WO2018214177A1 - Additive for polymer and preparation method therefor - Google Patents

Additive for polymer and preparation method therefor Download PDF

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Publication number
WO2018214177A1
WO2018214177A1 PCT/CN2017/087387 CN2017087387W WO2018214177A1 WO 2018214177 A1 WO2018214177 A1 WO 2018214177A1 CN 2017087387 W CN2017087387 W CN 2017087387W WO 2018214177 A1 WO2018214177 A1 WO 2018214177A1
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sodium
additive
polymer
weight
sulfonate
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PCT/CN2017/087387
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French (fr)
Chinese (zh)
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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 AU2018100240A priority Critical patent/AU2018100240A4/en
Publication of WO2018214177A1 publication Critical patent/WO2018214177A1/en

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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to an additive for a polymer, in particular to a dialkyl phosphinate containing a trace amount of sodium metal element and a preparation method 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 invention has been studied and unexpectedly found that when the flame retardant dialkyl phosphinate contains a trace amount of sodium metal element, not only the high flame retardancy of the polymer composition can be ensured, but also the polymer composition can be greatly reduced.
  • the heat-reducing weight loss rate was 0.001% by weight to 0.250% by weight using a PERKIN ELMER thermogravimetric measuring device Pyris 1TGA at a melting point of +10 ° C for 24 minutes under a nitrogen atmosphere.
  • 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;
  • the weight content is from 200 to 890 ppm, more preferably from 300 to 860 ppm by weight, still more preferably from 400 to 830 ppm by weight.
  • Test method for the weight content of sodium metal element Take 0.05 ⁇ 0.005g of the additive sample for the polymer, accurate to 0.001g, put it into the microwave digestion tank, and then add 10mL of digestion acid in the microwave digestion tank to completely immerse it. 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 sodium metal element is derived from a sodium-containing compound selected from the group consisting of D-sodium lactate, sodium L-lactate, sodium acetate, sodium sulfite, sodium oxide, sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, tartaric acid.
  • the source of the sodium metal 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 sodium-containing compound is used.
  • the weight content of the sodium element of the metal is based on the sodium metal element itself rather than the sodium-containing compound to which the metal sodium element is added.
  • the weight content of the sodium metal 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 a polyester.
  • the invention obtains an additive for a polymer by uniformly mixing a dialkyl hypophosphite and a sodium-containing compound in a high-mixer;
  • the sodium-containing compound is sodium-containing compound: D-sodium lactate, sodium L-lactate, sodium acetate, sodium sulfite, sodium oxide, sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, sodium tartrate Dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium metabisulfite, sodium hexafluorosilicate, sodium diacetate, sodium acrylate, sodium acetylide, sodium ethoxide, sodium citrate, sodium oleate, water Sodium salicylate, sodium methoxide, sodium biphenylate, sodium phenolate, sodium 1-butane sulfonate, sodium 1-propane thiolate, sodium 1-dodecane sulfonate, sodium 1-decane sulfonate, 1-heptane Sodium sulfonate, sodium 1-decane sulfonate, sodium 2-
  • 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 polyester.
  • 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 dialkyl phosphinate prepared by the invention containing a specific range of content of sodium metal element, as an additive for a polymer the additive is applied to the polymer, not only can ensure high resistance of the polymer composition
  • the burning performance can also greatly reduce the heat loss rate of the polymer composition.
  • the weight loss rate is 0.101% by weight when kept at a melting point of +10 ° C for 240 minutes. 0.250 wt%.
  • 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; sodium metal element content: not detected;
  • PBT PBT 1100-211M (Taiwan Changchun Group)
  • Antioxidant 1010, (Jinhai Yabao)
  • the test method for the weight content of the metal sodium 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, slowly add 1-2 mL of hydrogen peroxide to repeat the previous digestion step.
  • 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 amount is used.
  • Rinse the microwave digestion vessel several times with distilled water and transfer the rinse solution to the volumetric flask, dilute it to 50mL with distilled water, shake it, and test it; use Agilent's model 720ES full-automatic inductively coupled plasma atomic emission spectrometer to analyze The weight content of the metal sodium element in the sample was measured, and the average of the three test values was the final result.
  • the polymer composition of the present invention has a heat-reducing rate: a weight loss rate at a melting point of +10 ° C for 240 minutes in a nitrogen atmosphere using a PERKIN ELMER thermogravimetric measuring device, Pyris 1 TGA.
  • 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 sodium-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 sodium metal element content of the additive for the polymer of the present invention is adjusted and measured by the actual addition amount of the sodium-containing compound during the preparation.
  • 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.
  • the machine was melt extruded, cooled in a water bath, and granulated to obtain a polymer composition; and its UL-94 flame retardant grade and heat-resistant weight loss rate were measured. Specific test data are shown in Table 2.

Abstract

The invention discloses an additive for polymer, comprising: A: phosphinate with two substituent groups and having a following structural formula (I), wherein R1 and R2 are the same or different and represent H, C1-C6 alkyl or C6-C18 aryl, M is Al, and m is 3; B: metallic sodium, wherein the weight content of the metallic sodium in the total additive is 100-900 ppm. The additive containing a specific range content of metallic sodium is simple in preparation process and low in production cost. When the additive is applied into polymer, the heat-resistant and weight-reduction rate of a polymer composition can be greatly reduced. Using a heating and weight measuring device Pyris 1 TGA from PERKIN ELMER, when the additive is kept under the nitrogen atmosphere at a temperature of the melting point + 10 DEG C for 240 minutes, the weight reduction rate is 0.101-0.250 wt%, and at the same time, the excellent flame retardancy of the polymer composition can be maintained.

Description

一种用于聚合物的添加剂及其制备方法Additive for polymer and preparation method thereof 技术领域Technical field
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钠元素的二烷基次膦酸盐及其制备方法。The invention relates to an additive for a polymer, in particular to a dialkyl phosphinate containing a trace amount of sodium metal element and a preparation method thereof.
背景技术Background technique
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。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. U.S. Patent No. 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.
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。Thermoplastics are widely used in electronics, automotive, construction and other industries due to their excellent electrical properties and processing properties. In order to meet the flame retardant requirements and environmental requirements of the industry, halogen-free flame retardants are usually added to thermoplastics to meet the requirements of materials. The above requirements.
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。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.
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钠元素时，不但可以保证聚合物组合物较高的阻燃性能，可大幅降低聚合物组合物的耐热减重率，使用PERKIN ELMER制热重量测定装置Pyris 1TGA，在熔点+10℃氮气气氛下保持240分钟时减重率为0.101wt％-0.250wt％。The invention has been studied and unexpectedly found that when the flame retardant dialkyl phosphinate contains a trace amount of sodium metal element, not only the high flame retardancy of the polymer composition can be ensured, but also the polymer composition can be greatly reduced. The heat-reducing weight loss rate was 0.001% by weight to 0.250% by weight using a PERKIN ELMER thermogravimetric measuring device Pyris 1TGA at a melting point of +10 ° C for 24 minutes under a nitrogen atmosphere.
发明内容Summary of the invention
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钠元素，能使得到的聚合物组合物具备优异的阻燃性能和显著降低的耐热减重率。It is an object of the present invention to provide an additive for a polymer which can provide an excellent flame retardancy and remarkable performance of a polymer composition obtained by adding a trace amount of a metal sodium element to a dialkylphosphinate. Reduced heat and weight loss rate.
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。 Another object of the present invention is to provide a process for the preparation of the above-mentioned additive for a polymer.
本发明是通过以下技术方案实现的：The invention is achieved by the following technical solutions:
一种用于聚合物的添加剂，其中包括：An additive for polymers, including:
A：二烷基次膦酸盐，具有如下结构式(Ⅰ)，A: a dialkylphosphinate having the following structural formula (I),
Figure PCTCN2017087387-appb-000001
Figure PCTCN2017087387-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；Wherein 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为Al；m为3；M is Al; m is 3;
B：金属钠元素，其中金属钠元素在总添加剂中的重量含量为100-900ppm。优选重量含量为200-890ppm，更优选重量含量为300-860ppm，进一步优选重量含量为400-830ppm。B: a metallic sodium element in which the metallic sodium element is present in the total additive in an amount of from 100 to 900 ppm by weight. Preferably, the weight content is from 200 to 890 ppm, more preferably from 300 to 860 ppm by weight, still more preferably from 400 to 830 ppm by weight.
金属钠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钠元素的重量含量，取三次测试值的平均为最终结果。Test method for the weight content of sodium metal element: Take 0.05±0.005g of the additive sample for the polymer, accurate to 0.001g, put it into the microwave digestion tank, and then add 10mL of digestion acid in the microwave digestion tank to completely immerse it. 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 μm 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. In the bottle, dilute with distilled water to the mark line 50mL, shake it, and test it; use Agilent's model 720ES fully automatic inductively coupled plasma atomic emission spectrometer to analyze the metal sodium in the sample to be tested. Content by weight, taking the average value of three tests for the final result.
所述金属钠元素来自含钠化合物，含钠化合物选自D-乳酸钠、L-乳酸钠、乙酸钠、亚硫酸钠、氧化钠、氨基钠、硝酸钠、硫化钠、硫酸钠、磷酸钠、草酸钠、酒石酸钠二元二水合物、亚氯酸钠、***钠、偏硅酸钠、偏重亚硫酸钠、六氟硅酸钠、双乙酸钠、丙烯酸钠、乙炔钠、乙醇钠、柠檬酸钠、油酸钠、水杨酸钠、甲醇钠、联苯钠、苯酚钠、1-丁烷磺酸钠、1-丙烷硫醇钠、1-十二烷磺酸钠、1-壬烷磺酸钠、1-庚烷磺酸 钠、1-癸烷磺酸钠、2-丙烷硫醇钠、2-萘磺酸钠、丁二酸二钠、丁二酸钠、丙酮酸钠、丙酸钠、二甲苯磺酸钠、十二烷基硫酸钠、叔丁醇钠中的一种或几种。本发明所指出的金属钠元素的来源不仅限于上述举例，无论使用哪种形式的含钠化合物，都能够使用原子发射光谱法检测到。金属钠元素的重量含量是以金属钠元素本身而不是以添加金属钠元素的含钠化合物为基准的。以ppm表示的金属钠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。The sodium metal element is derived from a sodium-containing compound selected from the group consisting of D-sodium lactate, sodium L-lactate, sodium acetate, sodium sulfite, sodium oxide, sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, tartaric acid. Sodium dihydrate dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium metabisulfite, sodium hexafluorosilicate, sodium diacetate, sodium acrylate, sodium acetylide, sodium ethoxide, sodium citrate, oleic acid Sodium, sodium salicylate, sodium methoxide, sodium biphenylate, sodium phenolate, sodium 1-butanesulfonate, sodium 1-propanethiolate, sodium 1-dodecanesulfonate, sodium 1-decanesulfonate, 1 -heptanesulfonic acid Sodium, sodium 1-decane sulfonate, sodium 2-propane thiolate, sodium 2-naphthalene sulfonate, disodium succinate, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate, ten One or more of sodium dialkyl sulfate and sodium t-butoxide. The source of the sodium metal 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 sodium-containing compound is used. The weight content of the sodium element of the metal is based on the sodium metal element itself rather than the sodium-containing compound to which the metal sodium element is added. The weight content of the sodium metal element expressed in ppm is calculated based on the total weight of the additive for the polymer of the present invention.
所述聚合物为聚酯(如PBT、PET)、尼龙(PA6、PA66等)、PPE、TPE、TPU或环氧树脂，优选为聚酯。The polymer is a polyester (such as PBT, PET), nylon (PA6, PA66, etc.), PPE, TPE, TPU or epoxy resin, preferably a polyester.
本发明通过将二烷基次磷酸盐与含钠化合物在高混机中混合均匀，得到用于聚合物的添加剂；The invention obtains an additive for a polymer by uniformly mixing a dialkyl hypophosphite and a sodium-containing compound in a high-mixer;
其中，所述含钠化合物为含钠化合物为D-乳酸钠、L-乳酸钠、乙酸钠、亚硫酸钠、氧化钠、氨基钠、硝酸钠、硫化钠、硫酸钠、磷酸钠、草酸钠、酒石酸钠二元二水合物、亚氯酸钠、***钠、偏硅酸钠、偏重亚硫酸钠、六氟硅酸钠、双乙酸钠、丙烯酸钠、乙炔钠、乙醇钠、柠檬酸钠、油酸钠、水杨酸钠、甲醇钠、联苯钠、苯酚钠、1-丁烷磺酸钠、1-丙烷硫醇钠、1-十二烷磺酸钠、1-壬烷磺酸钠、1-庚烷磺酸钠、1-癸烷磺酸钠、2-丙烷硫醇钠、2-萘磺酸钠、丁二酸二钠、丁二酸钠、丙酮酸钠、丙酸钠、二甲苯磺酸钠、十二烷基硫酸钠、叔丁醇钠中的一种或几种。Wherein, the sodium-containing compound is sodium-containing compound: D-sodium lactate, sodium L-lactate, sodium acetate, sodium sulfite, sodium oxide, sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, sodium tartrate Dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium metabisulfite, sodium hexafluorosilicate, sodium diacetate, sodium acrylate, sodium acetylide, sodium ethoxide, sodium citrate, sodium oleate, water Sodium salicylate, sodium methoxide, sodium biphenylate, sodium phenolate, sodium 1-butane sulfonate, sodium 1-propane thiolate, sodium 1-dodecane sulfonate, sodium 1-decane sulfonate, 1-heptane Sodium sulfonate, sodium 1-decane sulfonate, sodium 2-propane thiolate, sodium 2-naphthalene sulfonate, disodium succinate, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate One or more of sodium lauryl sulfate and sodium t-butoxide.
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。The invention also discloses the use of the above additive for a polymer as a flame retardant.
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。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.
所述聚合物为聚酯(PBT、PET)、尼龙(PA6、PA66等)、PPE、TPE、TPU或环氧树脂，优选为聚酯。The polymer is polyester (PBT, PET), nylon (PA6, PA66, etc.), PPE, TPE, TPU or epoxy resin, preferably polyester.
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。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.
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。 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.
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，如抗氧化剂、润滑剂、脱模剂、成核剂、色剂、光稳定剂。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.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the invention has the following beneficial effects:
1)本发明制备得到的含有特定范围含量金属钠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，还可以大幅降低聚合物组合物的耐热减重率，使用PERKIN ELMER制热重量测定装置Pyris 1 TGA，在熔点+10℃氮气气氛下保持240分钟时减重率为0.101wt％-0.250wt％。1) The dialkyl phosphinate prepared by the invention containing a specific range of content of sodium metal element, as an additive for a polymer, the additive is applied to the polymer, not only can ensure high resistance of the polymer composition The burning performance can also greatly reduce the heat loss rate of the polymer composition. Using the PERKIN ELMER thermogravimetric device Pyris 1 TGA, the weight loss rate is 0.101% by weight when kept at a melting point of +10 ° C for 240 minutes. 0.250 wt%.
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。2) The additive for polymer of the present invention has a simple preparation process, low production cost, and is convenient for mass production.
具体实施方式detailed description
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。The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.
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：The raw materials selected in the examples and comparative examples are described below, but are not limited to these materials:
组分A二烷基次磷酸铝：市售；金属钠元素含量：未检出；Component A aluminum dialkyl hypophosphite: commercially available; sodium metal element content: not detected;
PBT：PBT 1100-211M(台湾长春集团)PBT: PBT 1100-211M (Taiwan Changchun Group)
乙酸钠：西格玛-奥德里奇(上海)贸易有限公司；Sodium acetate: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;
硫酸钠：西格玛-奥德里奇(上海)贸易有限公司；Sodium sulfate: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;
叔丁醇钠：西格玛-奥德里奇(上海)贸易有限公司；Sodium tert-butoxide: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;
联苯钠：西格玛-奥德里奇(上海)贸易有限公司；Sodium Biphenyl: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;
玻璃纤维：ECS13-4.5-534(巨石集团)Glass fiber: ECS13-4.5-534 (Jushi Group)
抗氧剂：1010,(金海雅宝)Antioxidant: 1010, (Jinhai Yabao)
本发明所述金属钠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钠元素的重量含量，取三次测试值的平均为最终结果。The test method for the weight content of the metal sodium 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, slowly add 1-2 mL of hydrogen peroxide to repeat the previous digestion step. If the second time is still not completely resolved, the clear solution obtained by filtering the digestion solution is required to be tested. Specifically, the solution in the microwave digestion tank is transferred to a volumetric flask with a 0.45 μm filter membrane, and the amount is used. Rinse the microwave digestion vessel several times with distilled water and transfer the rinse solution to the volumetric flask, dilute it to 50mL with distilled water, shake it, and test it; use Agilent's model 720ES full-automatic inductively coupled plasma atomic emission spectrometer to analyze The weight content of the metal sodium element in the sample was measured, and the average of the three test values was the final result.
本发明所述聚合物组合物耐热减重率：使用PERKIN ELMER制热重量测定装置Pyris 1 TGA，在熔点+10℃氮气气氛下保持240分钟时的减重率。The polymer composition of the present invention has a heat-reducing rate: a weight loss rate at a melting point of +10 ° C for 240 minutes in a nitrogen atmosphere using a PERKIN ELMER thermogravimetric measuring device, Pyris 1 TGA.
本发明所述燃烧性能：UL94塑料燃烧性能测试；The combustion performance of the present invention: UL94 plastic burning performance test;
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：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：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-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：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-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：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。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.
不可分类(ncl)：不满足燃烧等级V-2。Non-classifiable (ncl): Does not meet the burning level V-2.
对比例1-2(D1-D2)和实施例1-11(B1-B11)Comparative Example 1-2 (D1-D2) and Example 1-11 (B1-B11)
按表1所式的组成，称取前述制备的组分A和含钠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。According to the composition of the formula of Table 1, the component A and the sodium-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.
其中，本发明用于聚合物的添加剂金属钠元素含量是在制备过程中通过含钠化合物的实际添加量来进行调整并测得的。Among them, the sodium metal element content of the additive for the polymer of the present invention is adjusted and measured by the actual addition amount of the sodium-containing compound during the preparation.
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Table 1 Comparative Examples 1-2 (D1-D2) and Examples 1-11 (B1-B11) for Polymer Additives
Figure PCTCN2017087387-appb-000002
Figure PCTCN2017087387-appb-000002
Figure PCTCN2017087387-appb-000003
Figure PCTCN2017087387-appb-000003
对比例3-5，实施例12-22Comparative Example 3-5, Examples 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；并测定其UL-94阻燃等级以及耐热减重率，具体测试数据列于表2中。According to the ratio in Table 2, 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. The machine was melt extruded, cooled in a water bath, and granulated to obtain a polymer composition; and its UL-94 flame retardant grade and heat-resistant weight loss rate were measured. Specific test data are shown in Table 2.
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Table 2 Comparative examples 3-5, specific proportions (parts by weight) of each composition in Examples 12-22 and test results thereof
Figure PCTCN2017087387-appb-000004
Figure PCTCN2017087387-appb-000004
Figure PCTCN2017087387-appb-000005
Figure PCTCN2017087387-appb-000005

Claims (13)

  1. 一种用于聚合物的添加剂，其中包括：An additive for polymers, including:
    A：二烷基次膦酸盐，具有如下结构式(Ⅰ)，A: a dialkylphosphinate having the following structural formula (I),
    Figure PCTCN2017087387-appb-100001
    Figure PCTCN2017087387-appb-100001
    其中，R1，R2相同或不同，表示为H、C1-C6烷基或C6-C18芳基；Wherein R 1 and R 2 are the same or different and are represented by H, C1-C6 alkyl or C6-C18 aryl;
    M为Al；m为3；M is Al; m is 3;
    B：金属钠元素，其中金属钠元素在总添加剂中的重量含量为100-900ppm。B: a metallic sodium element in which the metallic sodium element is present in the total additive in an amount of from 100 to 900 ppm by weight.
  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，所述金属钠元素在总添加剂中的重量含量为200-890ppm，优选重量含量为300-860ppm，更优选重量含量为400-830ppm。The additive for a polymer according to claim 1, wherein the metal sodium element is contained in the total additive in an amount of from 200 to 890 ppm, preferably from 300 to 860 ppm by weight, more preferably by weight. 400-830ppm.
  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，金属钠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钠元素的重量含量，取三次测试值的平均为最终结果。The additive for a polymer according to claim 1 or 2, wherein the weight content of the sodium metal element is tested by taking 0.05 ± 0.005 g of the additive sample for the polymer to the nearest 0.001 g. Put into the microwave digestion tank, add 10mL of digestion acid in the microwave digestion tank, completely immerse the sample, slowly add 1-2mL hydrogen peroxide, react the sample with digestive acid for 1-2min, cover, seal The digestion tank was digested in a 220 ° C blast oven, and the digestion time was 2 h. After the digestion was completed, the digestion tank was taken out and cooled to room temperature for testing; if some of the particles were not digested, then slowly drip 1-2 mL. Hydrogen peroxide repeats the previous digestion step, to be tested; if the second solution is still not completely resolved, the clear solution obtained by filtering the digestion solution is required to be tested, specifically, the solution in the microwave digestion tank is used with a 0.45 μm filter membrane. Transfer to a volumetric flask, rinse the microwave digestion vessel with appropriate amount of distilled water, transfer the rinse solution to a volumetric flask, dilute to 50 mL of the mark with distilled water, shake well, and test; use Agilent's model 720ES Inductively coupled plasma atomic emission spectrometry sodium weight content of metal elements in the test sample, the average value of three tests taken as the final result.
  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。 An additive for a polymer according to claim 1, wherein R1, R2 are represented by an ethyl group, a propyl group, a butyl group, a hexyl group or a cyclohexyl group.
  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，所述金属钠元素来自含钠化合物，含钠化合物选自D-乳酸钠、L-乳酸钠、乙酸钠、亚硫酸钠、氧化钠、氨基钠、硝酸钠、硫化钠、硫酸钠、磷酸钠、草酸钠、酒石酸钠二元二水合物、亚氯酸钠、***钠、偏硅酸钠、偏重亚硫酸钠、六氟硅酸钠、双乙酸钠、丙烯酸钠、乙炔钠、乙醇钠、柠檬酸钠、油酸钠、水杨酸钠、甲醇钠、联苯钠、苯酚钠、1-丁烷磺酸钠、1-丙烷硫醇钠、1-十二烷磺酸钠、1-壬烷磺酸钠、1-庚烷磺酸钠、1-癸烷磺酸钠、2-丙烷硫醇钠、2-萘磺酸钠、丁二酸二钠、丁二酸钠、丙酮酸钠、丙酸钠、二甲苯磺酸钠、十二烷基硫酸钠、叔丁醇钠中的一种或几种。The additive for a polymer according to claim 1, wherein the sodium metal element is derived from a sodium-containing compound, and the sodium-containing compound is selected from the group consisting of D-sodium lactate, sodium L-lactate, sodium acetate, sodium sulfite, and sodium oxide. , sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, sodium tartrate dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium metabisulfite, sodium hexafluorosilicate , sodium diacetate, sodium acrylate, sodium acetylide, sodium ethoxide, sodium citrate, sodium oleate, sodium salicylate, sodium methoxide, sodium biphenyl, sodium phenolate, sodium 1-butane sulfonate, 1-propane thiol Sodium, sodium 1-dodecanesulfonate, sodium 1-decanesulfonate, sodium 1-heptanesulfonate, sodium 1-decanesulfonate, sodium 2-propanethiolate, sodium 2-naphthalenesulfonate, sodium One or more of disodium diacid, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate, sodium lauryl sulfate, and sodium t-butoxide.
  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。An additive for a polymer according to claim 1, wherein the polymer is polyester, nylon, PPE, TPE, TPU or epoxy.
  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，所述聚合物为聚酯。An additive for a polymer according to claim 6, wherein the polymer is a polyester.
  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钠化合物在高混机中混合均匀，得到用于聚合物的添加剂；A method for preparing an additive for a polymer according to any one of claims 1 to 7, wherein the dialkyl hypophosphite is uniformly mixed with the sodium-containing compound in a high-mixer to obtain a polymer. additive;
    其中，所述含钠化合物为D-乳酸钠、L-乳酸钠、乙酸钠、亚硫酸钠、氧化钠、氨基钠、硝酸钠、硫化钠、硫酸钠、磷酸钠、草酸钠、酒石酸钠二元二水合物、亚氯酸钠、***钠、偏硅酸钠、偏重亚硫酸钠、六氟硅酸钠、双乙酸钠、丙烯酸钠、乙炔钠、乙醇钠、柠檬酸钠、油酸钠、水杨酸钠、甲醇钠、联苯钠、苯酚钠、1-丁烷磺酸钠、1-丙烷硫醇钠、1-十二烷磺酸钠、1-壬烷磺酸钠、1-庚烷磺酸钠、1-癸烷磺酸钠、2-丙烷硫醇钠、2-萘磺酸钠、丁二酸二钠、丁二酸钠、丙酮酸钠、丙酸钠、二甲苯磺酸钠、十二烷基硫酸钠、叔丁醇钠中一种或几种。Wherein, the sodium-containing compound is D-sodium lactate, L-sodium lactate, sodium acetate, sodium sulfite, sodium oxide, sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, sodium tartrate dihydrate, Sodium chlorite, sodium selenite, sodium metasilicate, sodium metabisulfite, sodium hexafluorosilicate, sodium diacetate, sodium acrylate, sodium acetylide, sodium ethoxide, sodium citrate, sodium oleate, sodium salicylate, Sodium methoxide, sodium biphenylate, sodium phenolate, sodium 1-butane sulfonate, sodium 1-propane thiolate, sodium 1-dodecane sulfonate, sodium 1-decane sulfonate, sodium 1-heptane sulfonate, Sodium 1-decane sulfonate, sodium 2-propane thiolate, sodium 2-naphthalene sulfonate, disodium succinate, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate, dodecane One or more of sodium sulfate and sodium t-butoxide.
  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。Use of an additive for a polymer as a flame retardant according to claims 1-7.
  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。A polymeric material comprising an additive for a polymer according to claims 1-7, comprising 5-25 parts by weight of an additive for a polymer, 50-75 parts by weight of a polymer or a mixture thereof.
  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。Polymer material according to claim 10, characterized in that the polymer is polyester, nylon, PPE, TPE, TPU or epoxy resin, preferably polyester, nylon or PPE.
  12. 如权利要求11所述的聚合物材料，其特征在于，所述聚合物为聚酯。 The polymeric material of claim 11 wherein the polymer is a polyester.
  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。 The polymeric material of claim 10 further comprising 15-40 parts by weight of filler and 0.1-5 parts by weight of adjuvant.
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