or waste polyethylene. The high-density polyethylene refers to commercially available pure high-density polyethylene; the waste polyethylene can be taken from milk bottles or plastic barrels, but is not limited thereto.
於本發明實施例中,該改質矽藻土的矽藻土原料選自矽藻土新料或生產過程產生之廢棄矽藻土。本發明改質矽藻土的矽藻土原料可使用市售可取得的矽藻土新料或者在生產過程產生之廢棄矽藻土;進一步地,該廢棄矽藻土較佳取自釀酒過程中過濾用之矽藻土,但不限於此。In the embodiment of the present invention, the diatomite raw material of the modified diatomite is selected from new diatomite materials or waste diatomite produced during the production process. The diatomaceous earth raw material of the modified diatomite of the present invention can use commercially available new diatomaceous earth materials or waste diatomaceous earth produced during the production process; further, the waste diatomaceous earth is preferably taken from the brewing process Diatomaceous earth for filtration, but not limited to this.
於本發明實施例中,該矽藻土原料的熱處理條件是在200至600℃的溫度下進行2至4小時;該矽藻土原料較佳於200℃的溫度條件下進行3小時的熱處理。熱處理後的矽藻土原料係透過噴灑溶於揮發性溶劑的改質劑進行化學改質;該揮發性溶劑選自甲醇、乙醇、丙酮或二氯甲烷中的一種,該改質劑選自丙三甲氧矽烷、乙烯基三乙氧矽烷、丙三乙氧矽烷或3-氨丙基三乙氧基矽烷中的一種;其中,該揮發性溶劑較佳為丙酮溶液,該改質劑較佳為丙三甲氧矽烷,且該丙三甲氧矽烷與該丙酮溶液的體積比例為1:1,該丙三甲氧矽烷與該矽藻土的體積比例為1:1。In the embodiment of the present invention, the heat treatment condition of the diatomaceous earth material is at a temperature of 200 to 600°C for 2 to 4 hours; the diatomaceous earth material is preferably heat treated at a temperature of 200°C for 3 hours. The heat-treated diatomaceous earth material is chemically modified by spraying a modifying agent dissolved in a volatile solvent; the volatile solvent is selected from one of methanol, ethanol, acetone or dichloromethane, and the modifying agent is selected from propylene One of trimethoxysilane, vinyl triethoxysilane, triethoxysilane, or 3-aminopropyl triethoxysilane; wherein, the volatile solvent is preferably an acetone solution, and the modifier is preferably The volume ratio of the glycerol and the acetone solution is 1:1, and the volume ratio of the glycerol and the diatomaceous earth is 1:1.
於本發明實施例中,該混合步驟更包含進行一攪拌動作,該攪拌動作的攪拌速率為50至80轉/每分鐘。於本發明實施例中,該聚烯烴高分子材料、該改質矽藻土、該聚磷酸胺、該膨脹石墨的混合環境溫度為150至180℃;該攪拌動作的執行時間較佳為8至10分鐘。較佳地,該混合步驟的混合環境溫度為160℃、執行時間為10分鐘。In the embodiment of the present invention, the mixing step further includes performing a stirring action, and the stirring rate of the stirring action is 50 to 80 revolutions per minute. In the embodiment of the present invention, the mixing environment temperature of the polyolefin polymer material, the modified diatomaceous earth, the polyphosphate amine, and the expanded graphite is 150 to 180°C; the execution time of the stirring action is preferably 8 to 10 minutes. Preferably, the mixing environment temperature of the mixing step is 160° C., and the execution time is 10 minutes.
如表一至表四所示,本發明的樣品包括實施例1至實施例6,其中:實施例1(樣品名稱縮寫:HDPE),無添加矽藻土、聚磷酸胺、膨脹石墨及木粉的高密度聚乙烯(HDPE);實施例2(樣品名稱縮寫:A12E12)是無添加矽藻土、添加12wt%聚磷酸胺(A)、12wt%膨脹石墨(E)及10wt%木粉的聚烯烴高分子材料;實施例3(樣品名稱縮寫:A14E12)是無添加矽藻土、添加14wt%聚磷酸胺(A)、12wt%膨脹石墨(E)及10wt%木粉的聚烯烴高分子材料;實施例4(樣品名稱縮寫:A7E12D)是添加7wt%矽藻土、7wt%聚磷酸胺(A)、12wt%膨脹石墨(E)及10wt%木粉的聚烯烴高分子材料;實施例5(樣品名稱縮寫:A6E08D)是添加7wt%矽藻土、6wt%聚磷酸胺(A)、8wt%膨脹石墨(E)及10wt%木粉的聚烯烴高分子材料;實施例6(樣品名稱縮寫:SA6E08D)是添加7wt%經丙三甲氧矽烷預處理(S)的矽藻土(D)、6wt%聚磷酸胺(A)、8wt%膨脹石墨(E)及10wt%木粉的聚烯烴高分子材料。As shown in Table 1 to Table 4, the samples of the present invention include Examples 1 to 6, in which: Example 1 (abbreviation of sample name: HDPE), without adding diatomaceous earth, polyphosphate amine, expanded graphite and wood powder High-density polyethylene (HDPE); Example 2 (sample name abbreviation: A12E12) is a polyolefin without adding diatomaceous earth, adding 12wt% amine polyphosphate (A), 12wt% expanded graphite (E) and 10wt% wood powder Polymer material; Example 3 (sample name abbreviation: A14E12) is a polyolefin polymer material without adding diatomaceous earth, adding 14wt% amine polyphosphate (A), 12wt% expanded graphite (E) and 10wt% wood powder; Example 4 (abbreviation of sample name: A7E12D) is a polyolefin polymer material added with 7wt% diatomaceous earth, 7wt% amine polyphosphate (A), 12wt% expanded graphite (E) and 10wt% wood powder; Example 5 ( Sample name abbreviation: A6E08D) is a polyolefin polymer material added with 7wt% diatomaceous earth, 6wt% amine polyphosphate (A), 8wt% expanded graphite (E) and 10wt% wood powder; Example 6 (sample name abbreviation: SA6E08D) is a polyolefin polymer containing 7wt% diatomaceous earth (D) pretreated with glycerin (S), 6wt% amine polyphosphate (A), 8wt% expanded graphite (E) and 10wt% wood powder material.
近幾十年來,因傳統鹵系化合物具有毒性及造成的環境問題,取代其之材料廣受關注。這些材料必須具有阻燃及自熄的性能,膨脹石墨(EG)因其高阻燃效率和低成本而受到越來越多的關注。型態上,膨脹石墨是石墨化合物,其中在碳層之間添加硫酸和高錳酸鉀。當對膨脹石墨施加熱量時,氣體推動碳層,膨脹石墨中的晶面的間距從0.335nm增加到大約0.789nm,產生大量的絕緣層,從而改善複合材料的阻燃性。而在膨脹型阻燃劑中添加聚磷酸胺,對提高限氧指數(LOI)及抗滴落性能具有協同作用。In recent decades, due to the toxicity of traditional halogen compounds and the environmental problems they cause, the materials that replace them have received widespread attention. These materials must have flame retardant and self-extinguishing properties. Expanded graphite (EG) has attracted more and more attention due to its high flame retardant efficiency and low cost. In terms of form, expanded graphite is a graphite compound in which sulfuric acid and potassium permanganate are added between carbon layers. When heat is applied to the expanded graphite, the gas pushes the carbon layer, and the spacing of the crystal planes in the expanded graphite increases from 0.335nm to about 0.789nm, creating a large amount of insulating layers, thereby improving the flame retardancy of the composite material. The addition of amine polyphosphate to intumescent flame retardants has a synergistic effect on improving the limiting oxygen index (LOI) and anti-dripping performance.
然而單獨使用膨脹型阻燃劑通常需要相對高的添加量,依表一至表四的實驗結果可知,聚乙烯高分子材料要達到耐燃UL94等級,聚磷酸胺+膨脹石墨最低添加量必須大於26wt%(表四:A14E12),且其機械性能因阻燃劑添加量較多,降低幅度大,耐衝擊強度(25 J/m)較純料(28.5 J/m)降低12.28%(表二),拉伸強度(23.2 MPa)較純料(30.9 MPa)降低24.92%(表三);然而,在添加矽藻土後,達耐燃等級之聚磷酸胺+膨脹石墨最低添加量降低至19wt%(表四: A7E12D),耐衝擊強度(26 J/m)較純料降低8.77%,拉伸強度(20.5 MPa)較純料降低33.66%;因此,本發明使用熱處理及丙三甲氧矽烷改質矽藻土,增加聚乙烯高分子材料與矽藻土之親和性,可降低阻燃劑聚磷酸胺+膨脹石墨添加量至14%(表4: SA6E08D),耐衝擊強度(33.9 J/m)較純料提升了18.95%,拉伸強度(27.9 MPa)較純料僅降低9.71%,拉伸強度降低幅度明顯減小,且耐衝擊強度甚至有提升之趨勢,本發明阻燃高分子複合材料可達到耐燃等級又維持其機械強度,同時降低成本及符合環保趨勢。However, the use of intumescent flame retardants alone usually requires a relatively high amount of addition. According to the experimental results in Tables 1 to 4, it can be seen that for polyethylene polymer materials to reach the flame resistance UL94 level, the minimum addition amount of polyphosphate amine + expanded graphite must be greater than 26wt% (Table 4: A14E12), and its mechanical properties are greatly reduced due to the large amount of flame retardant added, and the impact strength (25 J/m) is 12.28% lower than that of pure material (28.5 J/m) (Table 2), The tensile strength (23.2 MPa) is 24.92% lower than that of the pure material (30.9 MPa) (Table 3); however, after adding diatomaceous earth, the minimum addition amount of polyphosphate amine + expanded graphite that reaches the flame resistance level is reduced to 19wt% (Table 3) Four: A7E12D), the impact strength (26 J/m) is 8.77% lower than the pure material, and the tensile strength (20.5 MPa) is 33.66% lower than the pure material; therefore, the present invention uses heat treatment and glycerol to modify diatoms Soil, increase the affinity of polyethylene polymer material and diatomaceous earth, can reduce the flame retardant polyphosphate amine + expanded graphite to 14% (Table 4: SA6E08D), the impact strength (33.9 J/m) is relatively pure The material has increased by 18.95%, the tensile strength (27.9 MPa) is only 9.71% lower than that of the pure material, the decrease in tensile strength has been significantly reduced, and the impact strength has even increased. The flame-retardant polymer composite material of the present invention can reach The flame resistance grade maintains its mechanical strength, while reducing costs and complying with environmental protection trends.
綜上,本發明使用經表面熱處理及改質之矽藻土,可降低阻燃劑之使用量,不僅可維持高分子的物性,還可降低成本及兼具環保、耐燃、循環再利用之優點。本發明製程中材料混合步驟的溫度低、時間短,所需投資設備成本低廉(可使用一般高分子加工及生產設備)、製程環保節能,未來可應用在建築裝修、家居用品、塑木材料等領域,具有應用範疇廣泛的功效。In summary, the present invention uses surface heat-treated and modified diatomaceous earth, which can reduce the amount of flame retardant used, not only maintains the physical properties of the polymer, but also reduces costs and has the advantages of environmental protection, flame resistance, and recycling. . The material mixing step in the process of the present invention has low temperature, short time, low cost of investment equipment required (general polymer processing and production equipment can be used), environmental protection and energy saving of the process, and can be used in building decoration, household goods, plastic wood materials, etc. Field, has a wide range of applications.
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