WO2017193463A1 - 一种含多dopo环状磷酸酯的复合结构磷阻燃剂及其制备方法 - Google Patents

一种含多dopo环状磷酸酯的复合结构磷阻燃剂及其制备方法 Download PDF

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WO2017193463A1
WO2017193463A1 PCT/CN2016/088521 CN2016088521W WO2017193463A1 WO 2017193463 A1 WO2017193463 A1 WO 2017193463A1 CN 2016088521 W CN2016088521 W CN 2016088521W WO 2017193463 A1 WO2017193463 A1 WO 2017193463A1
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dopo
flame retardant
composite structure
phosphorus flame
phosphorus
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刘长坤
郑洪良
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淮安领创新材料有限公司
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Priority to US16/071,083 priority Critical patent/US11078223B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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 invention relates to the technical field of flame retardants, in particular to a composite structure phosphorus flame retardant containing multiple DOPO cyclic phosphates and a preparation method thereof.
  • the bromine-based flame retardant has a good flame retarding effect, has little influence on the performance of the flame-retardant polymer material, and is cost-effective and thus widely used.
  • the flame retardant has defects in environmental protection, and harmful harmful carcinogens (such as dioxins) and a large amount of harmful fumes are generated in the flame retardant. Therefore, the EU RoHS Directive prohibits harmful substances such as polybrominated diphenyl ethers from being used in electrical and electronic equipment. use.
  • Some states in the United States have also introduced similar regulations. At the same time, some multinational companies have also set their own environmental standards, and the restrictions on the use of halogens are an important part of this.
  • the global organophosphorus (excluding P-X) flame retardant dosage was about 180,000 tons, which is widely used in engineering plastics and polyurethane foams.
  • the annual growth rate of the annual dosage will be higher than the annual growth rate of the total amount of the flame retardant.
  • Most of the existing organophosphorus flame retardants are alkane or aromatic phosphate compounds, such as BDP (bisphenol A tetraphenyl bisphosphate oligomer), which has the disadvantages of low decomposition temperature, volatility and hydrolysis (solubilization). High in nature, easy to migrate during processing, can only be applied to general plastics with lower processing temperature, flame retardant efficiency can not be satisfactory.
  • DOPO-derived compounds have a unique cyclic phosphate structure, which has a higher decomposition temperature than ordinary alkane and aramid phosphates. It is very suitable for processing polyester and polyether substrates with higher temperature. The low decomposition temperature flame retardant is better combined with the flame retardant effect. In the process of use, it is divided into two types: addition type and reaction type.
  • the addition type DOPO-derived flame retardant is usually reacted with DOPO and a small molecule compound to obtain a new compound containing a DOPO structure, which is added as a flame retardant additive to the substrate.
  • the reactive DOPO-derived combustion improver is usually synthesized by first obtaining a reactive monomer containing a DOPO structural unit, and the active monomer is inserted into the polymer chain after polymerization or condensation reaction.
  • CN201010206426.4 describes a method for accessing DOPO on an aromatic diol polymerization monomer. Methods for the reaction of DOPO with itaconic acid or itaconic acid compounds and their use in flame retardant polyester fibers are described in DE19522876. J. Appl. Poly. Sci. 78, 2000, 228-235 describes a process for preparing flame retardant epoxy resins using an adduct of DOPO reacted with maleic acid and itaconic acid followed by diglycidyl or bis Phenol A reaction.
  • the reactive DOPO cyclic phosphate structure is incorporated into the molecular structure of the matrix polymer (on the main chain or side chain), it has a great influence on the physical properties of the polymer (such as glass transition temperature, tensile strength, etc.). Be very cautious when using it.
  • the object of the present invention is to provide a composite structure phosphorus flame retardant containing multiple DOPO cyclic phosphates which is simple in synthesis, convenient to use, high in phosphorus content and better in flame retardant effect, and a preparation method thereof, and the present invention is proposed to solve the above background art.
  • the problem is to provide a composite structure phosphorus flame retardant containing multiple DOPO cyclic phosphates which is simple in synthesis, convenient to use, high in phosphorus content and better in flame retardant effect, and a preparation method thereof, and the present invention is proposed to solve the above background art. The problem.
  • the present invention provides the following technical solutions:
  • a composite structure phosphorus flame retardant containing multiple DOPO cyclic phosphates comprising not less than one organophosphate and not less than two DOPO cyclic phosphates in the structural formula.
  • the structure of the composite structure phosphorus flame retardant is as shown in the structural formula (c), wherein at least one of R 1 , R 2 and R 3 is any one of the structural formula (a) or the structural formula (b). And R 1 , R 2 or R 3 other than this is an alkyl group or an aromatic group; in the structural formula (a) or the structural formula (b), R is hydrogen, an alkyl group, an aromatic group, a carboxyl group, a carboxyl aryl group or a hydroxy alkane. Alkoxyalkyl, aryloxyalkyl, hydroxyaryl, alkoxyaryl or aryloxyaryl, and R is the same or different substituent; n, m, p, q is the number 1 -20;
  • the preparation method of the composite structure phosphorus flame retardant containing multiple DOPO cyclic phosphates is carried out in two steps:
  • DOPO is mixed with a polyhydroxyalkane or a substituted chain hydrocarbon, wherein the number of hydroxyl groups of the polyhydroxyalkane is ⁇ 3, the carbon number of the chain hydrocarbon in the substituted chain hydrocarbon is ⁇ 3, and the mixture is heated to 195-210 ° C under a protective gas. -17 hours, wherein at least one of the hydroxyl groups does not participate in the reaction to obtain a DOPO cyclic phosphate;
  • the shielding gas is nitrogen.
  • the mixture is heated to 200 ° C for 14 hours under a protective gas, and further reacted at 205 ° C for 2 hours.
  • the structure of the DOPO cyclic phosphate includes, but is not limited to, the structural formula (a) or the structural formula (b).
  • R is hydrogen, alkyl, aryl, carboxyl, carboxyaryl, hydroxyalkyl, alkoxyalkyl, aryloxyalkyl, hydroxyaryl, alkoxyaryl or aryloxyaryl, and R is the same or different substituent; n, m, p, q are the numbers 1-20.
  • the temperature is raised to 60 ° C for 2 hours.
  • the polyhydroxyalkane is mixed with p-xylene, 1,1-bis(3,4-dimethylphenyl)ethane and an alcohol solution containing sodium iodide.
  • the mass ratio of p-xylene, 1,1-bis(3,4-dimethylphenyl)ethane and an alcohol solution containing sodium iodide is 100-101:800:55-65.
  • the mass ratio of sodium iodide to alcohol in the alcohol solution is 4.35:1 g/mol
  • the alcohol is glycerol, butyl triol or pentaerythritol.
  • the phosphorus oxyphosphorus is phosphorus oxychloride.
  • the invention is distinguished by the fact that a molecule comprising two phosphate structures, a common phosphate ester and a cyclic phosphate ester, provides flame retardancy at two decomposition temperatures, one occurring between 230-310 ° C and the other Appears after 345 ° C.
  • the flame retardant actually functions as a flame retardant of a common phosphate ester and a cyclic phosphate ester composite flame retardant.
  • the DOPO cyclic phosphate structure includes a plurality of P-C bonds, which ensures high flame retardant efficiency and is suitable for polymer substrates having higher processing temperatures.
  • the invention is an additive-type halogen-free phosphorus-based flame retardant, which has simple synthesis, convenient use, high phosphorus content and better flame retardant effect.
  • the present invention is distinguished from the DOPO-derived compounds disclosed in the prior art, in which a plurality of DOPO-based cyclic phosphates linked by carbon-carbon bonds are condensed into a compound molecule by a common phosphate.
  • Figure 1 is a graph showing the results of a test according to a fourth embodiment of the present invention.
  • a 3 liter four-necked flask was fitted with a mechanical stirrer, a h-type water separator and a reflux condenser, a dropping funnel and a nitrogen inlet.
  • 253.3 g (1.172 mol) of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), 100.6 g of p-xylene, and 800 g of PXE (1,1-double) were added thereto.
  • (3,4-Dimethylphenyl)ethane) solvent and 56.45 g of glycerol solution (53.9 g (0.586 mol) glycerol dissolved 2.55 g of sodium iodide).
  • the reaction mixture was heated to 200 ° C for 14 hours under the protection of a nitrogen stream, and the generated water was continuously discharged through the oil-water separator during the reaction.
  • the reaction temperature is raised to 205 ° C and further reacted for 2 hours.
  • the temperature of the system was lowered to room temperature, and 29.94 g (0.195 mol) of phosphorus oxychloride was added dropwise through a dropping funnel.
  • the hydrogen chloride gas generated by the reaction is neutralized and absorbed by a 20% NaOH solution.
  • Example 2 According to the procedure of Example 1, only 56.45 g of the glycerol solution of the reactant was replaced with 64.67 g of succinyl alcohol solution (62.12 g of 1.2.4-butanetriol dissolved 2.55 g of sodium iodide), and other reactants and solvents were not used. change. After the reaction mixture was brought to room temperature, 150 ml of pyridine was added to the reaction flask before the dropwise addition of phosphorus oxychloride. The reaction product was a pale yellow syrupy liquid, labeled P2, with a yield of about 81% and a phosphorus content of 13.98%.
  • Thermogravimetric analysis The flame retardants P1, P2 and P3 prepared in Examples 1-3 were tested. The test was carried out on a Netzsch STA449F3A analyzer with an air atmosphere, a test temperature range of 20-600 ° C and a heating rate of 10 ° C/min. The result is shown in Figure 1.
  • Combustion performance test Appropriate amount of flame retardant P1, P2, P3 prepared in Examples 1-3, flame retardant aluminum hydroxide (1000 mesh, Chinalco Shandong) and 40 g epoxy resin E-44 were stirred at 150 ° C. After 1 hour, after cooling to 100 ° C, 7.5 g of diaminodiphenylmethane was added, mixed uniformly, and then rapidly poured into a mold of 10 cm ⁇ 10 cm ⁇ 3 mm (length ⁇ width ⁇ thickness), and the temperature was raised to 150 ° C for 3 hours. After cooling to room temperature, it is demolded to obtain a flame retardant epoxy resin sample to be tested. The limiting oxygen index was measured by an oxygen index meter, and the burning level was measured by a vertical burner. The results are summarized in Table 1.
  • Weight percentage refers to the weight percentage of the additive relative to the epoxy resin E-44; b.
  • the determination of the limiting oxygen index refers to the national standard method GB/T2406-93.

Abstract

本发明公开了一种含多DOPO环状磷酸酯的复合结构磷阻燃剂及其制备方法，该复合结构磷阻燃剂，其结构式中包括不少于1个有机磷酸酯和不少于2个DOPO环状磷酸酯。DOPO与多羟基链烷烃或取代链烃混合，其中多羟基链烷烃的羟基数目≥3，取代链烃中链烃碳数≥3，在保护气体下加热混合物至195-210℃反应14-17小时，降至室温，再加入卤代氧磷或不完全酯化卤代氧磷，然后升温至55-65℃反应1.5-3小时，降至室温即得。本发明提供在两种分解温度时的阻燃作用，一个出现在230-310℃之间，另一个出现在345℃之后，合成简单，使用方便，磷含量高，阻燃效果更好。

Description

一种含多DOPO环状磷酸酯的复合结构磷阻燃剂及其制备方法 技术领域
本发明涉及阻燃剂技术领域，具体是一种含多DOPO环状磷酸酯的复合结构磷阻燃剂及其制备方法。
背景技术
传统阻燃剂中，溴类阻燃剂由于阻燃效果好，对阻燃高分子材料性能影响小，性价比高从而得到广泛使用。但该阻燃剂在环保性上存在缺陷，阻燃中会产生有害致癌物质(如二噁英)和大量有害烟雾，因此欧盟RoHS法令禁止多溴二苯醚等有害物质在电子电气设备中的使用。美国一部分州也出台了类似法规。同时，一些跨国公司也制定了各自的环保标准，对使用卤素的限制要求是其中的一项重要内容。2007年，国际电子工业连接协会(IPC)提出的标准草案建议在整个电子业界推行“无/低卤化”。可以预见全球的“无/低卤化”要求将给应用于电子产品的阻燃剂带来一次新的革命。而磷酸酯阻燃剂由于其无卤、低毒、高效的特点被认为是溴类阻燃剂理想的替代产品。
2010年全球有机磷(不包括P-X系)阻燃剂用量约为18万吨，广泛的应用于工程塑料和聚氨酯泡沫塑料中。随着阻燃剂无卤化进程的加快，其年用量的年增长率会高于阻燃剂总用量的年增长率。现有有机磷阻燃剂绝大部分是烷烃或芳烃磷酸酯类化合物，如BDP(双酚A四苯基双磷酸酯低聚物)其的缺点是分解温度低，挥发性和水解(溶)性较高，在加工过程中易迁移，只能适用于具有较低加工温度的一般塑料，阻燃效率不能尽如人意。这些均限制了普通有机磷阻燃剂的应用，也呼唤新型结构的有磷阻燃剂的诞生。
DOPO衍生类化合物其具有独特的环状磷酸酯结构，与普通烷烃和芳烃基磷酸酯相比其分解温度较高，非常适用于加工温度较高的聚酯和聚醚类基体，如果与其他较低分解温度的阻燃剂配合使用阻燃效果更好。在使用过程中其分添加型和反应型两类。添加型DOPO衍生类阻燃剂通常由DOPO和小分子化合物反应，得到含DOPO结构的新化合物，该类化合物做为阻燃添加剂加入到底物中。中国专利申请CN201080022027.0(WO2010135398)公布一种典型的添加型DOPO衍生类阻燃剂6H-二苯并[c，e][1，2]氧杂磷己环，6，6，-(1，4-乙 烷二基)双-6，6’-二氧化物(DIDOPO)，其开始1％质量损失的分解温度为348℃，5％质量损失的分解温度为382℃。对于酚醛清漆环氧树脂层和板，添加DIDOPO至磷含量为3％时可达到UL-94V-1级阻燃标准。而当DIDOPO与二氧化硅和/或聚磷酸三聚氰胺复合使用时，6.6％的DIDOPO添加量就可获得V-0级阻燃标准。该阻燃剂虽然性能优异但由于它分子刚性较强与被阻燃聚合物基体的相容性较差，在聚合物基体中不易分散均匀，因而影响其广泛使用。
反应型DOPO衍生类助燃剂通常是先合成得到含DOPO结构单元的活性单体，该活性单体经聚合或缩合反应后嵌入到聚合物链中。CN201010206426.4介绍一种在芳香基二元醇聚合单体上接入DOPO的方法。DE19522876中介绍DOPO与衣康酸或衣康酸化合物反应的方法，以及它们在阻燃聚酯纤维的应用。J.Appl.Poly.Sci.78，2000，228-235描述一种制备阻燃环氧树脂的方法，使用DOPO与马来酸和衣康酸反应的加成物再与二环氧甘油或双酚A反应。由于反应型DOPO环状磷酸酯结构被接入到基体聚合物分子结构中(主链或侧链上)，对聚合物的本身物理性能(如玻璃化转变温度，抗张强度等)影响较大，使用时要非常谨慎。
发明内容
本发明的目的在于提供一种合成简单、使用方便、磷含量高、阻燃效果更好的含多DOPO环状磷酸酯的复合结构磷阻燃剂及其制备方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种含多DOPO环状磷酸酯的复合结构磷阻燃剂，其结构式中包括不少于1个有机磷酸酯和不少于2个DOPO环状磷酸酯。
作为本发明进一步的方案：所述复合结构磷阻燃剂的结构如结构式(c)所示，其中R1、R2、R3至少有一个为结构式(a)或结构式(b)中任意一种，除此之外的R1、R2或R3是烷基、芳香基；结构式(a)或结构式(b)中R为氢、烷基、芳香基、羧基、羧基芳基、羟基烷基、烷氧基烷基、芳氧基烷基、羟基芳基、烷氧基芳基或芳氧基芳基，并且R是相同或不同的取代基；n，m，p，q为数字1-20；
Figure PCTCN2016088521-appb-000001
所述含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其过程分两步进行：
(1)DOPO与多羟基链烷烃或取代链烃混合，其中多羟基链烷烃的羟基数目≥3，取代链烃中链烃碳数≥3，在保护气体下加热混合物至195-210℃反应14-17小时，使得其中至少有一个羟基没有参与反应，制得DOPO环状磷酸酯；
(2)降至室温，再加入卤代氧磷或不完全酯化卤代氧磷，然后升温至55-65℃反应1.5-3小时，使得代氧磷或不完全酯化卤代氧磷与DOPO环状磷酸酯中未反应的羟基反应，降至室温即得复合结构磷阻燃剂。
作为本发明进一步的方案：步骤(1)中，保护气体为氮气。
作为本发明进一步的方案：步骤(1)中，在保护气体下加热混合物至200℃反应14小时，再在205℃下反应2小时。
作为本发明进一步的方案：步骤(1)中，DOPO环状磷酸酯的结构包括但不限于结构式(a)或结构式(b)，
Figure PCTCN2016088521-appb-000002
其中R为氢、烷基、芳香基、羧基、羧基芳基、羟基烷基、烷氧基烷基、芳氧基烷基、羟基芳基、烷氧基芳基或芳氧基芳基，并且R是相同或不同的取代基；n，m，p，q为数字1-20。
作为本发明进一步的方案：步骤(2)中，升温至60℃反应2小时。
作为本发明进一步的方案：步骤(1)中，多羟基链烷烃采用对二甲苯、1，1-双(3，4-二甲基苯基)乙烷和含有碘化钠的醇溶液混合而成，对二甲苯、1，1-双(3，4-二甲基苯基)乙烷和含有碘化钠的醇溶液的质量比为100-101∶800∶55-65。
作为本发明进一步的方案：醇溶液中碘化钠与醇的质量摩尔比为4.35∶1g/mol，醇为丙三醇、丁三醇或季戊四醇。
作为本发明进一步的方案：卤代氧磷采用三氯氧磷。
与现有技术相比，本发明的有益效果是：
1.该发明显著特征为一个分子中包括两种磷酸酯结构即普通磷酸酯和环状磷酸酯，提供在两种分解温度时的阻燃作用，一个出现在230-310℃之间，另一个出现在345℃之后。该阻燃剂实际起到普通磷酸酯和环状磷酸酯复合阻燃剂的阻燃效果。
2.普通磷酸酯结构和长链烃连接环状磷酸酯结构(链烃碳数≥3)，提供分子相对的柔性，与聚醚、聚酯类基体具有较好的相容性。
3.DOPO环状磷酸酯结构中包括多个P-C键，保证了其具有较高的阻燃效率，并且适用于具有较高加工温度的聚合物基体。
4.本发明为添加型无卤磷系阻燃剂，合成简单，使用方便，磷含量高，阻燃效果更好。
本发明区别于已有专利揭示的DOPO衍生化合物，在该复合结构中通过普通磷酸酯将多个通过碳-碳键连接的DOPO类环状磷酸酯结构缩合到一个化合物分子中。
附图说明
图1是本发明实施例4的测试结果图。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
在一个3升的四颈烧瓶上安装上机械搅拌器、h型油水分离器和回流冷凝管、滴液漏斗和氮气入口。往其中加入253.3克(1.172mol)DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)、100.6克对二甲苯、800克PXE(1，1-双(3，4-二甲基苯基)乙烷)溶剂和56.45克丙三醇溶液(53.9克(0.586mol)丙三醇溶解2.55克碘化钠)。在油水分离器中加满对二甲苯后，在氮气流保护下加热反应混合物至200℃反应14小时，反应过程中通过油水分离器不断排出产生的水。反应后期生成的水较少，则提高反应温度至205℃再反应2小时。反应结束后待体系温度降至室温，通过滴液漏斗逐滴加入29.94克(0.195mol)三氯氧磷， 反应生成的氯化氢气体用20％的NaOH溶液中和吸收，三氯氧磷滴加完后，提高反应温度至60℃再反应2小时，反应混合物降到室温后，产品以白色至淡黄色蜡状固体从溶剂中析出，产品标记为P1。产品收率(基于DOPO原料)约为85％，磷含量14.36％。1HNMR：7.15-7.95ppm，m，16H(H-Ar)；2.87ppm，d，4H(CH2)；3.60ppm，m，1H(CH)。13CNMR：119.9-150.2ppm(C-Ar)；39.2ppm(CH2)；50.1ppm(CH)。31PNMR：37.14-37.34ppm(DOPO chirals)；-5.8ppm((-O-)3P(O))。
实施例2
按照实施例1程序，仅将其中反应物56.45克丙三醇溶液换成64.67克丁三醇溶液(62.12克1.2.4-丁三醇溶解2.55克碘化钠)，其他反应物和溶剂用量不变。并在反应混合物降到室温后在滴加三氯氧磷之前，先向反应瓶中加入150毫升吡啶。反应产物为淡黄色糖浆状液体，标记为P2，产率约为81％，磷含量为13.98％。1HNMR：7.13-7.95ppm，m，16H(H-Ar)；2.60-2.88-ppm，m，6H(CH2)；3.54ppm，m，1H(CH)。13CNMR：119.9-150.2ppm(C-Ar)；38.8-39.3ppm(CH2)；50.1ppm(CH)。31PNMR：37.12-37.34ppm(DOPO结构手性异构体混合物)；-5.8ppm((-O-)3P(O))。
实施例3
将53.13克(0.391mol)季戊四醇溶解于160毫升乙醇中，向其中加入2.55克碘化钠，混合物加热回流2小时，然后将乙醇逐渐蒸出，制得季戊四醇与碘化钠的反应混合物。将该混合物取代实施例1中的丙三醇溶液作为反应物，其他反应物和溶剂用量不变，按照实施例1的程序反应。并在反应混合物降到室温后在滴加三氯氧磷之前，先向反应瓶中加入150毫升吡啶。产品为白色固体，标记为P3，产率为86％，磷含量13.84％。1HNMR：7.29-8.02ppm，m，24H(H-Ar)；2.42ppm，s，6H(P-CH2-C)；3.89ppm，s，2H(C-CH2-O)。13CNMR：119.9-150.2ppm(C-Ar)；39.7ppm(CH2)；69.0ppm(CH2)，-4.8ppm(tert-C)。31PNMR：37.12-37.34ppm(DOPO结构手性异构体混合物)；-5.6ppm((-O-)3P(O))。
实施例4
热重分析测试实施例1-3中制备的阻燃剂P1，P2和P3。测试在Netzsch STA449F3A分析仪上进行，空气气氛，测试温度范围20-600℃，加热速率10℃/分钟。结果如图1所示。
实施例5
燃烧性能测试：取适量的实施例1-3制备的阻燃剂P1，P2，P3，阻燃级氢氧化铝(1000目，中铝山东)和40克环氧树脂E-44在150℃搅拌1小时，降温到100℃后加入7.5克二氨基二苯甲烷，混合均匀后快速浇模到10厘米×10厘米×3毫米(长×宽×厚)的模具中，升温到150℃固化3小时，自然冷却至室温后脱模得待测阻燃环氧树脂样品。用氧指数仪测定其极限氧指数，用垂直燃烧仪测定其燃烧级别，结果总结如表1所示。
表1
Figure PCTCN2016088521-appb-000003
a.重量百分比指添加物相对于环氧树脂E-44的重量百分比；b.极限氧指数的测定参考国标方法GB/T2406-93。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权 利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (10)

  1. 一种含多DOPO环状磷酸酯的复合结构磷阻燃剂，其特征在于，其结构式中包括不少于1个有机磷酸酯和不少于2个DOPO环状磷酸酯。
  2. 根据权利要求1所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂，其特征在于，所述复合结构磷阻燃剂的结构如结构式(c)所示，其中R1、R2、R3至少有一个为结构式(a)或结构式(b)中任意一种，除此之外的R1、R2或R3是烷基、芳香基；结构式(a)或结构式(b)中R为氢、烷基、芳香基、羧基、羧基芳基、羟基烷基、烷氧基烷基、芳氧基烷基、羟基芳基、烷氧基芳基或芳氧基芳基，并且R是相同或不同的取代基；n，m，p，q为数字1-20；
    Figure PCTCN2016088521-appb-100001
  3. 一种含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，其过程分两步进行：
    (1)DOPO与多羟基链烷烃或取代链烃混合，其中多羟基链烷烃的羟基数目≥3，取代链烃中链烃碳数≥3，在保护气体下加热混合物至195-210℃反应14-17小时，使得其中至少有一个羟基没有参与反应，制得DOPO环状磷酸酯；
    (2)降至室温，再加入卤代氧磷或不完全酯化卤代氧磷，然后升温至55-65℃反应1.5-3小时，使得代氧磷或不完全酯化卤代氧磷与DOPO环状磷酸酯中未反应的羟基反应，降至室温即得复合结构磷阻燃剂。
  4. 根据权利要求3所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，步骤(1)中，保护气体为氮气。
  5. 根据权利要求3所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，步骤(1)中，在保护气体下加热混合物至200℃反应14小时，再在205℃下反应2小时。
  6. 根据权利要求3所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，步骤(1)中，DOPO环状磷酸酯的结构包括但不限于结构式(a)或结构式(b)，
    Figure PCTCN2016088521-appb-100002
    其中R为氢、烷基、芳香基、羧基、羧基芳基、羟基烷基、烷氧基烷基、芳氧基烷基、羟基芳基、烷氧基芳基或芳氧基芳基，并且R是相同或不同的取代基；n，m，p，q为数字1-20。
  7. 根据权利要求3所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，步骤(2)中，升温至60℃反应2小时。
  8. 根据权利要求3所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，步骤(1)中，多羟基链烷烃采用对二甲苯、1，1-双(3，4-二甲基苯基)乙烷和含有碘化钠的醇溶液混合而成，对二甲苯、1，1-双(3，4-二甲基苯基)乙烷和含有碘化钠的醇溶液的质量比为100-101∶800∶55-65。
  9. 根据权利要求8所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，醇溶液中碘化钠与醇的质量摩尔比为4.35∶1g/mol，醇为丙三醇、丁三醇或季戊四醇。
  10. 根据权利要求3所述的含多DOPO环状磷酸酯的复合结构磷阻燃剂的制备方法，其特征在于，卤代氧磷采用三氯氧磷。
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