CN115181435A - Surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chip - Google Patents
Surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chipDownload PDFInfo
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明涉及一种原位聚合聚酯切片用炭黑阻燃颜料的表面改性方法，属于精细化工技术领域。The invention relates to a surface modification method of carbon black flame retardant pigment for in-situ polymerization of polyester chips, belonging to the technical field of fine chemicals.
背景技术Background technique
原液着色法根据着色剂添加的阶段不同，可细分为：聚合阶段染色、纺丝阶段染色。聚合阶段染色又称原位聚合染色法，是将着色剂在合成PET大分子缩聚阶段加入，制备出有色PET切片，再将有色PET切片熔融纺丝制备有色PET纤维的方法。原位聚合染色法是聚酯纤维原液着色最早实现工业化生产的方法，此种方法不仅生产成本低、可大批量生产，还可解决原液着色聚酯中颜料粒子于基体相容性差的问题。The dope dyeing method can be subdivided into: polymerization stage dyeing and spinning stage dyeing according to the different stages of colorant addition. Polymerization stage dyeing, also known as in-situ polymerization dyeing method, is a method of adding colorants in the polycondensation stage of synthetic PET macromolecules to prepare colored PET chips, and then melt spinning the colored PET chips to prepare colored PET fibers. The in-situ polymerization dyeing method is the earliest method for industrialized production of polyester fiber dope dyeing. This method not only has low production cost and can be mass-produced, but also solves the problem of poor compatibility of pigment particles in dope dyed polyester with the matrix.
在保证服用性能优异的同时还应赋予纤维功能性应用，以提升产品竞争力。目前，世界各地都在竞相开发PET阻燃制品，但现有的阻燃PET母粒在实际应用中往往存在许多问题，比如：有些阻燃PET母粒制成的聚酯纤维在燃烧时会产生浓烟及有毒有害气体，难以达到使用要求；有些阻燃PET母粒阻燃性能优良，但加入阻燃剂后对聚酯结构破坏严重，严重堵塞喷丝孔，使得纤维力学性能下降，难以成纤。While ensuring excellent wearing performance, functional applications should also be given to fibers to enhance product competitiveness. At present, all parts of the world are competing to develop PET flame retardant products, but the existing flame retardant PET masterbatch often has many problems in practical applications, such as: some polyester fibers made of flame retardant PET masterbatch will produce Thick smoke and toxic and harmful gases are difficult to meet the requirements for use; some flame retardant PET masterbatches have excellent flame retardant properties, but after adding flame retardants, the polyester structure is seriously damaged, the spinneret holes are seriously blocked, the mechanical properties of the fibers are reduced, and it is difficult to produce fiber.
发明内容SUMMARY OF THE INVENTION
为了解决上述问题，本发明提供了一种原位聚合聚酯切片用炭黑阻燃颜料的表面改性方法，使得得到的炭黑阻燃颜料用于制备原位聚合聚酯纤维不仅能提升炭黑阻燃颜料在聚酯纤维中的分散性能，又能赋予阻燃性能，达到无卤阻燃的效果，解决了传统阻燃母粒可纺性差、过滤压力高、阻燃效果欠佳的问题。In order to solve the above problems, the present invention provides a surface modification method of carbon black flame retardant pigment for in situ polymerization of polyester chips, so that the obtained carbon black flame retardant pigment is used to prepare in situ polymerized polyester fiber, which can not only improve carbon black The dispersion properties of black flame retardant pigments in polyester fibers can also impart flame retardant properties to achieve the effect of halogen-free flame retardant, which solves the problems of poor spinnability, high filtration pressure and poor flame retardant effect of traditional flame retardant masterbatches .
本发明的第一个目的是提供一种原位聚合聚酯切片用炭黑阻燃颜料的表面改性方法，包括如下步骤：The first object of the present invention is to provide a kind of surface modification method of carbon black flame retardant pigment for in-situ polymerization of polyester chips, comprising the steps:
将异氰酸酯化炭黑、有机溶剂和阻燃剂混合，机械搅拌下冰浴反应30～60min后加热至100～120℃继续反应30～60min；反应结束后，将反应产物过滤、洗涤、干燥，得到所述的炭黑阻燃颜料；Isocyanated carbon black, an organic solvent and a flame retardant are mixed, reacted in an ice bath under mechanical stirring for 30-60 minutes, then heated to 100-120° C. to continue the reaction for 30-60 minutes; after the reaction, the reaction product is filtered, washed and dried to obtain The carbon black flame retardant pigment;
其中，所述阻燃剂的结构为磷酸酯、膦酸酯、磷杂菲、氧化膦结构中的一种或多种。Wherein, the structure of the flame retardant is one or more of phosphate ester, phosphonate ester, phosphaphenanthrene, and phosphine oxide structure.
在本发明的一种实施方式中，所述的阻燃剂包括三羟基乙基磷酸酯、苯基膦酸、三羟甲基氧化膦中的一种或几种。In an embodiment of the present invention, the flame retardant includes one or more of trihydroxyethyl phosphate, phenylphosphonic acid, and trimethylolphosphine oxide.
在本发明的一种实施方式中，所述的所述有机溶剂为甲苯、丙酮、丁酮中的一种。In one embodiment of the present invention, the organic solvent is one of toluene, acetone and butanone.
在本发明的一种实施方式中，所述的异氰酸酯化炭黑和阻燃剂的质量比为1：2～5。In an embodiment of the present invention, the mass ratio of the isocyanated carbon black and the flame retardant is 1:2-5.
在本发明的一种实施方式中，所述的异氰酸酯化炭黑和有机溶剂的用量比为1～20g：350mL。In an embodiment of the present invention, the dosage ratio of the isocyanated carbon black and the organic solvent is 1-20 g: 350 mL.
在本发明的一种实施方式中，所述的机械搅拌的转速为200～400r/min。In an embodiment of the present invention, the rotational speed of the mechanical stirring is 200-400 r/min.
在本发明的一种实施方式中，所述的异氰酸酯化炭黑的制备方法为：In one embodiment of the present invention, the preparation method of described isocyanate carbon black is:
采用液相氧化剂对炭黑进行氧化改性，得到氧化炭黑；之后将氧化炭黑分散在有机溶剂中，得到氧化炭黑分散液；再在氧化炭黑分散液中加入二异氰酸酯，在冰浴条件下反应30～60min，后升温至80～120℃继续反应30～60min；反应完成后旋蒸除去未反应的二异氰酸酯，得到所述的异氰酸酯化炭黑；The carbon black is oxidized and modified with a liquid-phase oxidant to obtain oxidized carbon black; then the oxidized carbon black is dispersed in an organic solvent to obtain an oxidized carbon black dispersion; then diisocyanate is added to the oxidized carbon black dispersion, and the oxidized carbon black is added in an ice bath. The reaction is carried out for 30 to 60 min under the conditions, and then the temperature is raised to 80 to 120° C. to continue the reaction for 30 to 60 min; after the reaction is completed, the unreacted diisocyanate is removed by rotary evaporation to obtain the isocyanated carbon black;
其中，所述液相氧化剂为过氧化氢溶液、硝酸溶液、饱和过硫酸铵溶液、高氯酸、次氯酸钠溶液、高锰酸钾溶液中的一种；所述炭黑与液相氧化剂的用量比为1～50g：100mL，进一步优选为5～50g：100mL，更进一步优选为10～50g：100mL；氧化改性是25～100℃下氧化改性0.5～10h，进一步优选为50～80℃下氧化改性3～5h；所述有机溶剂为甲苯、丙酮、丁酮中的一种；氧化炭黑和有机溶剂的用量比为10～40g：100mL；所述的二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)中的一种，进一步优选为二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)中的一种；二异氰酸酯和氧化炭黑的质量比为18～25：50；旋蒸的温度为75～85℃；炭黑的粒径为1～50μm。Wherein, the liquid-phase oxidant is one of hydrogen peroxide solution, nitric acid solution, saturated ammonium persulfate solution, perchloric acid, sodium hypochlorite solution, and potassium permanganate solution; the consumption ratio of the carbon black to the liquid-phase oxidant is It is 1-50g: 100mL, more preferably 5-50g: 100mL, still more preferably 10-50g: 100mL; the oxidation modification is 0.5-10h at 25-100°C, more preferably at 50-80°C Oxidative modification for 3 to 5 hours; the organic solvent is one of toluene, acetone, and methyl ethyl ketone; the dosage ratio of oxidized carbon black and organic solvent is 10 to 40 g: 100 mL; the diisocyanate is toluene diisocyanate (TDI ), a kind of in isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), more preferably the diisocyanate is toluene diisocyanate (TDI), isocyanurate A kind of phorone diisocyanate (IPDI); the mass ratio of diisocyanate and oxidized carbon black is 18-25:50; the temperature of rotary steaming is 75-85°C; the particle size of carbon black is 1-50 μm.
在本发明的一种实施方式中，所述的阻燃剂的结构如下：In one embodiment of the present invention, the structure of the flame retardant is as follows:
本发明的第二个目的是本发明所述的方法制备得到的炭黑阻燃颜料。The second object of the present invention is the carbon black flame retardant pigment prepared by the method of the present invention.
本发明的第三个目的是提供一种制备阻燃黑色聚酯切片的方法，包括如下步骤：The third object of the present invention is to provide a method for preparing flame-retardant black polyester chips, comprising the steps:
(1)将本发明的炭黑阻燃颜料、聚酯型分散剂、多元醇混合均匀，进行研磨，得到黑色阻燃颜料分散体；(1) uniformly mix the carbon black flame retardant pigment of the present invention, polyester dispersant and polyol, and grind to obtain black flame retardant pigment dispersion;
(2)在聚酯酯化前加入黑色阻燃颜料分散体，进行聚合，得到所述的阻燃黑色聚酯。(2) adding a black flame retardant pigment dispersion before polyester esterification, and carrying out polymerization to obtain the flame retardant black polyester.
在本发明的一种实施方式中，步骤(1)中所述的黑色阻燃颜料分散体中炭黑阻燃颜料的质量浓度为18～25％，聚酯型分散剂的用量为炭黑阻燃颜料的质量的15～20％；其余为多元醇。In one embodiment of the present invention, the mass concentration of the carbon black flame retardant pigment in the black flame retardant pigment dispersion described in step (1) is 18-25%, and the amount of the polyester dispersant is carbon black flame retardant pigment. 15-20% of the mass of the burning pigment; the rest are polyols.
在本发明的一种实施方式中，步骤(1)中所述的多元醇为乙二醇。In one embodiment of the present invention, the polyol described in step (1) is ethylene glycol.
在本发明的一种实施方式中，步骤(1)中所述的聚酯型分散剂为SUA-300分散剂(世名科技)；重均分子量为5000～45000，进一步优选为8000～38000，更进一步优选为10000～25000；数均分子量在1000～15000，进一步优选为2500～12000，更进一步优选为4000～10000。In one embodiment of the present invention, the polyester type dispersant described in step (1) is SUA-300 dispersant (World Famous Technology); the weight average molecular weight is 5000-45000, more preferably 8000-38000, More preferably, it is 10,000 to 25,000; the number average molecular weight is 1,000 to 15,000, more preferably 2,500 to 12,000, and even more preferably 4,000 to 10,000.
在本发明的一种实施方式中，步骤(1)中所述的研磨包括球磨碾磨、砂磨、超微磨碎机研磨或两辊或三辊研磨。In one embodiment of the present invention, the grinding described in step (1) includes ball milling, sand milling, attritor milling, or two-roll or three-roll grinding.
在本发明的一种实施方式中，步骤(2)所述的在聚酯酯化前加入黑色阻燃颜料分散体进行聚合具体为：In one embodiment of the present invention, adding black flame retardant pigment dispersion to polymerize before polyester esterification described in step (2) is specifically:
将精对苯二甲酸、乙二醇混合后经第一、第二酯化釜反应得到聚酯酯化低聚物，其中催化剂醋酸锌在第二酯化釜中添加，用量一般在0.05％左右(对DMT重量)，然后将黑色阻燃颜料分散体添加进入聚酯酯化低聚物，再依次通过预缩聚釜、终缩聚釜后，按照国家标准《GB/T 14190-2017纤维级聚酯(PET)切片试验方法》制成阻燃黑色聚酯切片。After mixing purified terephthalic acid and ethylene glycol, the first and second esterification kettles are reacted to obtain polyester esterified oligomers, wherein the catalyst zinc acetate is added in the second esterification kettle, and the dosage is generally about 0.05% (to the weight of DMT), then add the black flame retardant pigment dispersion into the polyester esterified oligomer, and then pass through the pre-polycondensation kettle and the final polycondensation kettle in turn, according to the national standard "GB/T 14190-2017 fiber grade polyester (PET) Chip Test Method" to make flame retardant black polyester chips.
本发明的第四个目的是本发明所述的方法制备得到的阻燃黑色聚酯切片。The fourth object of the present invention is the flame-retardant black polyester chips prepared by the method of the present invention.
本发明的第五个目的是提供一种阻燃黑色聚酯纤维，其是采用本发明所述的阻燃聚酯切片进行熔体直纺得到。The fifth object of the present invention is to provide a flame-retardant black polyester fiber, which is obtained by melt-spinning the flame-retardant polyester chips of the present invention.
本发明的第六个目的是本发明所述的炭黑阻燃颜料、阻燃黑色聚酯切片、阻燃黑色聚酯纤维在功能纺织品中的应用。The sixth object of the present invention is the application of the carbon black flame retardant pigment, the flame retardant black polyester chip, and the flame retardant black polyester fiber of the present invention in functional textiles.
本发明的有益效果：Beneficial effects of the present invention:
(1)本发明通过在炭黑表面接枝阻燃剂，可以使得炭黑在原位聚合聚酯切片中保持良好分散的同时，提升炭黑颜料的阻燃性能；另外本发明采用聚酯型分散剂在多元醇体系中分散研磨处理炭黑，降低了炭黑的粒径，有利于在聚酯纤维原位聚合中的应用。(1) In the present invention, by grafting the flame retardant on the surface of the carbon black, the carbon black can be kept well dispersed in the in-situ polymerized polyester chips, and at the same time, the flame retardant performance of the carbon black pigment can be improved; in addition, the present invention adopts the polyester type The dispersant disperses and grinds the carbon black in the polyol system, reduces the particle size of the carbon black, and is beneficial to the application in the in-situ polymerization of polyester fibers.
(2)本发明所述的表面改性炭黑阻燃颜料在用于制备原位聚合聚酯切片时，可以更均匀的分散于树脂载体中，进而提高在制备原液着色纤维时颜料的分散均匀性和相容性，避免出现颜料颗粒团聚等现象，进而解决了后续纺丝所出现的压滤值过高、可纺性差、纤维中颜料颗粒分布不均匀等问题，提高了原液着色纤维的品质。(2) When the surface-modified carbon black flame retardant pigment of the present invention is used to prepare in-situ polymerized polyester chips, it can be more uniformly dispersed in the resin carrier, thereby improving the uniform dispersion of the pigment in the preparation of dope colored fibers It avoids the phenomenon of pigment particle agglomeration, and then solves the problems of high filtration value, poor spinnability, uneven distribution of pigment particles in the fiber, etc. in the subsequent spinning, and improves the quality of the dope dyed fiber. .
(3)本发明制备得到的炭黑阻燃颜料初始粒径较小，且保存30天之后粒径变化较小，保存周期长，储存稳定性好。(3) The initial particle size of the carbon black flame retardant pigment prepared by the present invention is small, and the particle size change is small after being stored for 30 days, the storage period is long, and the storage stability is good.
(4)利用本发明的炭黑阻燃颜料制备得到的聚酯纤维，其压滤值低，达到0.7MPa以下；可纺性好；阻燃性能良好，极限氧指数达到28％以上。(4) The polyester fiber prepared by using the carbon black flame retardant pigment of the present invention has a low filter pressure value of less than 0.7 MPa; good spinnability;
附图说明Description of drawings
图1为炭黑阻燃颜料的质量分数2％的聚酯切片制备得到的聚酯纤维的SEM图，其中(a)为含有实施例1的炭黑阻燃颜料的聚酯切片制备得到的聚酯纤维，(b)为含有实施例2的炭黑阻燃颜料的聚酯切片制备得到的聚酯纤维，(c)为含有实施例3的炭黑阻燃颜料的聚酯切片制备得到的聚酯纤维，(d)为含有对比例1的炭黑的聚酯切片制备得到的聚酯纤维。Fig. 1 is the SEM image of polyester fiber prepared from polyester chips with a mass fraction of 2% of carbon black flame retardant pigment, wherein (a) is a polyester fiber prepared from polyester chips containing carbon black flame retardant pigment of Example 1. Ester fiber, (b) is the polyester fiber prepared from the polyester chips containing the carbon black flame retardant pigment of Example 2, (c) is the polyester fiber prepared from the polyester chips containing the carbon black flame retardant pigment of Example 3. Ester fiber, (d) is polyester fiber prepared from polyester chips containing carbon black of Comparative Example 1.
具体实施方式Detailed ways
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。The preferred embodiments of the present invention will be described below, and it should be understood that the embodiments are used to better explain the present invention and are not intended to limit the present invention.
测试方法：testing method:
粒径分布的测试：使用Nano-ZS90激光粒度仪测定，并测试常温下放置30天后的粒径。Test of particle size distribution: use Nano-ZS90 laser particle size analyzer, and test the particle size after 30 days at room temperature.
过滤性能测试：将500gPET切片加入冲洗设备，使熔体压力曲线运行平稳，记录初始压力P0；然后加入4000g阻燃黑色聚酯切片，待料用尽后再加入500g PET切片，记录测试过程中最高压力Pmax，已知阻燃黑色聚酯切片中黑色颜料的含量为80g，压力差ΔP＝Pmax-P0。实验采用10μm过滤网。通过该测试，用来评估阻燃黑色聚酯切片的可纺性。Filtration performance test: add 500g PET chips to the washing equipment, make the melt pressure curve run smoothly, record the initial pressure P0 ; then add 4000g flame-retardant black polyester chips, add 500g PET chips after the material is used up, record the test process The highest pressure Pmax , the content of black pigment in the known flame retardant black polyester chips is 80g, the pressure difference ΔP=Pmax -P0 . A 10 μm filter was used in the experiment. This test is used to evaluate the spinnability of flame retardant black polyester chips.
纤维表面形态观察：分别将制备的聚酯纤维放于铝箔上，在加速电压30kV的条件下喷金处理，用Zeiss Sigma500型扫描电子显微镜观察样品表面形态。与同等工艺下未加颜料的聚酯纤维原丝对比，√表示基本与聚酯纤维原丝表面形态类似，Δ表示有少许颗粒，╳表示有明显颗粒。Observation of fiber surface morphology: The prepared polyester fibers were placed on aluminum foil respectively, and treated by gold spraying under the condition of an accelerating voltage of 30kV, and the surface morphology of the samples was observed with a Zeiss Sigma500 scanning electron microscope. Compared with the unpigmented polyester fiber precursor under the same process, √ indicates that the surface morphology is basically similar to that of the polyester fiber precursor, Δ indicates that there are a few particles, and ╳ indicates that there are obvious particles.
极限氧指数测试：根据GB/T8924-2005标准进行氧指数测试，采用南京炯雷仪器设备有限公司的JF-3氧指数仪测。开始测量之前需要先在离点火的一端50mm处划一条刻度线，然后将另一端装在试件夹上并保持样条垂直，测量时应先根据所测材料的预判极限氧值进行调试且测试过程中流量和氧浓度均不得随意改变。Limiting oxygen index test: According to GB/T8924-2005 standard, the oxygen index test is carried out, and the JF-3 oxygen index instrument of Nanjing Jionglei Instrument Equipment Co., Ltd. is used to measure. Before starting the measurement, it is necessary to draw a scale line 50mm from one end of the ignition, and then install the other end on the specimen holder and keep the spline vertical. During the test, the flow rate and oxygen concentration shall not be changed arbitrarily.
氧指数理论公式：LOI＝[O2]/([O2]+[N2])×100％Theoretical formula of oxygen index: LOI=[O2 ]/([O2 ]+[N2 ])×100%
式中：LOI为极限氧指数；[O2]为氧气流量(L/min)；[N2]为氮气的流量(L/min)。In the formula: LOI is the limiting oxygen index; [O2 ] is the oxygen flow rate (L/min); [N2 ] is the nitrogen flow rate (L/min).
实施例1Example 1
一种原位聚合聚酯切片用炭黑阻燃颜料的表面改性方法，包括如下步骤：A method for surface modification of carbon black flame retardant pigment for in-situ polymerization of polyester chips, comprising the following steps:
将50g市售炭黑(粒径为15μm)、300mL体积浓度为30％的过氧化氢溶液依次加入到500mL的三口烧瓶中，设定温度为70℃，反应4h，进行冷却、过滤、水洗涤至淋出液pH值为7；滤饼80℃烘干，即得到氧化炭黑；50g of commercially available carbon black (particle size is 15μm) and 300mL of hydrogen peroxide solution with a volume concentration of 30% were sequentially added to a 500mL three-necked flask, the temperature was set to 70°C, and the reaction was performed for 4h, followed by cooling, filtration, and water washing. The pH value of the leachate is 7; the filter cake is dried at 80°C to obtain oxidized carbon black;
称取50g氧化炭黑加入到装有300mL甲苯的三口烧瓶中进行分散，得到氧化炭黑分散液；再在氧化炭黑分散液中加入18g甲苯二异氰酸酯(TDI)在冰浴条件下反应30min，后升温至120℃继续反应30min；反应完成后于80℃旋蒸除去未反应的甲苯二异氰酸酯，得到所述的异氰酸酯化炭黑；Weigh 50g of oxidized carbon black and add it to a three-necked flask equipped with 300mL of toluene to disperse to obtain an oxidized carbon black dispersion; then add 18g of toluene diisocyanate (TDI) to the oxidized carbon black dispersion and react for 30min under ice bath conditions, Then, the temperature was raised to 120 °C and the reaction was continued for 30 min; after the reaction was completed, the unreacted toluene diisocyanate was removed by rotary evaporation at 80 °C to obtain the isocyanated carbon black;
将350mL甲苯、10g异氰酸酯化炭黑与50g三羟基乙基磷酸酯加入三口烧瓶中混合，200r/min机械搅拌下冰浴反应30min后加热至120℃继续反应60min；将反应产物冷却、过滤、洗涤、烘干，得到所述的炭黑阻燃颜料。Add 350 mL of toluene, 10 g of isocyanated carbon black and 50 g of trihydroxyethyl phosphate into a three-necked flask and mix, react in an ice bath under mechanical stirring at 200 r/min for 30 min, and then heat to 120 °C for 60 min; the reaction product is cooled, filtered and washed and drying to obtain the carbon black flame retardant pigment.
实施例2Example 2
一种原位聚合聚酯切片用炭黑阻燃颜料的表面改性方法，包括如下步骤：A method for surface modification of carbon black flame retardant pigment for in-situ polymerization of polyester chips, comprising the following steps:
将50g市售炭黑(粒径为15μm)、100mL体积浓度为68％的硝酸溶液依次加入到500mL的三口烧瓶中，设定温度为25℃，反应2h，进行冷却、过滤、水洗涤至淋出液pH值为7；滤饼80℃烘干，即得到氧化炭黑；50g of commercially available carbon black (particle size is 15μm) and 100mL of nitric acid solution with a volume concentration of 68% were sequentially added to a 500mL three-necked flask, the temperature was set to 25°C, and the reaction was performed for 2h, followed by cooling, filtration, and water washing until leaching. The pH value of the effluent is 7; the filter cake is dried at 80 °C to obtain oxidized carbon black;
称取50g氧化炭黑加入到装有300mL丙酮的三口烧瓶中进行分散，得到氧化炭黑分散液；再在氧化炭黑分散液中加入23g异佛尔酮二异氰酸酯(IPDI)在冰浴条件下反应40min，后升温至110℃继续反应30min；反应完成后于80℃旋蒸除去未反应异佛尔酮二异氰酸酯(IPDI)，得到所述的异氰酸酯化炭黑；Weigh 50g of oxidized carbon black and add it to a three-necked flask equipped with 300mL of acetone and disperse to obtain an oxidized carbon black dispersion; then add 23g of isophorone diisocyanate (IPDI) to the oxidized carbon black dispersion under ice bath conditions The reaction was carried out for 40 min, and then the temperature was raised to 110° C. to continue the reaction for 30 min; after the reaction was completed, the unreacted isophorone diisocyanate (IPDI) was removed by rotary evaporation at 80° C. to obtain the isocyanated carbon black;
将350mL丙酮、10g异氰酸酯化炭黑与50g苯基膦酸加入三口烧瓶中混合，200r/min机械搅拌下冰浴反应30min后加热至120℃继续反应60min；将反应产物冷却、过滤、洗涤、烘干，得到所述的炭黑阻燃颜料。Add 350 mL of acetone, 10 g of isocyanated carbon black and 50 g of phenylphosphonic acid into a three-necked flask and mix, react in an ice bath under mechanical stirring at 200 r/min for 30 min, and then heat to 120 °C for 60 min. The reaction product is cooled, filtered, washed, and dried. dry to obtain the carbon black flame retardant pigment.
实施例3Example 3
一种原位聚合聚酯切片用炭黑阻燃颜料的表面改性方法，包括如下步骤：A method for surface modification of carbon black flame retardant pigment for in-situ polymerization of polyester chips, comprising the following steps:
将50g市售炭黑(粒径为15μm)、100mL饱和过硫酸铵溶液依次加入到500mL的三口烧瓶中，设定温度为60℃，反应3h，进行冷却、过滤、水洗涤至淋出液pH值为7；滤饼80℃烘干，即得到氧化炭黑；Add 50g of commercially available carbon black (particle size is 15μm) and 100mL of saturated ammonium persulfate solution into a 500mL three-necked flask in turn, set the temperature to 60°C, react for 3h, cool, filter, and wash with water until the pH of the eluate The value is 7; the filter cake is dried at 80°C to obtain oxidized carbon black;
称取50g氧化炭黑加入到装有300mL丁酮的三口烧瓶中进行分散，得到氧化炭黑分散液；再在氧化炭黑分散液中加入25g二苯基甲烷-4,4'-二异氰酸酯(4,4'-MDI)在冰浴条件下反应40min，后升温至110℃继续反应30min；反应完成后于80℃旋蒸除去未反应二苯基甲烷-4,4'-二异氰酸酯(4,4'-MDI)，得到所述的异氰酸酯化炭黑；Weigh 50g carbon black oxide and add it to the there-necked flask equipped with 300mL butanone and disperse to obtain carbon black oxide dispersion; then add 25g diphenylmethane-4,4'-diisocyanate ( 4,4'-MDI) was reacted under ice bath conditions for 40 min, and then the temperature was raised to 110 °C to continue the reaction for 30 min; after the reaction was completed, the unreacted diphenylmethane-4,4'-diisocyanate (4,4'-diisocyanate (4,4'-diisocyanate) was removed by rotary evaporation at 80 °C after the reaction was completed. 4'-MDI) to obtain the described isocyanated carbon black;
将350mL甲苯、10g异氰酸酯化炭黑与50g三羟甲基氧化膦加入三口烧瓶中混合，200r/min机械搅拌下冰浴反应30min后加热至120℃继续反应60min；将反应产物冷却、过滤、洗涤、烘干，得到所述的炭黑阻燃颜料。Add 350 mL of toluene, 10 g of isocyanated carbon black and 50 g of trimethylol phosphine oxide into a three-necked flask to mix, react in an ice bath under mechanical stirring at 200 r/min for 30 min, and then heat to 120 °C for 60 min. The reaction product is cooled, filtered and washed. and drying to obtain the carbon black flame retardant pigment.
对比例1Comparative Example 1
直接采用市售的炭黑(粒径为15μm)。Commercially available carbon black (particle size: 15 μm) was used as it was.
对比例2Comparative Example 2
调整实施例1中的阻燃剂三羟基乙基磷酸酯为聚磷酸铵，其他和实施例1保持一致，得到炭黑阻燃颜料。The flame retardant trihydroxyethyl phosphate in Example 1 was adjusted to be ammonium polyphosphate, and the others were the same as those in Example 1 to obtain a carbon black flame retardant pigment.
对比例3Comparative Example 3
将10g异氰酸酯化炭黑与50g三羟基乙基磷酸酯阻燃剂简单物理混合，得到炭黑阻燃颜料。10 g of isocyanated carbon black and 50 g of trihydroxyethyl phosphate flame retardant are simply and physically mixed to obtain a carbon black flame retardant pigment.
对比例4Comparative Example 4
将350mL甲苯、10g市售炭黑与50g三羟基乙基磷酸酯加入三口烧瓶中混合，200r/min机械搅拌下冰浴反应30min后加热至120℃继续反应60min；将反应产物冷却、过滤、洗涤、烘干，得到所述的炭黑阻燃颜料。Add 350 mL of toluene, 10 g of commercially available carbon black and 50 g of trihydroxyethyl phosphate into a three-necked flask to mix, react in an ice bath for 30 min under mechanical stirring at 200 r/min, then heat to 120 °C for 60 min; cool, filter, and wash the reaction product and drying to obtain the carbon black flame retardant pigment.
对比例5Comparative Example 5
调整实施例1中异氰酸酯化炭黑和阻燃剂的反应为直接加热至120℃反应60min，其他和实施例1保持一致，得到炭黑阻燃颜料。The reaction between the isocyanated carbon black and the flame retardant in Example 1 was adjusted to be directly heated to 120° C. for 60 min, and the others were the same as those in Example 1 to obtain a carbon black flame retardant pigment.
对比例6Comparative Example 6
省略实施例1中的过氧化氢溶液，其他和实施例1保持一致，得到炭黑阻燃颜料。The hydrogen peroxide solution in Example 1 was omitted, and the others were the same as those in Example 1 to obtain a carbon black flame retardant pigment.
分别取50g实施例1～3的炭黑阻燃颜料和对比例1～6得到的炭黑、8g SUA-300分散剂(世名科技)和200g乙二醇于研磨缸中分散30min，加入300g玻璃珠研磨2h，得到颜料分散体。Take 50g of the carbon black flame retardant pigments of Examples 1-3 and the carbon black obtained in Comparative Examples 1-6, 8g of SUA-300 dispersant (World Famous Technology) and 200g of ethylene glycol to disperse in a grinding cylinder for 30min, add 300g The glass beads were ground for 2 h to obtain a pigment dispersion.
将得到的分散体进行粒径分布测试以及常温放置30天之后的粒径分布测试，测试结果如下：The obtained dispersion is subjected to particle size distribution test and the particle size distribution test after placing at room temperature for 30 days, and the test results are as follows:
从表1可以看出：实施例1～3中经改性处理后的炭黑阻燃颜料初始粒径较小，且保存30天之后粒径变化较小。而未经改性处理的炭黑粒径较大，保存周期短，储存稳定性差。It can be seen from Table 1 that the initial particle size of the modified carbon black flame retardant pigments in Examples 1 to 3 is small, and the particle size changes little after being stored for 30 days. The unmodified carbon black has larger particle size, shorter storage period and poor storage stability.
表1实施例1～3和对比例1制备的炭黑颜料分散体的粒径Table 1 Particle size of carbon black pigment dispersions prepared in Examples 1 to 3 and Comparative Example 1
实施例4Example 4
一种制备阻燃黑色聚酯切片的方法，包括如下步骤：A method for preparing flame-retardant black polyester chips, comprising the steps of:
(1)分别取50g实施例1～3和对比例1～6制备得到的炭黑颜料、8g SUA-300分散剂(世名科技)和200g乙二醇于研磨缸中分散30min，加入300g玻璃珠研磨2h，得到颜料分散体；(1) Disperse 50g of carbon black pigments prepared in Examples 1 to 3 and Comparative Examples 1 to 6, 8g of SUA-300 dispersant (World Famous Technology) and 200g of ethylene glycol respectively in a grinding cylinder for 30min, add 300g of glass Bead grinding for 2h to obtain a pigment dispersion;
(2)将精对苯二甲酸、乙二醇混合后经第一、第二酯化釜反应得到聚酯酯化低聚物，其中，催化剂醋酸锌在第二酯化釜中添加，用量一般在0.05％(相对于DMT(对苯二甲酸二甲酯)的重量)，然后将黑色阻燃颜料分散体添加进入聚酯酯化低聚物，再依次通过预缩聚釜、终缩聚釜后，按照国家标准《GB/T 14190-2017纤维级聚酯(PET)切片试验方法》制成着色切片，得到所述的阻燃黑色聚酯切片；其中炭黑阻燃颜料在阻燃黑色聚酯切片中的质量百分比为2％。(2) after mixing purified terephthalic acid and ethylene glycol, the polyester esterification oligomer is obtained through the first and the second esterification kettle reaction, wherein, the catalyst zinc acetate is added in the second esterification kettle, and the dosage is generally At 0.05% (relative to the weight of DMT (dimethyl terephthalate)), then add the black flame retardant pigment dispersion into the polyester esterified oligomer, and then pass through the pre-polycondensation kettle and the final polycondensation kettle in turn, According to the national standard "GB/T 14190-2017 Test Method for Fiber Grade Polyester (PET) Chips", colored chips were made to obtain the flame retardant black polyester chips; wherein the carbon black flame retardant pigment was used in the flame retardant black polyester chips. The mass percentage in is 2%.
采用单螺杆挤出机对阻燃黑色聚酯切片进行熔体直纺，制备出规格为150D/36F的聚酯纤维。The flame-retardant black polyester chips were melt-spun by a single-screw extruder to prepare polyester fibers with a specification of 150D/36F.
将得到的切片和聚酯纤维进行性能测试，测试结果如下：The obtained chips and polyester fibers were tested for performance, and the test results were as follows:
表2测试结果Table 2 Test results
从表2可以看出：实施例1～3制备的表面改性炭黑阻燃颜料分散体储存稳定性能优良，粒径小；制得的原位聚合聚酯切片压滤值低，可纺性好，制得的聚酯纤维具有较高的极限氧指数，阻燃性能良好。对比例1中采用市售炭黑，阻燃性能较差，且未改性的炭黑分散稳定性较差；对比例2中采用聚磷酸铵作为阻燃剂，与异氰酸酯化炭黑反应程度低，未将阻燃剂完全接枝到炭黑上，致使阻燃性能较差；对比例3～4中简单物理混合，未能将阻燃剂完全接枝到炭黑表面，使得阻燃性能差；对比例5中直接加热到120℃，使得溶液中的甲苯直接挥发，溶液粘度增大，反应进行缓慢；对比例6中对炭黑未进行氧化处理，使得炭黑表面的反应基团数量减少，未能与异氰酸酯反应完全，使得炭黑的分散稳定性能和阻燃性能降低。It can be seen from Table 2 that the surface-modified carbon black flame retardant pigment dispersions prepared in Examples 1-3 have excellent storage stability and small particle size; Well, the obtained polyester fiber has high limiting oxygen index and good flame retardancy. Commercially available carbon black is used in Comparative Example 1, which has poor flame retardancy and unmodified carbon black has poor dispersion stability; in Comparative Example 2, ammonium polyphosphate is used as a flame retardant, which has a low degree of reaction with isocyanate carbon black. , the flame retardant was not completely grafted to the carbon black, resulting in poor flame retardant performance; the simple physical mixing in Comparative Examples 3 to 4 failed to completely graft the flame retardant to the surface of carbon black, resulting in poor flame retardant performance ; In Comparative Example 5, it was directly heated to 120 °C, so that the toluene in the solution was directly volatilized, the viscosity of the solution increased, and the reaction proceeded slowly; in Comparative Example 6, the carbon black was not oxidized, which reduced the number of reactive groups on the surface of the carbon black. , failed to react completely with isocyanate, which reduced the dispersion stability and flame retardancy of carbon black.
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention should be defined by the claims.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB566202A (en)* | 1942-04-10 | 1944-12-19 | Ici Ltd | Copolymers of vinylethinylcarbinols and acrylic type esters |
| CN101671567A (en)* | 2009-09-27 | 2010-03-17 | 中国科学技术大学 | Moisture cured phosphorus-containing flame-retardant material and preparation method thereof |
| CN104672812A (en)* | 2013-12-02 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | Core-shell-structure-toughened halogen-free flame-retardancy-modified PET (polyethylene terephthalate) material |
| CN104845352A (en)* | 2014-02-19 | 2015-08-19 | 东曹株式会社 | Flame-retardant polyurethane foam and preparation method thereof |
| CN105566699A (en)* | 2016-03-10 | 2016-05-11 | 安徽海源特种电缆有限公司 | High-strength and oil-resistant electric power cable |
| CN105860506A (en)* | 2016-04-19 | 2016-08-17 | 滁州环球聚氨酯科技有限公司 | Composite flame retardant modified polyurethane composite material |
| CN106987227A (en)* | 2017-04-20 | 2017-07-28 | 安徽春辉仪表线缆集团有限公司 | A kind of isocyanation esterification Carbon Black/polyurethane Conductive sealant and preparation method thereof |
| CN113956425A (en)* | 2020-09-17 | 2022-01-21 | 昆明理工大学 | Reactive flame-retardant polyurethane foam containing phosphate ester structure and preparation method thereof |
| CN113956686A (en)* | 2021-11-09 | 2022-01-21 | 苏州世名科技股份有限公司 | Carbon black dispersion and preparation method and application thereof |
| CN114605906A (en)* | 2022-04-08 | 2022-06-10 | 中国科学技术大学 | A kind of preparation method of phosphorus-containing silicon transparent flame retardant coating |
- 2022
- 2022-06-28CNCN202210783994.3Apatent/CN115181435B/enactiveActive
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB566202A (en)* | 1942-04-10 | 1944-12-19 | Ici Ltd | Copolymers of vinylethinylcarbinols and acrylic type esters |
| CN101671567A (en)* | 2009-09-27 | 2010-03-17 | 中国科学技术大学 | Moisture cured phosphorus-containing flame-retardant material and preparation method thereof |
| CN104672812A (en)* | 2013-12-02 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | Core-shell-structure-toughened halogen-free flame-retardancy-modified PET (polyethylene terephthalate) material |
| CN104845352A (en)* | 2014-02-19 | 2015-08-19 | 东曹株式会社 | Flame-retardant polyurethane foam and preparation method thereof |
| CN105566699A (en)* | 2016-03-10 | 2016-05-11 | 安徽海源特种电缆有限公司 | High-strength and oil-resistant electric power cable |
| CN105860506A (en)* | 2016-04-19 | 2016-08-17 | 滁州环球聚氨酯科技有限公司 | Composite flame retardant modified polyurethane composite material |
| CN106987227A (en)* | 2017-04-20 | 2017-07-28 | 安徽春辉仪表线缆集团有限公司 | A kind of isocyanation esterification Carbon Black/polyurethane Conductive sealant and preparation method thereof |
| CN113956425A (en)* | 2020-09-17 | 2022-01-21 | 昆明理工大学 | Reactive flame-retardant polyurethane foam containing phosphate ester structure and preparation method thereof |
| CN113956686A (en)* | 2021-11-09 | 2022-01-21 | 苏州世名科技股份有限公司 | Carbon black dispersion and preparation method and application thereof |
| CN114605906A (en)* | 2022-04-08 | 2022-06-10 | 中国科学技术大学 | A kind of preparation method of phosphorus-containing silicon transparent flame retardant coating |
Non-Patent Citations (2)
| Title |
|---|
| 张通;郑玉婴;陈德贤;王攀;: "合成反应型磷酸酯及其对TPU阻燃和力学性能的影响", 功能材料, no. 13* |
| 邢亚琳;郭来;赵倩琼;袁永;范瑞兰;: "反应型膦酸酯阻燃剂的合成及在聚氨酯阻燃中的应用", 高分子材料科学与工程, no. 08* |
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