TW202208534A - High-performance halogen-free flame retarding pc/cnt conductive material and products thereof - Google Patents
High-performance halogen-free flame retarding pc/cnt conductive material and products thereof Download PDFInfo
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本發明涉及高分子材料技術領域，尤其涉及一種高性能無鹵阻燃PC/CNT導電材料及其製品。The invention relates to the technical field of polymer materials, in particular to a high-performance halogen-free flame-retardant PC/CNT conductive material and its products.
聚碳酸酯（PC）是分子鏈中含有碳酸酯基的高分子聚合物，根據酯基的結構可分爲脂肪族、芳香族、脂肪族－芳香族等多種類型。其中由於脂肪族和脂肪族－芳香族聚碳酸酯的機械性能較低，從而限制了其在工程塑料方面的應用。Polycarbonate (PC) is a high molecular polymer containing carbonate groups in the molecular chain. According to the structure of the ester groups, it can be divided into aliphatic, aromatic, aliphatic-aromatic and other types. Among them, the low mechanical properties of aliphatic and aliphatic-aromatic polycarbonates limit their application in engineering plastics.
碳奈米管(CNT)作爲一微奈米材料，重量輕，六邊形結構連接完美，具有許多異常的力學、電學和化學性能。近些年隨著碳奈米管及奈米材料研究的深入其廣闊的應用前景也不斷地展現出來。Carbon nanotubes (CNTs), as one-micron nanomaterials, are light in weight, with perfectly connected hexagonal structures, and possess many unusual mechanical, electrical, and chemical properties. In recent years, with the in-depth research of carbon nanotubes and nanomaterials, their broad application prospects are also constantly showing.
在以PC爲基的碳奈米管導電材料中，因爲碳奈米管的長徑比大、比表面積大，每100質量份的導電材料成品中添加3.5～7質量份的碳奈米管即可達到10^3Ohm～10^4Ohm，然而，該碳奈米管在燃燒時存在嚴重的燈芯效應，需要加入較多的磷酸酯阻燃劑，從而直接導致該導電材料的性能下降較多，且無法達到1.0mmV-0的阻燃等級，降低了自身的物理特性。In PC-based carbon nanotube conductive materials, due to the large aspect ratio and specific surface area of carbon nanotubes, 3.5 to 7 parts by mass of carbon nanotubes are added per 100 parts by mass of the finished conductive material. It can reach 10^3Ohm～10^4Ohm, however, the carbon nanotubes have a serious wicking effect during combustion, and more phosphate ester flame retardants need to be added, which directly leads to a large decrease in the performance of the conductive material, and The flame retardant grade of 1.0mmV-0 cannot be achieved, which reduces its own physical properties.
有鑒於此，實有必要提供一種高性能無鹵阻燃PC/CNT導電材料及其製品，以解決因碳奈米管的燈芯效應及加入較多磷酸酯阻燃劑而導致該導電材料性能下降、無法達到1.0mmV-0的阻燃等級及自身物理特性降低的問題。In view of this, it is necessary to provide a high-performance halogen-free flame retardant PC/CNT conductive material and its products to solve the performance degradation of the conductive material due to the wicking effect of carbon nanotubes and the addition of more phosphate flame retardants. , Unable to reach the flame retardant grade of 1.0mmV-0 and the problem of reducing its own physical properties.
本發明的目的在於提供一種高性能無鹵阻燃PC/CNT導電材料及其製品，以解決因碳奈米管的燈芯效應及加入較多磷酸酯阻燃劑而導致該導電材料性能下降、無法達到1.0mmV-0的阻燃等級及自身物理特性降低的問題。The purpose of the present invention is to provide a high-performance halogen-free flame-retardant PC/CNT conductive material and its products, so as to solve the problem that the performance of the conductive material is reduced due to the wick effect of carbon nanotubes and the addition of more phosphate flame retardants. The flame retardant grade of 1.0mmV-0 and the reduction of its own physical properties are the problems.
爲了實現上述目的，本發明提供一種高性能無鹵阻燃PC/CNT導電材料，每100質量份的導電材料成品，包括以下質量份的組分： 聚碳酸酯，20～90份； 碳奈米管，3～7份；及 阻燃劑，6.5～14份。In order to achieve the above purpose, the present invention provides a high-performance halogen-free flame-retardant PC/CNT conductive material, and every 100 parts by mass of the finished conductive material includes the following components by mass: Polycarbonate, 20 to 90 parts; Carbon nanotubes, 3 to 7 servings; and Flame retardant, 6.5 to 14 parts.
在一些實施例中，所述聚碳酸酯爲雙酚A型聚碳酸酯、聚酯型聚碳酸酯、有機矽共聚型PC、環己烷雙酚A型聚碳酸酯、雙酚A-有機矽氧烷共聚聚碳酸酯、雙酚TMC合成的耐高溫聚碳酸酯的兩種或兩種以上的複配。In some embodiments, the polycarbonate is bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer PC, cyclohexane bisphenol A polycarbonate, bisphenol A-organosilicon The compound of two or more kinds of oxane copolymer polycarbonate and high temperature resistant polycarbonate synthesized by bisphenol TMC.
在一些實施例中，在溫度300℃和負荷爲1.2Kg條件下，所述聚碳酸酯的熔體質量流動速率在3g/10min～50g/10min之間。In some embodiments, the melt mass flow rate of the polycarbonate is between 3 g/10 min and 50 g/10 min at a temperature of 300° C. and a load of 1.2 Kg.
在一些實施例中，所述碳奈米管爲單壁碳奈米管、雙壁碳奈米管及多壁碳奈米管的一種或一種以上的複配。In some embodiments, the carbon nanotubes are one or more compounds of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
在一些實施例中，所述碳奈米管的直徑在0.7nm～7nm之間，所述0.7nm～7.0nm直徑的碳奈米管品質份數占總碳奈米管質量的50%以上，所述碳奈米管的長徑比在500以上、吸油值在300ml/100g以上、氮吸附比表面積在250m2 /g以上以及碘吸附值在400mg/g以上。In some embodiments, the diameter of the carbon nanotubes is between 0.7 nm and 7 nm, and the quality fraction of the carbon nanotubes with a diameter of 0.7 nm to 7.0 nm accounts for more than 50% of the mass of the total carbon nanotubes, The aspect ratio of the carbon nanotube is above 500, the oil absorption value is above 300ml/100g, the nitrogen adsorption specific surface area is above 250m 2 /g and the iodine adsorption value is above 400mg/g.
在一些實施例中，所述高性能無鹵阻燃PC/CNT導電材料中，導電介質由碳奈米管組成，每100質量份的導電材料成品中添加3.5～7質量份的碳奈米管，所述導電材料的表面電阻可降至10^3Ohm～10^5Ohm。In some embodiments, in the high-performance halogen-free flame-retardant PC/CNT conductive material, the conductive medium is composed of carbon nanotubes, and 3.5-7 parts by mass of carbon nanotubes are added to every 100 parts by mass of the finished conductive material. , the surface resistance of the conductive material can be reduced to 10^3 Ohm ~ 10^5 Ohm.
在一些實施例中，所述阻燃劑爲次磷酸鹽阻燃劑、有機矽系阻燃劑及苯氧基環磷腈的兩種或兩種以上的複配。In some embodiments, the flame retardant is a compound of two or more of hypophosphite flame retardant, organosilicon-based flame retardant and phenoxycyclophosphazene.
在一些實施例中，所述次磷酸鹽阻燃劑爲乙烯基次磷酸鋁阻燃劑，所述有機矽系阻燃劑爲聚矽硼烷及其衍生物阻燃劑、聚甲氧基苯基矽烷及其衍生物、羥甲基矽烷及其衍生物、交聯的聚二甲基矽氧烷（PDMS）及其衍生物阻燃劑的一種或一種以上的複配。In some embodiments, the hypophosphite flame retardant is vinyl aluminum hypophosphite flame retardant, and the organosilicon-based flame retardant is polysilaborane and its derivatives flame retardant, polymethoxybenzene One or more compounds of siloxane and its derivatives, methylolsilane and its derivatives, cross-linked polydimethylsiloxane (PDMS) and its derivatives flame retardants.
在一些實施例中，所述苯氧基環磷腈的磷含量大於13%、氮含量含量大於5.8%、雜離子濃度小於0.01%、重均分子量爲693以及其純度大於98.5%。In some embodiments, the phenoxycyclophosphazene has a phosphorus content of more than 13%, a nitrogen content of more than 5.8%, a heteroion concentration of less than 0.01%, a weight average molecular weight of 693, and a purity of more than 98.5%.
在一些實施例中，每100質量份的導電材料成品中，當含有3質量份的次磷酸鹽阻燃劑、1%的羥基苯基矽烷阻燃劑以及6%的BDP阻燃劑時，所述導電材料的阻燃等級爲1.6mmV-0。In some embodiments, when each 100 parts by mass of the finished conductive material contains 3 parts by mass of hypophosphite flame retardant, 1% of hydroxyphenylsilane flame retardant and 6% of BDP flame retardant, the The flame retardant grade of the conductive material is 1.6mmV-0.
在一些實施例中，每100質量份的導電材料成品中，加入0.5～1份的抗滴落劑。In some embodiments, 0.5-1 part of anti-drip agent is added to every 100 parts by mass of the finished conductive material.
本發明還提供一種製品，所述製品使用上述的一種高性能無鹵阻燃PC/CNT導電材料製備而成。The present invention also provides a product prepared by using the above-mentioned high-performance halogen-free flame-retardant PC/CNT conductive material.
相較於先前技術，本發明的高性能無鹵阻燃PC/CNT導電材料及其製品，透過在導電材料中加入一定比例的聚碳酸酯，碳奈米管作爲導電介質，透過加入次磷酸鹽阻燃劑、苯氧基環磷腈、有機矽阻燃劑複配，使總阻燃劑添加份數降低至於10%以下，使阻燃劑對導電材料本身的物性影響降到最小，從而達到1.0mmV-0的阻燃等級，利用本發明的高性能無鹵阻燃PC/CNT導電材料及其製品，碳奈米管作爲導電介質，不僅使該導電材料獲得較好的抗靜電性能、阻燃等級達到1.0mmV-0，還保留50%以上自身較好的物理特性，並且，所得製品具備較好的抗靜電性能、阻燃性及抗衝擊能力。Compared with the prior art, the high-performance halogen-free flame-retardant PC/CNT conductive material and its products of the present invention are made by adding a certain proportion of polycarbonate and carbon nanotubes as the conductive medium in the conductive material, and by adding hypophosphite. The compounding of flame retardant, phenoxy cyclophosphazene, and organosilicon flame retardant reduces the total number of flame retardants to less than 10%, and minimizes the impact of flame retardants on the physical properties of the conductive material itself, so as to achieve The flame retardant grade of 1.0mmV-0, using the high-performance halogen-free flame-retardant PC/CNT conductive material and its products of the present invention, and carbon nanotubes as the conductive medium, not only make the conductive material obtain better antistatic performance, resistance to The combustion grade reaches 1.0mmV-0, and more than 50% of its own good physical properties are retained, and the obtained product has good antistatic properties, flame retardancy and impact resistance.
本發明提供一種高性能無鹵阻燃PC/CNT導電材料，每100質量份的導電材料成品，包括以下質量份的組分： 聚碳酸酯，20～90份； 碳奈米管，3～7份；及 阻燃劑，6.5～14份。The invention provides a high-performance halogen-free flame-retardant PC/CNT conductive material, and every 100 parts by mass of the finished conductive material includes the following components by mass: Polycarbonate, 20 to 90 parts; Carbon nanotubes, 3 to 7 servings; and Flame retardant, 6.5 to 14 parts.
在一些實施例中，所述聚碳酸酯爲雙酚A型聚碳酸酯、聚酯型聚碳酸酯、有機矽共聚型PC、環己烷雙酚A型聚碳酸酯、雙酚A-有機矽氧烷共聚聚碳酸酯、雙酚TMC合成的耐高溫聚碳酸酯的兩種或兩種以上的複配。In some embodiments, the polycarbonate is bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer PC, cyclohexane bisphenol A polycarbonate, bisphenol A-organosilicon The compound of two or more kinds of oxane copolymer polycarbonate and high temperature resistant polycarbonate synthesized by bisphenol TMC.
在一些實施例中，在溫度300℃和負荷爲1.2Kg條件下，所述聚碳酸酯的熔體質量流動速率在3g/10min～50g/10min之間。In some embodiments, the melt mass flow rate of the polycarbonate is between 3 g/10 min and 50 g/10 min at a temperature of 300° C. and a load of 1.2 Kg.
在一些實施例中，所述碳奈米管爲單壁碳奈米管、雙壁碳奈米管及多壁碳奈米管的一種或一種以上的複配。In some embodiments, the carbon nanotubes are one or more compounds of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
在一些實施例中，所述碳奈米管的直徑在0.7nm～7nm之間，所述0.7nm～7.0nm直徑的碳奈米管品質份數占總碳奈米管質量的50%以上，所述碳奈米管的長徑比在500以上、吸油值在300ml/100g以上、氮吸附比表面積在250m2 /g以上以及碘吸附值在400mg/g以上。In some embodiments, the diameter of the carbon nanotubes is between 0.7 nm and 7 nm, and the quality fraction of the carbon nanotubes with a diameter of 0.7 nm to 7.0 nm accounts for more than 50% of the mass of the total carbon nanotubes, The aspect ratio of the carbon nanotube is above 500, the oil absorption value is above 300ml/100g, the nitrogen adsorption specific surface area is above 250m 2 /g and the iodine adsorption value is above 400mg/g.
在一些實施例中，所述高性能無鹵阻燃PC/CNT導電材料中，導電介質由碳奈米管組成，每100質量份的導電材料成品中添加3.5～7質量份的碳奈米管，所述導電材料的表面電阻可降至10^3Ohm～10^5Ohm。In some embodiments, in the high-performance halogen-free flame-retardant PC/CNT conductive material, the conductive medium is composed of carbon nanotubes, and 3.5-7 parts by mass of carbon nanotubes are added to every 100 parts by mass of the finished conductive material. , the surface resistance of the conductive material can be reduced to 10^3 Ohm ~ 10^5 Ohm.
在一些實施例中，所述阻燃劑爲次磷酸鹽阻燃劑、有機矽系阻燃劑及苯氧基環磷腈的兩種或兩種以上的複配。In some embodiments, the flame retardant is a compound of two or more of hypophosphite flame retardant, organosilicon-based flame retardant and phenoxycyclophosphazene.
在一些實施例中，所述次磷酸鹽阻燃劑爲乙烯基次磷酸鋁阻燃劑，所述有機矽系阻燃劑爲聚矽硼烷及其衍生物阻燃劑、聚甲氧基苯基矽烷及其衍生物、羥甲基矽烷及其衍生物、交聯的聚二甲基矽氧烷（PDMS）及其衍生物阻燃劑的一種或一種以上的複配。In some embodiments, the hypophosphite flame retardant is vinyl aluminum hypophosphite flame retardant, and the organosilicon-based flame retardant is polysilaborane and its derivatives flame retardant, polymethoxybenzene One or more compounds of siloxane and its derivatives, methylolsilane and its derivatives, cross-linked polydimethylsiloxane (PDMS) and its derivatives flame retardants.
在一些實施例中，所述苯氧基環磷腈的磷含量大於13%、氮含量含量大於5.8%、雜離子濃度小於0.01%、重均分子量爲693以及其純度大於98.5%。In some embodiments, the phenoxycyclophosphazene has a phosphorus content of more than 13%, a nitrogen content of more than 5.8%, a heteroion concentration of less than 0.01%, a weight average molecular weight of 693, and a purity of more than 98.5%.
在一些實施例中，每100質量份的導電材料成品中，當含有3質量份的次磷酸鹽阻燃劑、1%的羥基苯基矽烷阻燃劑以及6%的BDP阻燃劑時，所述導電材料的阻燃等級爲1.6mmV-0。In some embodiments, when each 100 parts by mass of the finished conductive material contains 3 parts by mass of hypophosphite flame retardant, 1% of hydroxyphenylsilane flame retardant and 6% of BDP flame retardant, the The flame retardant grade of the conductive material is 1.6mmV-0.
在一些實施例中，每100質量份的導電材料成品中，加入0.5～1份的抗滴落劑。In some embodiments, 0.5-1 part of anti-drip agent is added to every 100 parts by mass of the finished conductive material.
本發明還提供一種製品，所述製品使用上述的一種高性能無鹵阻燃PC/CNT導電材料製備而成。其中，在製備過程中加入適量的抗滴落劑，使該導電材料具有受熱收縮的特點及達到阻燃和防滴落的作用，其中，加入一定比例的聚碳酸酯、碳奈米管，以及加入次磷酸鹽阻燃劑、苯氧基環磷腈、有機矽阻燃劑的複配，使該導電材料具有較好的抗靜電性能、阻燃性及抗衝擊能力。The present invention also provides a product prepared by using the above-mentioned high-performance halogen-free flame-retardant PC/CNT conductive material. Among them, an appropriate amount of anti-drip agent is added in the preparation process, so that the conductive material has the characteristics of thermal shrinkage and achieves the effect of flame retardant and anti-drip, wherein a certain proportion of polycarbonate, carbon nanotubes, and The compound of hypophosphite flame retardant, phenoxy cyclophosphazene and organosilicon flame retardant is added to make the conductive material have good antistatic properties, flame retardancy and impact resistance.
下面通過具體實施方式來進一步說明本發明的技術方案。The technical solutions of the present invention are further described below through specific embodiments.
實施例1：一種高性能無鹵阻燃PC/CNT導電材料，每100質量份的導電材料成品，包括86份的聚碳酸酯、2份的乙烯基次磷酸鋁、7份的苯氧基環磷腈、1份的羥基苯基矽烷、3.5份的碳奈米管及0.5份的抗滴落劑。其中，聚碳酸酯爲雙酚A型聚碳酸酯、聚酯型聚碳酸酯、有機矽共聚型PC、環己烷雙酚A型聚碳酸酯、雙酚A-有機矽氧烷共聚聚碳酸酯、雙酚TMC合成的耐高溫聚碳酸酯的兩種或兩種以上的複配，在溫度300℃和負荷爲1.2Kg條件下，聚碳酸酯的熔體質量流動速率在3g/10min～50g/10min之間，碳奈米管爲單壁碳奈米管、雙壁碳奈米管及多壁碳奈米管的一種或一種以上的複配，碳奈米管的直徑在0.7nm～7nm之間，所述0.7nm～7.0nm直徑的碳奈米管品質份數占總碳奈米管質量的50%以上，碳奈米管的長徑比在500以上、吸油值在300ml/100g以上、氮吸附比表面積在250m2 /g以上以及碘吸附值在400mg/g以上，導電介質由碳奈米管組成，每100質量份的導電材料成品中添加3.5～7質量份的碳奈米管，所述導電材料的表面電阻可降至10^3Ohm～10^5Ohm，阻燃劑爲次磷酸鹽阻燃劑、有機矽系阻燃劑及苯氧基環磷腈的兩種或兩種以上的複配，次磷酸鹽阻燃劑爲乙烯基次磷酸鋁阻燃劑，有機矽系阻燃劑爲聚矽硼烷及其衍生物阻燃劑、聚甲氧基苯基矽烷及其衍生物、羥甲基矽烷及其衍生物、交聯的聚二甲基矽氧烷（PDMS）及其衍生物阻燃劑的一種或一種以上的複配，苯氧基環磷腈的磷含量大於13%、氮含量含量大於5.8%、雜離子濃度小於0.01%、重均分子量爲693以及其純度大於98.5%。每100質量份的導電材料成品中，當含有3質量份的次磷酸鹽阻燃劑、1%的羥基苯基矽烷阻燃劑以及6%的BDP阻燃劑時，所述導電材料的阻燃等級爲1.6mmV-0。Example 1: A high-performance halogen-free flame-retardant PC/CNT conductive material, each 100 parts by mass of the finished conductive material includes 86 parts of polycarbonate, 2 parts of vinyl aluminum hypophosphite, and 7 parts of phenoxy ring Phosphazene, 1 part of hydroxyphenylsilane, 3.5 parts of carbon nanotubes, and 0.5 part of anti-drip agent. Among them, polycarbonate is bisphenol A polycarbonate, polyester polycarbonate, organosilicon copolymer PC, cyclohexane bisphenol A polycarbonate, bisphenol A-organosiloxane copolymer polycarbonate , two or more compounds of high temperature resistant polycarbonate synthesized by bisphenol TMC, under the condition of temperature 300℃ and load of 1.2Kg, the melt mass flow rate of polycarbonate is 3g/10min～50g/ Within 10 minutes, the carbon nanotubes are one or more compounds of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes, and the diameter of the carbon nanotubes is between 0.7nm and 7nm. During the period, the quality fraction of the carbon nanotubes with a diameter of 0.7 nm to 7.0 nm accounts for more than 50% of the total carbon nanotube quality, the aspect ratio of the carbon nanotubes is more than 500, the oil absorption value is more than 300ml/100g, The nitrogen adsorption specific surface area is above 250m 2 /g and the iodine adsorption value is above 400mg/g, the conductive medium is composed of carbon nanotubes, and 3.5 to 7 parts by mass of carbon nanotubes are added to every 100 parts by mass of the finished conductive material. The surface resistance of the conductive material can be reduced to 10^3Ohm～10^5Ohm, and the flame retardant is two or more of hypophosphite flame retardant, organosilicon flame retardant and phenoxy cyclophosphazene. Compound, hypophosphite flame retardant is vinyl aluminum hypophosphite flame retardant, organosilicon flame retardant is polysilaborane and its derivatives flame retardant, polymethoxyphenyl silane and its derivatives, One or more combinations of hydroxymethylsilane and its derivatives, cross-linked polydimethylsiloxane (PDMS) and its derivatives flame retardants, the phosphorus content of phenoxycyclophosphazene is more than 13% , nitrogen content is greater than 5.8%, impurity ion concentration is less than 0.01%, weight average molecular weight is 693 and its purity is greater than 98.5%. In every 100 parts by mass of the finished conductive material, when it contains 3 parts by mass of hypophosphite flame retardant, 1% of hydroxyphenylsilane flame retardant and 6% of BDP flame retardant, the flame retardant of the conductive material The rating is 1.6mmV-0.
秤取上述相應重量的各組分，將各組分攪拌均勻後加入到雙螺桿擠出機中進行熔融擠出造粒。Weigh each component of the above-mentioned corresponding weight, stir each component evenly, and then add it to a twin-screw extruder for melt extrusion and granulation.
比較例1：一種高性能無鹵阻燃PC/CNT導電材料，每100質量份的導電材料成品，包括80份的聚碳酸酯、2份的乙烯基次磷酸鋁、13份的磷酸酯阻燃劑（BDP）、1份的羥基苯基矽烷、3.5份的碳奈米管及0.5份的抗滴落劑。其中，聚碳酸酯爲雙酚A型聚碳酸酯、聚酯型聚碳酸酯、有機矽共聚型PC、環己烷雙酚A型聚碳酸酯、雙酚A-有機矽氧烷共聚聚碳酸酯、雙酚TMC合成的耐高溫聚碳酸酯的兩種或兩種以上的複配，在溫度300℃和負荷爲1.2Kg條件下，聚碳酸酯的熔體質量流動速率在3g/10min～50g/10min之間，碳奈米管爲單壁碳奈米管、雙壁碳奈米管及多壁碳奈米管的一種或一種以上的複配，碳奈米管的直徑在0.7nm～7nm之間，所述0.7nm～7.0nm直徑的碳奈米管品質份數占總碳奈米管質量的50%以上，碳奈米管的長徑比在500以上、吸油值在300ml/100g以上、氮吸附比表面積在250m2 /g以上以及碘吸附值在400mg/g以上，導電介質由碳奈米管組成，每100質量份的導電材料成品中添加3.5～7質量份的碳奈米管，所述導電材料的表面電阻可降至10^3Ohm～10^5Ohm，阻燃劑爲次磷酸鹽阻燃劑、有機矽系阻燃劑及苯氧基環磷腈的兩種或兩種以上的複配，次磷酸鹽阻燃劑爲乙烯基次磷酸鋁阻燃劑，有機矽系阻燃劑爲聚矽硼烷及其衍生物阻燃劑、聚甲氧基苯基矽烷及其衍生物、羥甲基矽烷及其衍生物、交聯的聚二甲基矽氧烷（PDMS）及其衍生物阻燃劑的一種或一種以上的複配，苯氧基環磷腈的磷含量大於13%、氮含量含量大於5.8%、雜離子濃度小於0.01%、重均分子量爲693以及其純度大於98.5%。每100質量份的導電材料成品中，當含有3質量份的次磷酸鹽阻燃劑、1%的羥基苯基矽烷阻燃劑以及6%的BDP阻燃劑時，所述導電材料的阻燃等級爲1.6mmV-0。Comparative Example 1: A high-performance halogen-free flame retardant PC/CNT conductive material, each 100 parts by mass of the finished conductive material includes 80 parts of polycarbonate, 2 parts of vinyl aluminum hypophosphite, and 13 parts of phosphate ester flame retardant agent (BDP), 1 part of hydroxyphenylsilane, 3.5 parts of carbon nanotubes and 0.5 part of anti-drip agent. Among them, polycarbonate is bisphenol A polycarbonate, polyester polycarbonate, organosilicon copolymer PC, cyclohexane bisphenol A polycarbonate, bisphenol A-organosiloxane copolymer polycarbonate , two or more compounds of high temperature resistant polycarbonate synthesized by bisphenol TMC, under the condition of temperature 300℃ and load of 1.2Kg, the melt mass flow rate of polycarbonate is 3g/10min～50g/ Within 10 minutes, the carbon nanotubes are one or more compounds of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes, and the diameter of the carbon nanotubes is between 0.7nm and 7nm. During the period, the quality fraction of the carbon nanotubes with a diameter of 0.7 nm to 7.0 nm accounts for more than 50% of the total carbon nanotube quality, the aspect ratio of the carbon nanotubes is more than 500, the oil absorption value is more than 300ml/100g, The nitrogen adsorption specific surface area is above 250m 2 /g and the iodine adsorption value is above 400mg/g, the conductive medium is composed of carbon nanotubes, and 3.5 to 7 parts by mass of carbon nanotubes are added to every 100 parts by mass of the finished conductive material. The surface resistance of the conductive material can be reduced to 10^3Ohm～10^5Ohm, and the flame retardant is two or more of hypophosphite flame retardant, organosilicon flame retardant and phenoxy cyclophosphazene. Compound, hypophosphite flame retardant is vinyl aluminum hypophosphite flame retardant, organosilicon flame retardant is polysilaborane and its derivatives flame retardant, polymethoxyphenyl silane and its derivatives, One or more combinations of hydroxymethylsilane and its derivatives, cross-linked polydimethylsiloxane (PDMS) and its derivatives flame retardants, the phosphorus content of phenoxycyclophosphazene is more than 13% , nitrogen content is greater than 5.8%, impurity ion concentration is less than 0.01%, weight average molecular weight is 693 and its purity is greater than 98.5%. In every 100 parts by mass of the finished conductive material, when it contains 3 parts by mass of hypophosphite flame retardant, 1% of hydroxyphenylsilane flame retardant and 6% of BDP flame retardant, the flame retardant of the conductive material The rating is 1.6mmV-0.
秤取上述相應重量的各組分，將各組分攪拌均勻後加入到雙螺桿擠出機中進行熔融擠出造粒。Weigh each component of the above-mentioned corresponding weight, stir each component evenly, and then add it to a twin-screw extruder for melt extrusion and granulation.
對以上各實施例及比較例的一種高性能無鹵阻燃PC/CNT導電材料熔融擠出造粒後，將各實施例及比較例中的粒子在塑膠射出成形機上射出成型標準測試樣條，按標準測試所得材料的機械性能，測試結果如表1所示：After melt extrusion and granulation of a high-performance halogen-free flame-retardant PC/CNT conductive material of the above examples and comparative examples, the particles in each example and comparative example were injection-molded on a plastic injection molding machine. Standard test strips , the mechanical properties of the obtained materials are tested according to the standard, and the test results are shown in Table 1:
表1測試結果：
將上述實施例1與比較例1作比對可知，在製備高性能無鹵阻燃PC/CNT導電材料中，當加入一定比例的聚碳酸酯、碳奈米管及抗滴落劑時，雖然比較例1的阻燃劑中有加入適量的乙烯基次磷酸鋁和羥基苯基矽烷，但是沒有加入苯氧基環磷腈的複配，使得該導電材料沒有達到阻燃等級1.0mmV-0，也沒有符合阻燃劑爲次磷酸鹽阻燃劑、有機矽系阻燃劑及苯氧基環磷腈的兩種或兩種以上複配的條件，因此，實施例1中製備高性能無鹵阻燃PC/CNT導電材料中加入一定比例的聚碳酸酯、碳奈米管及抗滴落劑，且加入複配阻燃劑的乙烯基次磷酸鋁、苯氧基環磷腈及羥基苯基矽烷，其中，碳奈米管作爲導電介質，使得該導電材料具有較好的抗靜電性能、且阻燃等級達到1.0mmV-0，還保留了50%以上自身較好的物理特性。Comparing the above Example 1 with Comparative Example 1, it can be seen that in the preparation of high-performance halogen-free flame retardant PC/CNT conductive materials, when a certain proportion of polycarbonate, carbon nanotubes and anti-drip agents are added, although the In the flame retardant of Comparative Example 1, an appropriate amount of vinyl aluminum hypophosphite and hydroxyphenyl silane was added, but no phenoxy cyclophosphazene was added, so that the conductive material did not reach the flame retardant grade of 1.0mmV-0. It also does not meet the conditions that the flame retardant is a hypophosphite flame retardant, an organosilicon flame retardant and a phenoxy cyclophosphazene. A certain proportion of polycarbonate, carbon nanotubes and anti-drip agents are added to the flame retardant PC/CNT conductive material, and vinyl aluminum hypophosphite, phenoxy cyclophosphazene and hydroxyphenyl are added with compound flame retardants Silane, among which, carbon nanotubes are used as conductive medium, so that the conductive material has good antistatic properties, and the flame retardant grade reaches 1.0mmV-0, and also retains more than 50% of its own good physical properties.
相較於先前技術，本發明的高性能無鹵阻燃PC/CNT導電材料及其製品，透過在導電材料中加入一定比例的聚碳酸酯，碳奈米管作爲導電介質，透過加入次磷酸鹽阻燃劑、苯氧基環磷腈、有機矽阻燃劑複配，使總阻燃劑添加份數降低至於10%以下，使阻燃劑對導電材料本身的物性影響降到最小，從而達到1.0mmV-0的阻燃等級，利用本發明的高性能無鹵阻燃PC/CNT導電材料及其製品，碳奈米管作爲導電介質，不僅使該導電材料獲得較好的抗靜電性能、阻燃等級達到1.0mmV-0，還保留50%以上自身較好的物理特性，並且，所得製品具備較好的抗靜電性能、阻燃性及抗衝擊能力。Compared with the prior art, the high-performance halogen-free flame-retardant PC/CNT conductive material and its products of the present invention are made by adding a certain proportion of polycarbonate and carbon nanotubes as the conductive medium in the conductive material, and by adding hypophosphite. The compounding of flame retardant, phenoxy cyclophosphazene, and organosilicon flame retardant reduces the total number of flame retardants to less than 10%, and minimizes the impact of flame retardants on the physical properties of the conductive material itself, so as to achieve The flame retardant grade of 1.0mmV-0, using the high-performance halogen-free flame-retardant PC/CNT conductive material and its products of the present invention, and carbon nanotubes as the conductive medium, not only make the conductive material obtain better antistatic performance, resistance to The combustion grade reaches 1.0mmV-0, and more than 50% of its own good physical properties are retained, and the obtained product has good antistatic properties, flame retardancy and impact resistance.
以上結合具體實施例描述了本發明的技術原理，這些描述只是爲了解釋本發明原理，不能以任何方式解釋爲對本發明保護範圍的限制。基於此處解釋，本領域技術人員不需要付出進步性的工作即可聯想到本發明的其它具體實施方式，這些方式都將落入本發明的保護範圍之內。The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are only for explaining the principles of the present invention, and cannot be interpreted as limiting the protection scope of the present invention in any way. Based on the explanations herein, those skilled in the art can think of other specific embodiments of the present invention without making progressive work, and these methods will all fall within the protection scope of the present invention.
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