WO2018214178A1 - 一种用于聚合物的添加剂及其制备方法 - Google Patents

一种用于聚合物的添加剂及其制备方法 Download PDF

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WO2018214178A1
WO2018214178A1 PCT/CN2017/087391 CN2017087391W WO2018214178A1 WO 2018214178 A1 WO2018214178 A1 WO 2018214178A1 CN 2017087391 W CN2017087391 W CN 2017087391W WO 2018214178 A1 WO2018214178 A1 WO 2018214178A1
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additive
polymer
calcium
weight
digestion
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PCT/CN2017/087391
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English (en)
French (fr)
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涂志秀
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广州铂钡信息科技有限公司
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Priority to EP17861207.3A priority Critical patent/EP3431540B1/en
Priority to AU2018100153A priority patent/AU2018100153A4/en
Publication of WO2018214178A1 publication Critical patent/WO2018214178A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to an additive for a polymer, and in particular to a dialkyl phosphinate containing a trace amount of a calcium metal element and a process for the preparation thereof.
  • Dialkyl phosphinates are widely used as flame retardants and are known to be synthesized by various methods.
  • the use of a metal salt of a disubstituted phosphinic acid in the use of a polyester as a flame retardant is disclosed in the patent DE 44 093 032.
  • a process for the preparation of a metal salt of a disubstituted phosphinic acid is disclosed in the publications DE 199 092 022 and US Pat.
  • 6,359,171 B1 discloses a process for preparing aluminum dialkylphosphinate, which firstly synthesizes a monoalkylphosphinic acid ester using yellow phosphorus, and then reacts with an aluminum salt after hydrolysis to obtain an acid by radical polymerization.
  • Aluminum dialkyl phosphinate flame retardant discloses a process for preparing aluminum dialkylphosphinate, which firstly synthesizes a monoalkylphosphinic acid ester using yellow phosphorus, and then reacts with an aluminum salt after hydrolysis to obtain an acid by radical polymerization.
  • Aluminum dialkyl phosphinate flame retardant is a process for preparing aluminum dialkylphosphinate, which firstly synthesizes a monoalkylphosphinic acid ester using yellow phosphorus, and then reacts with an aluminum salt after hydrolysis to obtain an acid by radical polymerization.
  • Aluminum dialkyl phosphinate flame retardant discloses a process for preparing aluminum dialkylpho
  • thermoplastics are widely used in electronics, automotive, construction and other industries due to their excellent electrical properties and processing properties.
  • halogen-free flame retardants are usually added to thermoplastics to meet the requirements of materials. The above requirements.
  • dialkyl phosphinate As a high-efficiency halogen-free flame retardant, dialkyl phosphinate has high bulk density, low flame retardant dosage, good mechanical properties, good color, low smoke density, and high CTI (compared to tracking index). It is widely used in thermoplastic and thermosetting plastics such as polyamide, polyester, unsaturated resin, epoxy resin and polyurethane.
  • the present invention has been studied and unexpectedly found that when a trace amount of metal calcium is contained in the flame retardant dialkyl phosphinate, not only the high flame retardancy of the polymer composition can be ensured, but also the polymer composition can be greatly improved. The fatigue strength of the product.
  • the polymer composition article can be provided with excellent fatigue strength.
  • Another object of the present invention is to provide a process for the preparation of the above-mentioned additive for a polymer.
  • An additive for polymers including:
  • A a dialkylphosphinate having the following structural formula (I),
  • R 1 and R 2 are the same or different and are represented by H, C1-C6 alkyl or C6-C18 aryl, preferably ethyl, propyl, butyl, hexyl or cyclohexyl;
  • M is Al; m is 3;
  • B a metallic calcium element in which the metallic calcium element is contained in an amount of from 10 to 600 ppm by weight in the total additive. It is preferably 50-500 ppm by weight, more preferably 100-400 ppm by weight, still more preferably 150-300 ppm by weight.
  • Test method for the weight content of metallic calcium Take 0.05 ⁇ 0.005g of additive sample for polymer, accurate to 0.001g, put it into microwave digestion tank, then add 10mL of digestion acid in microwave digestion tank to make it completely immersed The sample was slowly dropped into 1-2 mL of hydrogen peroxide, and the sample was reacted with digestive acid for 1-2 min, the lid was closed, the digestion tank was sealed, and the digestion was carried out in a 220 ° C blast oven.
  • the digestion time was 2 h, and after the digestion was completed, Remove the digestion tank, cool to room temperature, to be tested; if some particles are still not digested, then slowly add 1-2mL of hydrogen peroxide to repeat the previous digestion step, to be tested; if the second is still not completely resolved, the digestion solution is needed
  • the clear solution obtained after filtration is a sample to be tested, specifically, the solution in the microwave digestion tank is transferred to a volumetric flask with a 0.45 ⁇ m filter membrane, and the microwave digestion vessel is washed several times with an appropriate amount of distilled water and the rinse liquid is transferred to a capacity.
  • the metal calcium element is derived from a calcium-containing compound selected from one or more of calcium oxide, calcium carbonate, calcium sulfate whiskers, calcium stearate or calcium montanate.
  • the source of the metal calcium element indicated by the present invention is not limited to the above examples, and it can be detected by atomic emission spectrometry regardless of which form of the calcium-containing compound is used.
  • the weight content of the metal calcium element is based on the metal calcium element itself rather than the calcium-containing compound to which the metal calcium element is added.
  • the weight content of the metallic calcium element expressed in ppm is calculated based on the total weight of the additive for the polymer of the present invention.
  • the polymer is a polyester (such as PBT, PET), nylon (PA6, PA66, etc.), PPE, TPE, TPU or epoxy resin, preferably nylon 6.
  • the invention obtains an additive for a polymer by uniformly mixing a dialkyl hypophosphite with a calcium-containing compound in a high-mixer;
  • the calcium-containing compound is selected from one or more of calcium oxide, calcium carbonate, calcium sulfate whisker, calcium stearate or calcium montanate.
  • the invention also discloses the use of the above additive for a polymer as a flame retardant.
  • the present invention also discloses a polymer material comprising the above additive for a polymer, comprising 5 to 25 parts by weight of an additive for a polymer, 50 to 75 parts by weight of a polymer or a mixture thereof.
  • the polymer is polyester (PBT, PET), nylon (PA6, PA66, etc.), PPE, TPE, TPU or epoxy resin, preferably nylon 6.
  • the polymer material of the present invention may be added with different auxiliary agents according to different performance requirements of the material, such as 15-40 parts by weight of filler and 0.1-5 parts by weight of auxiliary agent.
  • the filler of the present invention is a material generally used for strengthening or filling a polymer, and a mixture of two or more inorganic fillers and/or reinforcing agents, preferably glass fibers, may also be used.
  • the adjuvant may be an additional component that does not interfere with the aforementioned desirable properties but enhances other beneficial properties, such as antioxidants, lubricants, mold release agents, nucleating agents, colorants, light stabilizers.
  • the invention has the following beneficial effects:
  • the burning property can also greatly increase the fatigue strength of the polymer composition article.
  • the additive for polymer of the present invention has a simple preparation process, low production cost, and is convenient for mass production.
  • Component A aluminum dialkyl hypophosphite commercially available; metal calcium content: not detected;
  • PA6 PA6M2000 (Guangdong Xinhui Meida Nylon Co., Ltd.)
  • Glass fiber ECS301-HP (Chongqing International Composite Materials Co., Ltd.);
  • Antioxidant 1010, (Jinhai Yabao);
  • the calcium-containing compounds used in the examples and comparative examples of the present invention are all commercially available.
  • the test method for the weight content of the metal calcium element of the invention taking 0.05 ⁇ 0.005g of the additive sample for the polymer, accurate to 0.001g, into the microwave digestion tank, and then adding 10mL of the digestion acid in the microwave digestion tank, Make it completely immersed in the sample, slowly instill 1-2mL of hydrogen peroxide, react the sample with the digestion acid for 1-2min, cover the lid, seal the digestion tank, and digest in a 220 °C blast oven, the digestion time is 2h, After the digestion is completed, the digestion tank is taken out and cooled to room temperature for testing; if some of the particles are still not digested, then slowly add 1-2 mL of hydrogen peroxide to repeat the previous digestion step, to be tested; if the second time is still not completely resolved, The clear solution obtained by filtering the digestion solution is required to be tested.
  • the solution in the microwave digestion tank is transferred to a volumetric flask with a 0.45 ⁇ m filter membrane, and the microwave digestion vessel is washed repeatedly with an appropriate amount of distilled water and rinsed.
  • the liquid was transferred to a volumetric flask, diluted with distilled water to a mark line of 50 mL, shaken, and tested; the Agilent model 720ES was used to analyze the sample to be tested by a fully automated inductively coupled plasma atomic emission spectrometer. By weight calcium content belongs, taking the average value of three tests for the final result.
  • Dyna Mess apparatus CIMTronic 2000 according to DIN 53442 and ISO 178, is calibrated to reference the number of rounds at which the initial bending stress is about 50 MPa to break.
  • the combustion performance of the present invention UL94 plastic burning performance test
  • the UL 94 burn rating was determined using test specimens having a thickness of 1.5 mm for test specimens from each of the polymer compositions. The following are the burn ratings specified by UL 94:
  • V-0 After the spline leaves the flame, the continuous burning time is no longer than 10s, the total burning time of the five splines for 10 times of ignition is not more than 50s, no droplets drip, the flame does not spread to the fixture phenomenon, the sample The afterglow burning time after the end of ignition is no longer than 30 s.
  • V-1 After the spline leaves the flame, the continuous burning time is no longer than 30s, the total burning time of the five splines for a total of 10 ignitions does not exceed 250s, and the afterglow burning time of the sample after the ignition is not longer than 60s, other The standard is like V-0.
  • V-2 After the spline leaves the flame, during the continuous combustion process, droplets appear, and the droplets will ignite the cotton wool indicator. Other standards are the same as V-1.
  • Non-classifiable (ncl) Does not meet the burning level V-2.
  • the component A and the calcium-containing compound prepared as described above were weighed and mixed uniformly in a high-mixer to obtain an additive for a polymer of the present invention.
  • the calcium metal element content of the additive for the polymer of the present invention is adjusted and measured by the actual addition amount of the calcium-containing compound in the preparation process.
  • the components were uniformly mixed in a high-speed stirring mixer and sent to a twin-screw extruder; the glass fibers were fed through a side feeding system of a twin-screw extruder, and subjected to twin-screw extrusion. Melt extrusion, cooling in a water bath, granulation, to obtain a polymer composition; then determining the UL-94 flame retardant grade of the polymer composition, and the fatigue strength of the polymer composition article, the specific test data is listed in In Table 2.

Abstract

本发明公开了一种用于聚合物的添加剂，其中包括：A：含有两个取代基团的次膦酸盐，具有如下结构式(Ⅰ)，其中，R1，R2相同或不同，表示为H、C1-C6烷基或C6-C18芳基；M为Al；m为3；B：金属钙元素，其中金属钙元素在总添加剂中的重量含量为10-600ppm。本发明含有特定范围含量金属钙元素的添加剂制备工艺简单，生产成本低，其应用于聚合物中，可大幅提高聚合物组合物制品的抗疲劳强度，同时还能保证聚合物组合物具有高效的阻燃性能。

Description

一种用于聚合物的添加剂及其制备方法 技术领域
本发明涉及一种用于聚合物的添加剂，具体涉及一种含有微量金属钙元素的二烷基次膦酸盐及其制备方法。
背景技术
二烷基次膦酸盐，广泛用作阻燃剂，已知其可通过不同的方法进行合成。如专利DE4430932公开了二取代次膦酸金属盐在聚酯用作阻燃剂，DE19910232、US6248921两篇专利公开了一种二取代次膦酸金属盐的制备方法。美国专利US6359171B1公开了一种二烷基次膦酸铝的制备方法，该方法首先采用黄磷合成单烷基次膦酸酯，然后利用自由基引发乙烯化后水解得酸后与铝盐反应得到二烷基次膦酸铝阻燃剂。
热塑性塑料，因其优异的电性能和加工性能广泛应用于电子电器、汽车、建筑等行业，为了满足行业的阻燃要求和环保要求，通常往热塑性塑料中加入无卤阻燃剂来满足材料的上述要求。
二烷基次膦酸盐作为一种高效无卤阻燃剂，具有堆积密度高，阻燃剂用量小，机械性能好，色泽佳，烟密度低，CTI(相比漏电起痕指数)值高的特点，广泛应用于聚酰胺、聚酯、不饱和树脂、环氧树脂、聚氨酯等热塑性和热固性塑料中。
本发明经研究，意外发现，当在阻燃剂二烷基次膦酸盐中含有微量金属钙元素时，不但可以保证聚合物组合物较高的阻燃性能，还可以大幅提高聚合物组合物制品的抗疲劳强度。
发明内容
本发明的目的在于提供一种用于聚合物的添加剂，该添加剂通过在二烷基次膦酸盐中添加微量的金属钙元素，能使得到的聚合物组合物具备优异的阻燃性能，还可以使聚合物组合物制品具备优异的抗疲劳强度。
本发明的另一目的在于提供一种上述用于聚合物的添加剂的制备方法。
本发明是通过以下技术方案实现的：
一种用于聚合物的添加剂，其中包括：
A：二烷基次膦酸盐，具有如下结构式(Ⅰ)，
Figure PCTCN2017087391-appb-000001
其中，R1，R2相同或不同，表示为H、C1-C6烷基或C6-C18芳基，优选为乙基、丙基、丁基、己基或环己基；
M为Al；m为3；
B：金属钙元素，其中金属钙元素在总添加剂中的重量含量为10-600ppm。优选重量含量为50-500ppm，更优选重量含量为100-400ppm，进一步优选重量含量为150-300ppm。
金属钙元素的重量含量的测试方法：取0.05±0.005g用于聚合物的添加剂样品，精确到0.001g，放入微波消解罐中，再加入10mL消解酸于微波消解罐中，使其完全浸没样品，慢慢滴入1-2mL过氧化氢，使样品与消解酸反应1-2min，盖上盖子，密封消解罐，在220℃鼓风烘箱中进行消解，消解时间为2h，消解完成后，取出消解罐，冷至室温，待测；如果仍有部分粒子未消解，再慢慢滴入1-2mL过氧化氢重复前面消解步骤，待测；如果二次仍未消解完全，需要将消解液经过过滤后得到的澄清溶液为待测样，具体为，将微波消解罐中的溶液用0.45μm的过滤膜转移至容量瓶中，用适量蒸馏水多次冲洗微波消解罐并将冲洗液转移至容量瓶中，再用蒸馏水稀释至刻度线50mL，摇匀，待测；采用Agilent公司型号为720ES的全自动电感耦合等离子体原子发射光谱仪分析待测样品中金属钙元素的重量含量，取三次测试值的平均为最终结果。
所述金属钙元素来自含钙化合物，所述含钙化合物选自氧化钙、碳酸钙、硫酸钙晶须、硬脂酸钙或褐煤酸钙中的一种或几种。本发明所指出的金属钙元素的来源不仅限于上述举例，无论使用哪种形式的含钙化合物，都能够使用原子发射光谱法检测到。金属钙元素的重量含量是以金属钙元素本身而不是以添加金属钙元素的含钙化合物为基准的。以ppm表示的金属钙元素的重量含量是以本发明用于聚合物的添加剂的总重量为基准计算的。
所述聚合物为聚酯(如PBT、PET)、尼龙(PA6、PA66等)、PPE、TPE、TPU或环氧树脂，优选尼龙6。
本发明通过将二烷基次磷酸盐与含钙化合物在高混机中混合均匀，得到用于聚合物的添加剂；
其中，所述含钙化合物选自氧化钙、碳酸钙、硫酸钙晶须、硬脂酸钙或褐煤酸钙中的一种或几种。
本发明还公开了上述用于聚合物的添加剂作为阻燃剂的用途。
本发明还公开了一种包含上述用于聚合物的添加剂的聚合物材料，包括5-25重量份的用于聚合物的添加剂，50-75重量份的聚合物或其混合物。
所述聚合物为聚酯(PBT、PET)、尼龙(PA6、PA66等)、PPE、TPE、TPU或环氧树脂，优选为尼龙6。
本发明所述的聚合物材料，可根据材料的不同性能需求，添加不同的助剂，如还包括15-40重量份的填料和0.1-5重量份的助剂。
本发明的填料是通常用来强化或填充聚合物的物质，也可使用两种或更多无机填料和/或增强剂的混合物，优选玻璃纤维。
所述助剂可以是不干扰前述希望性质但是提高其它有益性质的额外组分，如抗氧剂、润滑剂、脱模剂、成核剂、色剂、光稳定剂。
本发明与现有技术相比，具有如下有益效果：
1)本发明制备得到的含有特定范围含量金属钙元素的二烷基次膦酸盐，作为用于聚合物的添加剂，该添加剂应用于聚合物中，不但可以保证聚合物组合物较高的阻燃性能，还可以大幅提高聚合物组合物制品的抗疲劳强度。
2)本发明的用于聚合物的添加剂，制备工艺简单，生产成本低，便于大规模生产。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
现对实施例和对比例中所选用的原材料做如下说明，但不限于这些材料：
组分A二烷基次磷酸铝：市售；金属钙元素含量：未检出；
PA6：PA6M2000(广东新会美达锦纶股份有限公司)
玻璃纤维：ECS301-HP(重庆国际复合材料有限公司)；
抗氧剂：1010,(金海雅宝)；
本发明实施例和对比例所用含钙化合物均为市售。
本发明所述金属钙元素的重量含量的测试方法：取0.05±0.005g用于聚合物的添加剂样品，精确到0.001g，放入微波消解罐中，再加入10mL消解酸于微波消解罐中，使其完全浸没样品，慢慢滴入1-2mL过氧化氢，使样品与消解酸反应1-2min，盖上盖子，密封消解罐，在220℃鼓风烘箱中进行消解，消解时间为2h，消解完成后，取出消解罐，冷至室温，待测；如果仍有部分粒子未消解，再慢慢滴入1-2mL过氧化氢重复前面消解步骤，待测；如果二次仍未消解完全，需要将消解液经过过滤后得到的澄清溶液为待测样，具体为，将微波消解罐中的溶液用0.45μm的过滤膜转移至容量瓶中，用适量蒸馏水多次冲洗微波消解罐并将冲洗液转移至容量瓶中，再用蒸馏水稀释至刻度线50mL，摇匀，待测；采用Agilent公司型号为720ES的全自动电感耦合等离子体原子发射光谱仪分析待测样品中金属钙元素的重量含量，取三次测试值的平均为最终结果。
本发明所述聚合物组合物制品的抗疲劳强度测试方法：以Dyna Mess公司的装置CIMTronic 2000，依照DIN53442和ISO178，标定参考在起始的弯曲应力约50Mpa下至折断所经的回合数。
本发明所述燃烧性能：UL94塑料燃烧性能测试；
针对来自每种聚合物组合物的试验试样使用厚度1.5mm的试验试样测定UL 94燃烧等级。以下为UL 94规定的燃烧等级：
V-0：样条离开火焰后，持续燃烧时间不长于10s，5根样条共计10次点燃时的持续燃烧时间总和不超过50s，无熔滴滴落，火焰无蔓延至夹具现象，试样在点燃结束之后的余辉燃烧时间不长于30s。
V-1：样条离开火焰后，持续燃烧时间不长于30s，5根样条共计10次点燃时的持续燃烧时间总和不超过250s，试样在点燃结束之后的余辉燃烧时间不长于60s，其它标准如同V-0。
V-2：样条离开火焰后，持续燃烧过程中，出现熔滴，且熔滴会引燃脱脂棉指示物，其它标准同V-1。
不可分类(ncl)：不满足燃烧等级V-2。
对比例1-2(D1-D2)和实施例1-11(B1-B11)
按表1所式的组成，称取前述制备的组分A和含钙化合物在高混机中混合均匀，制得本发明用于聚合物的添加剂。
其中，本发明用于聚合物的添加剂金属钙元素含量是在制备过程中通过含钙化合物的实际添加量来进行调整并测得的。
表1 对比例1-2(D1-D2)及实施例1-11(B1-B11)的用于聚合物的添加剂
Figure PCTCN2017087391-appb-000002
对比例3-5，实施例12-22
按表2中的配比称取各组分在高速搅拌混料机中混合均匀后送入双螺杆挤出机中；玻璃纤维通过双螺杆挤出机的侧喂***加入，经双螺杆挤出机熔融挤出，在水浴中冷却、造粒，即得聚合物组合物；然后测定聚合物组合物的UL-94阻燃等级，以及聚合物组合物制品的抗疲劳强度，具体测试数据列于表2中。
表2 对比例3-5，实施例12-22中各组成的具体配比(重量份)及其测试结果
Figure PCTCN2017087391-appb-000003

Claims (13)

  1. 一种用于聚合物的添加剂，其中包括：
    A：二烷基次膦酸盐，具有如下结构式(Ⅰ)，
    Figure PCTCN2017087391-appb-100001
    其中，R1，R2相同或不同，表示为H、C1-C6烷基或C6-C18芳基；
    M为Al；m为3；
    B：金属钙元素，其中金属钙元素在总添加剂中的重量含量为10-600ppm。
  2. 如权利要求1所述的一种用于聚合物的添加剂，其特征在于，所述金属钙元素在总添加剂中的重量含量为50-500ppm，优选重量含量为100-400ppm，更优选重量含量为150-300ppm。
  3. 如权利要求1或2所述的一种用于聚合物的添加剂，其特征在于，金属钙元素的重量含量的测试方法：取0.05±0.005g用于聚合物的添加剂样品，精确到0.001g，放入微波消解罐中，再加入10mL消解酸于微波消解罐中，使其完全浸没样品，慢慢滴入1-2mL过氧化氢，使样品与消解酸反应1-2min，盖上盖子，密封消解罐，在220℃鼓风烘箱中进行消解，消解时间为2h，消解完成后，取出消解罐，冷至室温，待测；如果仍有部分粒子未消解，再慢慢滴入1-2mL过氧化氢重复前面消解步骤，待测；如果二次仍未消解完全，需要将消解液经过过滤后得到的澄清溶液为待测样，具体为，将微波消解罐中的溶液用0.45μm的过滤膜转移至容量瓶中，用适量蒸馏水多次冲洗微波消解罐并将冲洗液转移至容量瓶中，再用蒸馏水稀释至刻度线50mL，摇匀，待测；采用Agilent公司型号为720ES的全自动电感耦合等离子体原子发射光谱仪分析待测样品中金属钙元素的重量含量，取三次测试值的平均为最终结果。
  4. 如权利要求1所述的一种用于聚合物的添加剂，其特征在于，R1，R2表示为乙基、丙基、丁基、己基或环己基。
  5. 如权利要求1所述的一种用于聚合物的添加剂，其特征在于，所述金属钙元素来自含钙化合物，所述含钙化合物选自氧化钙、碳酸钙、硫酸钙晶须、硬脂酸钙或褐煤酸钙中的一种或几种。
  6. 如权利要求1所述的一种用于聚合物的添加剂，其特征在于，所述聚合物为聚酯、尼龙、PPE、TPE、TPU或环氧树脂。
  7. 如权利要求6所述的一种用于聚合物的添加剂，其特征在于，所述聚合物为尼龙6。
  8. 如权利要求1-7所述的一种用于聚合物的添加剂的制备方法，其特征在于，将二烷基次磷酸盐与含钙化合物在高混机中混合均匀，得到用于聚合物的添加剂；
    其中，所述含钙化合物选自氧化钙、碳酸钙、硫酸钙晶须、硬脂酸钙或褐煤酸钙中的一种或几种。
  9. 如权利要求1-7所述的一种用于聚合物的添加剂作为阻燃剂的用途。
  10. 一种包含如权利要求1-7所述用于聚合物的添加剂的聚合物材料，包括5-25重量份的用于聚合物的添加剂，50-75重量份的聚合物或其混合物。
  11. 如权利要求10所述的聚合物材料，其特征在于，所述聚合物为聚酯、尼龙、PPE、TPE、TPU或环氧树脂，优选聚酯、尼龙或PPE。
  12. 如权利要求11所述的聚合物材料，其特征在于，所述聚合物为尼龙6。
  13. 如权利要求10所述的聚合物材料，其特征在于，还包括15-40重量份的填料和0.1-5重量份的助剂。
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