WO2020228021A1 - 一种含dopo的磷氮型阻燃剂及其制备方法 - Google Patents

一种含dopo的磷氮型阻燃剂及其制备方法 Download PDF

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WO2020228021A1
WO2020228021A1 PCT/CN2019/087271 CN2019087271W WO2020228021A1 WO 2020228021 A1 WO2020228021 A1 WO 2020228021A1 CN 2019087271 W CN2019087271 W CN 2019087271W WO 2020228021 A1 WO2020228021 A1 WO 2020228021A1
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flame retardant
dopo
containing phosphorus
group
nitrogen flame
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PCT/CN2019/087271
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English (en)
French (fr)
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周崇福
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周崇福
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Priority to PCT/CN2019/087271 priority Critical patent/WO2020228021A1/zh
Publication of WO2020228021A1 publication Critical patent/WO2020228021A1/zh
Priority to US17/454,822 priority patent/US20220127533A1/en

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    • 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
    • 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 Table
    • 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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • 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'

Definitions

  • the invention belongs to the technical field of flame retardants, and in particular relates to a DOPO-containing phosphorus nitrogen type flame retardant and a preparation method thereof.
  • Polymer materials have the advantages of light weight, high specific strength, and good processing characteristics, so they have been widely used in various fields of the national economy. However, because they are mainly composed of carbon and hydrogen elements, they are extremely easy to burn. While bringing convenience to people's lives, they also hide huge fire safety hazards.
  • DOPO-based flame retardants have the advantages of good flame retardancy, halogen-free, non-toxic, and environmentally friendly, they have been widely used in epoxy resin (EP), polyester, polypropylene (PP) and other polymer materials in recent years.
  • DOPO is an organophosphorus intermediate, in which the PH bond is more active and can undergo addition reactions with unsaturated bonds, carbonyl groups, etc., using its ability to form a variety of derivatives, various types of DOPO-based flame retardants can be prepared Agent.
  • WO2010135398 reports a derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), which contains two phosphorus centers (DiDOPO) in one molecule and has good Thermal stability and flame retardancy.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • US8536256 discloses DiDOPO with different bridges as a flame retardant for epoxy resins.
  • the patent does not include aryl-substituted vinyl bridges.
  • JPH11-106619 reported the derivative of DOPO, DiDOPO, and the patent did not mention aromatic-substituted vinyl bridges.
  • DiDOPO flame retardants are all prepared by the Michaelis-Becker reaction of DOPO and dihalogenated alkanes under the action of strong bases, which require expensive strong bases as raw materials, have high production costs, and have the defects of low reaction yield.
  • CN1040865393A discloses that the bridge structure connecting two DOPO compounds is a vinyl group containing an aryl group. Due to the short bridge chain, the compound molecule has rigidity and greatly avoids plasticization. The aryl group on the vinyl group increases the steric hindrance, which not only greatly increases its chemical stability, but also reduces the volatility of the compound, which overcomes the deficiencies of the known DiDOPO flame retardants.
  • CN1563152A discloses a method for preparing a polymer-type phosphorus-containing flame retardant, using DOPO-modified hydroquinone or hydroquinone, phenyl or naphthyl substituted dichloro (bromo) oxyphosphorus as the reaction matrix A phosphorous-containing polymer flame retardant is obtained, but a catalyst must be used in the preparation process of the flame retardant, and a precipitant of 5-10 times the amount of the solvent is used in the separation process, which causes great environmental pollution.
  • CN101643650A discloses the reaction of DOPO-containing hydroquinone or hydroquinone and an olefin with reactive functional groups to form a flame retardant, but the compatibility with the polymer is not good, and there is a problem of leaching.
  • the DOPO-based flame retardant in the prior art has many problems such as poor compatibility, easy leaching, low hydrolysis resistance, high preparation method cost, low yield, and large environmental pollution. Therefore, the present invention has developed a DOPO-containing phosphorus-nitrogen flame retardant and a preparation method thereof.
  • the flame retardant of the present invention is an organic intumescent flame retardant and is formed by bulk polymerization.
  • the preparation method is relatively simple and the yield is high. , No pollution to the environment, green and environmental protection.
  • the purpose of the present invention is to provide a DOPO-containing phosphorus-nitrogen flame retardant and a preparation method thereof.
  • the DOPO-containing phosphorus-nitrogen flame retardant has excellent flame retardant effect, good compatibility with the substrate, does not ooze out in the substrate, has excellent hydrolysis resistance, low smoke and low toxicity, and the preparation process Simple, high yield, green and environmental protection.
  • a DOPO-containing phosphorus-nitrogen flame retardant the structure of the flame retardant is as follows:
  • R 1 and R 2 are selected from H, C1-C18 alkyl, C6-C18 aryl, C3-C18 heteroaryl, fused cycloalkyl aryl, fused cycloalkyl heteroaryl, fused heterocyclic group One or two of aryl, fused heterocyclic heteroaryl, and C1-C18 alkyl substituted with silicon, oxygen, sulfur, carbonyl or sulfonyl;
  • R 1 and R 2 are connected through a saturated/unsaturated alkyl group, or form a heteroaryl group, a condensed cycloalkylaryl group, a condensed cycloalkylheteroaryl group, a condensed heterocyclic aryl group or a condensed N atom. Heterocyclic group heteroaryl.
  • the heteroaryl group is a monocyclic or polycyclic aromatic group, the N atom is connected to the aromatic ring, and the heteroaryl group contains one, two or three heterocyclic groups selected from N, O and S.
  • the ring atoms, the remaining ring atoms are C.
  • one or more carbon atoms of the heteroaryl group is replaced by a carbonyl group.
  • heterocyclic group is a non-aromatic mono- or polycyclic group, wherein one or more ring atoms are heteroatoms selected from N, O, or S(O) n , wherein n is an integer from 0 to 2 , The remaining ring atoms are C.
  • alkyl group includes linear, branched or aromatic ring-containing alkyl groups.
  • the flame retardant may have the following structure:
  • n 1-100.
  • the above is an example of the structure of the DOPO-containing phosphorus-nitrogen flame retardant of the present invention, and is not limited to the above structure.
  • the present invention also provides a preparation method of the DOPO-containing phosphorus-nitrogen flame retardant, which includes the following steps:
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • the reaction is stirred for a period of time, then the temperature is increased and the stirring is continued until the reaction is completed, and then cooled to obtain a DOPO-containing phosphorus-nitrogen flame retardant.
  • a strong acid catalyst is further added in the step (2). Strong acid catalyst can speed up the reaction speed and improve production efficiency.
  • the strong acid catalyst is selected from one or more mixtures of p-benzenesulfonic acid, p-benzenesulfonic acid hydrate or its alcohol solution, phosphoric acid, hydrochloric acid or sulfuric acid.
  • the added amount of the strong acid catalyst is 0.01 to 5% of the mass of the raw material.
  • the heating temperature in step (1) is 215-221°C.
  • the temperature is increased to 225-230°C.
  • the viscosity of the system in the late stage of the reaction of the above preparation method increases, and the reaction can be effectively stirred by increasing the reaction temperature to promote the reaction.
  • the DOPO-containing phosphorus-nitrogen flame retardant of the present invention has excellent flame retardant effects and a wide range of applications. It is resistant to epoxy resin, ABS, PMMA, TPV, nylon, polyester, polyolefin, polyurethane, polycarbonate and other polymers. Burn effectively.
  • the flame retardant of the present invention belongs to organic macromolecules, so it has good substrate compatibility, does not ooze out in the substrate, and has excellent hydrolysis resistance.
  • the flame retardant of the present invention belongs to an intumescent flame retardant and has the properties of low smoke and low toxicity.
  • the preparation method of the present invention has simple process, few by-products, short reaction time, high yield, no solvents harmful to the environment, and environmental protection.
  • the polyether polyurethane TPU 5182 (Shanghai Yitan New Material Co., Ltd.) and the product obtained in Example 2 were mixed at a weight ratio of 85:15, and extruded on a twin screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm. It is water-cooled and granulated out of the strip. The extrusion temperature is 180°C, and the screw speed is 300 rpm. The material was dried and placed in a 1.7 mm thick mold, preheated in a 180°C flat vulcanizer for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 1.7 mm thick sheet, and then cut into test specimens. According to the national burning test standard GB/T2408-2008, the flame retardant level is 1.7mm UL-94V0.
  • Example 11 Flame retardant performance of flame retardant
  • Nylon 6YH800 (Yueyang Baling Petrochemical) and the product obtained in Example 1 were mixed by weight at a ratio of 85:15, and then extruded into a stranded water-cooled granulation in a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm.
  • the extrusion temperature is 200°C
  • the screw rotation speed is 300 rpm.
  • the material was dried and placed in a 1.7 mm thick mold, preheated in a 230°C plate vulcanizer for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 1.7 mm thick sheet, and then cut into test specimens.
  • the flame retardant level is 1.7mm UL-94V0.
  • Example 12 Flame retardant performance of flame retardant
  • Nylon 6,6 101F DuPont, USA
  • the product obtained in Example 1 are mixed by weight at a ratio of 90:10, and the strands are extruded in a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm. grain.
  • the extrusion temperature is 255°C
  • the screw rotation speed is 300 rpm.
  • the flame retardant level is 1.7mm UL-94V0.
  • the polyester PET FG600 (intrinsic viscosity: 0.675) (Sinopec Yizheng Chemical Fiber Co., Ltd.) and the product obtained in Example 1 are mixed at a ratio of 90:10 by weight, and are mixed in a twin-screw extruder with a diameter of 40 mm (manufactured by Nanjing Mianya Machinery). Co., Ltd.) Extrusion strand water-cooling granulation.
  • the extrusion temperature is 255°C, and the screw rotation speed is 300 rpm.
  • the material was dried and placed in a 3 mm thick mold, preheated in a flat vulcanizer at 260°C for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 3 mm thick sheet, and then cut into test specimens.
  • the flame retardant level is 3mm UL-94V0.
  • Polypropylene PP MR700 (Shanghai Jinshan Petrochemical Company) and the product obtained in Example 1 are mixed by weight at a ratio of 75:25, and extruded in a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm. grain.
  • the extrusion temperature is 220°C
  • the screw rotation speed is 300 rpm.
  • the material was dried and placed in a 3 mm thick mold, preheated in a plate vulcanizer at 220°C for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 3 mm thick sheet, and then cut into test specimens.
  • the flame retardant level is 3mm UL-94V0.
  • the polyether polyurethane TPU 5182 (Shanghai Yitan New Material Co., Ltd.) and the product obtained in Example 5 were mixed in a weight ratio of 90:10, and extruded on a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm. It is water-cooled and granulated out of the strip. The extrusion temperature is 180°C, and the screw speed is 300 rpm. The material was dried and placed in a 0.8 mm thick mold, preheated in a 180°C flat vulcanizer for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 0.8 mm thick sheet, and then cut into test specimens. According to the national burning test standard GB/T2408-2008, the flame retardant level is 0.8mm UL-94V0.
  • Example 16 Flame retardant performance of flame retardant
  • Nylon 6YH800 (Yueyang Baling Petrochemical) and the product obtained in Example 5 were mixed by weight at a ratio of 85:15, and extruded into a stranded water-cooled granulation in a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm.
  • the extrusion temperature is 200°C
  • the screw rotation speed is 300 rpm.
  • the material was dried and placed in a 1.7 mm thick mold, preheated in a 230°C plate vulcanizer for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 1.7 mm thick sheet, and then cut into test specimens.
  • the flame retardant level is 1.7mm UL-94V0.
  • Example 17 Flame retardant performance of flame retardant
  • Nylon 6YH800 (Yueyang Baling Petrochemical) and the product obtained in Example 8 were mixed by weight at a ratio of 85:15, and then extruded into a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm to be extruded and water-cooled to pelletize.
  • the extrusion temperature is 200°C
  • the screw rotation speed is 300 rpm.
  • the material was dried and placed in a 1.7 mm thick mold, preheated in a 230°C plate vulcanizer for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 1.7 mm thick sheet, and then cut into test specimens.
  • the flame retardant level is 1.7mm UL-94V0.
  • Nylon 6YH800 (Yueyang Baling Petrochemical) and the product obtained in Example 8 were mixed by weight at a ratio of 90:10, and then extruded into a twin-screw extruder (Nanjing Mianya Machinery Manufacturing Co., Ltd.) with a diameter of 40 mm to be extruded and water-cooled to pelletize.
  • the extrusion temperature is 200°C
  • the screw rotation speed is 300 rpm.
  • the material was dried and placed in a 1.7 mm thick mold, preheated in a 230°C plate vulcanizer for 5 minutes, and then hot pressed at 5 MPa for 3 minutes to prepare a 1.7 mm thick sheet, and then cut into test specimens.
  • the flame retardant level is 1.7mm UL-94V2.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

本发明公开了一种含DOPO的磷氮型阻燃剂及其制备方法。本发明的含DOPO的磷氮型阻燃剂化学结构式如图（aa)：其通过本体聚合制备而成。该含DOPO的磷氮型阻燃剂阻燃效果优异，与基材的相容性好，在基材中不会渗出，具有优异的抗水解性，低烟低毒的性能，且制备工艺简单，产率高，绿色环保。

Description

一种含DOPO的磷氮型阻燃剂及其制备方法 技术领域
本发明属于阻燃剂技术领域，特别是涉及一种含DOPO的磷氮型阻燃剂及其制备方法。
背景技术
高分子材料具有质轻、比强度大、加工特性好等优点，因此在国民经济的各个领域得到了广泛的应用。然而由于它们主要由碳、氢元素组成，极易燃烧，在给人民生活带来便利的同时，也隐藏着巨大的火灾安全隐患。
由于DOPO基阻燃剂有着阻燃性能良好、无卤无毒、环境友好等优点，近年来被广泛应用于环氧树脂(EP)、聚酯、聚丙烯(PP)和其他高分子材料中。DOPO是一种有机磷中间体，其中的P-H键较为活泼，可与不饱和键、羰基等发生加成反应，利用其可形成多种衍生物的能力，可以制备各种类型的DOPO基阻燃剂。
WO2010135398报道了9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物，该衍生物一个分子中含有2个磷中心(DiDOPO)，具有良好的热稳定性和阻燃性。
US8536256公开了具有不同桥链的DiDOPO作为环氧树脂的阻燃剂，该专利不包括芳基取代的乙烯基桥链。
JPH11-106619报道了DOPO的衍生物DiDOPO，该专利没有提到芳香基取代的乙烯基桥链。
上述几种DiDOPO阻燃剂都是通过DOPO和二卤代烷烃在强碱作用下的Michaelis-Becker反应制备，需要使用昂贵的强碱作为原料，生产成本较高，且具有反应产率低的缺陷。
CN1040865393A公开了连接两个DOPO类化合物之间的桥链结构是含有芳基的乙烯基，由于桥链短，此化合物分子具有刚性，极大避免了塑化性。乙 烯基上的芳基增加了空间位阻，不仅大幅增加了其化学稳定性，而且降低了化合物的挥发性，克服了已知的DiDOPO类阻燃剂不足。
CN1563152A公开了一种聚合物型含磷阻燃剂的制备方法，采用DOPO改性的对苯二酚或对苯二酚、苯基或萘基取代的二氯(溴)氧磷为反应基质来获得含磷的聚合物型阻燃剂，但该阻燃剂的制备过程中必须使用催化剂，分离过程中要使用5-10倍溶剂量的沉淀剂，对环境污染较大。
CN101643650A公开了通过含DOPO的对苯二酚或苯二酚和带有反应性官能团的烯烃进行反应形成阻燃剂，但是与聚合物相容性不好，存在浸出问题。
总之，现有技术中DOPO基阻燃剂存在相容性不好，容易浸出，抗水解性不高，制备方法成本高，产率低，对环境污染大等诸多问题。因此，本发明开发了一种含DOPO的磷氮型阻燃剂及其制备方法，本发明的阻燃剂是有机膨胀性阻燃剂，通过本体聚合而成，制备方法较简单，产率高，对环境无污染，绿色环保。
发明内容
本发明的目的在于提供一种含DOPO的磷氮型阻燃剂及其制备方法。该含DOPO的磷氮型阻燃剂阻燃效果优异，与基材的相容性好，在基材中不会渗出，具有优异的抗水解性，低烟低毒的性能，且制备工艺简单，产率高，绿色环保。
为了达到上述的目的，本发明采取以下技术方案：
一种含DOPO的磷氮型阻燃剂，该阻燃剂结构如下所示：
Figure PCTCN2019087271-appb-000001
其中，
R 1、R 2选自H、C1-C18烷基、C6-C18芳基、C3-C18杂芳基、稠合环烷基 芳基、稠合环烷基杂芳基、稠合杂环基芳基、稠合杂环基杂芳基、以及硅、氧、硫、羰基或硫酰基取代的C1-C18烷基中的一种或两种；
或者，
R 1、R 2通过饱和/不饱和烷基相连接，或与N原子构成杂芳基、稠合环烷基芳基、稠合环烷基杂芳基、稠合杂环基芳基或稠合杂环基杂芳基。
进一步地，所述杂芳基为单环或多环芳族基团，N原子连接到芳族环上，所述杂芳基中含有一、两或三个选自N、O和S的杂环原子，其余环原子为C。
进一步地，所述的杂芳基的一个或多个碳原子被羰基替代。
进一步地，所述杂环基为非芳族单或多环基团，其中一个或多个环原子是选自N、O或S(O) n的杂原子，其中n是0至2的整数，其余环原子是C。
进一步地，所述烷基包括直链、支链或含有芳香环的烷基。
例如，所述阻燃剂可以有如下所示结构：
Figure PCTCN2019087271-appb-000002
Figure PCTCN2019087271-appb-000003
Figure PCTCN2019087271-appb-000004
n＝1-100。
以上是本发明含DOPO的磷氮型阻燃剂结构举例，并不局限于上述结构。
本发明还提供上述含DOPO的磷氮型阻燃剂的制备方法，包括如下步骤：
(1)对9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)进行加热，使9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物全部熔融；
(2)在熔融的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物中加入如下结构化合物A：
Figure PCTCN2019087271-appb-000005
或其醚化衍生物；
搅拌反应一段时间，然后升高温度继续搅拌，直至反应结束，冷却，得到含DOPO的磷氮型阻燃剂。
进一步地，上述制备方法中，所述步骤(2)中进一步加入强酸催化剂。强酸催化剂能够加快反应速度，提高生产效率。
优选的，所述强酸催化剂选自对苯磺酸，对苯磺酸水合物或其醇溶液，磷酸，盐酸或硫酸中的一种或多种混合物。
进一步地，所述强酸催化剂加入量为原料质量的0.01-5％。
进一步地，上述制备方法中，所述步骤(1)加热温度为215～221℃。
加热温度以使其熔融即可，温度太高会增加能量消耗，使工艺成本增高。
进一步地，在上述制备方法中，所述步骤(2)搅拌反应30-40分钟后，升高温度为225-230℃。上述制备方法反应后期体系粘度增大，通过升高反应温度能够有效的进行搅拌，促进反应的进行。
本发明具有以下技术特点：
1)本发明含DOPO的磷氮型阻燃剂阻燃效果优异，应用范围广泛，对环氧树脂，ABS，PMMA，TPV，尼龙，聚酯，聚烯烃，聚氨酯，聚碳酸酯等高分子阻燃有效。
2)本发明的阻燃剂属于有机大分子，因此有较好的基材相容性，在基材中不会渗出，具有优异的抗水解性。
3)本发明的阻燃剂属于膨胀系阻燃剂，具有低烟低毒的性能。
4)本发明的制备方法工艺简单，副产物少，反应时间短，产率高，没有使用对环境有害的溶剂，绿色环保。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实 施例的技术方案进行清楚、完整的描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
除非另作定义，本公开所使用的技术术语或者科学术语应当为本发明所属领域内有一般技能的人士所理解的通常意义。
实施例1：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入490克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到170℃，等全部熔融后，加入210克六羟甲基三聚氰胺六甲醚，为了加快反应，可以加入0.1％的苯磺酸作为强酸催化剂，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物甲醇。30分钟之后，然后继续升温230℃，继续搅拌，直到几乎没有甲醇产生为止。冷却后，产品为淡黄色固体，产率84％，DSC检测此产物的玻璃化转变温度是140℃。
该反应反应方程式如下：
Figure PCTCN2019087271-appb-000006
实施例2：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入525克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到170℃，等全部熔融后，加入175克六羟甲基三聚氰胺六甲醚，为了加快反应，可以加入0.1％的苯磺酸作为强酸催化剂，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物甲醇。35分钟之后，然后继续升温235℃，继续搅拌，直到几乎没有甲醇产生为止。冷却后，产品 为无色透明固体，产率89％，DSC检测此产物的玻璃化转变温度是121℃。
实施例3：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入520克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到165℃，等全部熔融后，加入140克六羟甲基三聚氰胺，为了加快反应，可以加入0.1％的苯磺酸作为强酸催化剂，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物水。40分钟之后，然后继续升温240℃，继续搅拌，直到几乎没有水产生为止。冷却后，产品为浅黄色透明固体，产率89％，DSC检测此产物的玻璃化转变温度是147℃。
该反应反应方程式如下：
Figure PCTCN2019087271-appb-000007
实施例4：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入520.0克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到170℃，等全部熔融后，加入160.0克三羟甲基三聚氰胺三甲醚，为了加快反应，可以加入0.1％的苯磺酸作为强酸催化剂，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物甲醇和水。30分钟之后，然后继续升温230℃，继续搅拌，直到几乎没有甲醇和水产生为止。冷却后，得到阻燃剂产品。产品为浅黄色透明固体，产率86％，DSC检测此产物的玻璃化转变温度是145℃。
该反应反应方程式如下：
Figure PCTCN2019087271-appb-000008
实施例5：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入448.0克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到165℃，等全部熔融后，加入252.0克二羟甲基二羟乙烯脲，为了加快反应，可以加入少量强酸0.1％苯磺酸催化剂(催化剂可以不加)，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物水。40分钟之后，然后继续升温220℃，继续搅拌，直到几乎没有水蒸汽产生为止。冷却后，产品为暗红色固体，产率83％，DSC检测此产物的玻璃化转变温度是105℃。
实施例6：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入580.3克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到165℃，等全部熔融后，加入119.7克二羟甲基二羟乙烯脲，为了加快反应，可以加入少量强酸0.1％苯磺酸催化剂(催化剂可以不加)，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物水。40分钟之后，然后继续升温200℃，继续搅拌，直到几乎没有水蒸汽产生为止。冷却后，产品为暗红色固体，产率80％，DSC检测此产物的玻璃化转变温度是60℃。
实施例7：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入495.6克9，10-二氢-9-氧杂-10- 磷杂菲-10-氧化物(dopo)，加热到165℃，等全部熔融后，加入204.4克二羟甲基二羟乙烯脲，为了加快反应，可以加入少量强酸0.1％苯磺酸催化剂(催化剂可以不加)，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物水。40分钟之后，然后继续升温230℃，继续搅拌，直到几乎没有水蒸汽产生为止,大约50分钟后停止反应。冷却后，产品为暗红色固体，产率80％，DSC检测此产物的玻璃化转变温度是85℃。
实施例8：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入420.0克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到200℃，等全部熔融后，加入280.0克甲醚化的二羟甲基二羟乙烯脲，为了加快反应，可以加入少量强酸0.1％苯磺酸催化剂(催化剂可以不加)，持续强烈的搅拌，熔体粘度剧烈上升，同时产生副产物甲醇。40分钟之后，然后继续升温240℃，继续搅拌，直到几乎没有甲醇蒸汽产生为止。冷却后，产品为暗红色固体，产率80％，DSC检测此产物的玻璃化转变温度是100℃。
实施例9：阻燃剂的制备
在装有搅拌器的1000毫升三颈瓶中加入473.9克9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(dopo)，加热到180℃，等全部熔融后，加入226.1克甲醚化的二羟甲基二羟乙烯脲，为了加快反应，可以加入少量强酸0.1％苯磺酸催化剂(催化剂可以不加)，持续强烈的搅拌，熔体粘度上升，同时产生副产物甲醇。40分钟之后，然后继续升温220℃，继续搅拌，直到几乎没有甲醇蒸汽产生为止。冷却后，产品为暗红色固体，产率83％，DSC检测此产物的玻璃化转变温度是85℃。
实施例10：阻燃剂阻燃性能
将聚醚型聚氨酯TPU 5182(上海益弹新材料有限公司)和实施例2所得 产物以85:15比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是180℃，螺杆转速300转/分钟。将材料干燥后放在1.7毫米厚的模具中，在180℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备1.7毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为1.7毫米UL-94V0。
实施例11：阻燃剂阻燃性能
将尼龙6YH800(岳阳巴陵石化)和实施例1所得产物以85:15比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是200℃，螺杆转速300转/分钟。将材料干燥后放在1.7毫米厚的模具中，在230℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备1.7毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为1.7毫米UL-94V0。
实施例12：阻燃剂阻燃性能
将尼龙6,6 101F(美国杜邦公司)和实施例1所得产物以90:10比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是255℃，螺杆转速300转/分钟。将材料干燥后放在1.7毫米厚的模具中，在260℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备1.7毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为1.7毫米UL-94V0。
实施例13：阻燃剂阻燃性能
将聚酯PET FG600(特性粘度：0.675)(中国石化仪征化纤有限责任公司)和实施例1所得产物以90:10比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是255℃，螺杆转速300转/分钟。将材料干燥后放在3毫米厚的模具中，在260℃平板硫 化机中预热5分钟，然后在5MPa下热压3分钟制备3毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为3毫米UL-94V0。
实施例14：阻燃剂阻燃性能
聚丙烯PP MR700(上海金山石化公司)和上述实施例1所得产物以75:25比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是220℃，螺杆转速300转/分钟。将材料干燥后放在3毫米厚的模具中，在220℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备3毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为3毫米UL-94V0。
实施例15：阻燃剂阻燃性能
将聚醚型聚氨酯TPU 5182(上海益弹新材料有限公司)和实施例5所得产物以90:10比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是180℃，螺杆转速300转/分钟。将材料干燥后放在0.8毫米厚的模具中，在180℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备0.8毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为0.8毫米UL-94V0。
实施例16：阻燃剂阻燃性能
将尼龙6YH800(岳阳巴陵石化)和实施例5所得产物以85:15比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是200℃，螺杆转速300转/分钟。将材料干燥后放在1.7毫米厚的模具中，在230℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备1.7毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为1.7毫米UL-94V0。
实施例17：阻燃剂阻燃性能
将尼龙6YH800(岳阳巴陵石化)和实施例8所得产物以85:15比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是200℃，螺杆转速300转/分钟。将材料干燥后放在1.7毫米厚的模具中，在230℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备1.7毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为1.7毫米UL-94V0。
实施例14：阻燃剂阻燃性能
将尼龙6YH800(岳阳巴陵石化)和实施例8所得产物以90:10比例重量混合，在直径40毫米的双螺杆挤出机(南京棉亚机械制造有限公司)挤出拉条水冷造粒。挤出温度是200℃，螺杆转速300转/分钟。将材料干燥后放在1.7毫米厚的模具中，在230℃平板硫化机中预热5分钟，然后在5MPa下热压3分钟制备1.7毫米厚的薄片，然后切成测试样条。按照国家燃烧测试标准GB/T2408-2008测试，阻燃级别为1.7毫米UL-94V2。
以上实施例的说明只是用于帮助理解本发明方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求保护范围内。

Claims (10)

  1. 一种含DOPO的磷氮型阻燃剂，其特征在于，该阻燃剂结构如下所示：
    Figure PCTCN2019087271-appb-100001
    其中，
    R 1、R 2选自H、C1-C18烷基、C6-C18芳基、C3-C18杂芳基、稠合环烷基芳基、稠合环烷基杂芳基、稠合杂环基芳基、稠合杂环基杂芳基、以及硼，硅、氧、硫、羰基或硫酰基取代的C1-C18烷基中的一种或两种；
    或者，
    R 1、R 2通过饱和/不饱和烷基相连接，或与N原子构成杂芳基、稠合环烷基芳基、稠合环烷基杂芳基、稠合杂环基芳基或稠合杂环基杂芳基。
  2. 根据权利要求1所述的一种含DOPO的磷氮型阻燃剂，其特征在于，所述杂芳基为单环或多环芳族基团，N原子连接到芳族环上，所述杂芳基中含有一、两或三个选自N、O和S的杂环原子，其余环原子为C。
  3. 根据权利要求2所述的一种含DOPO的磷氮型阻燃剂，其特征在于，所述的杂芳基的一个或多个碳原子被羰基替代。
  4. 根据权利要求1所述的一种含DOPO的磷氮型阻燃剂，其特征在于，所述杂环基为非芳族单或多环基团，其中一个或多个环原子是选自N、O或S(O) n的杂原子，其中n是0至2的整数，其余环原子是C。
  5. 根据权利要求1所述的一种含含DOPO的磷氮型阻燃剂，其特征在于，所述烷基包括直链、支链或含有芳香环的烷基。
  6. 权利要求1-5任一项所述的含DOPO的磷氮型阻燃剂的制备方法，其特征在于，包括如下步骤：
    (1)对9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)进行加热，使9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物全部熔融；
    (2)在熔融的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物中加入如下结构化合物A：
    Figure PCTCN2019087271-appb-100002
    或其醚化衍生物；
    搅拌反应一段时间，然后升高温度继续搅拌，直至反应结束，冷却，得到含DOPO的磷氮型阻燃剂。
  7. 根据权利要求6所述的含DOPO的磷氮型阻燃剂的制备方法，其特征在于，步骤(2)中进一步加入强酸催化剂。
  8. 根据权利要求7所述的含DOPO的磷氮型阻燃剂的制备方法，其特征在于，所述强酸催化剂选自对苯磺酸，对苯磺酸水合物或其醇溶液，磷酸，盐酸或硫酸中的一种或多种混合物。
  9. 根据权利要求7所述的含DOPO的磷氮型阻燃剂的制备方法，其特征在于，所述强酸催化剂加入量为原料质量的0.01-5％。
  10. 根据权利要求6所述的含DOPO的磷氮型阻燃剂的制备方法，其特征在于，所述步骤(2)搅拌反应30-40分钟后，升高温度为225-230℃。
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Citations (3)

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Publication number Priority date Publication date Assignee Title
US4086206A (en) * 1976-07-05 1978-04-25 Sanko Kaihatsu Kagaku Kenkyosho Organophosphorus compounds and process for the production thereof
CN1681865A (zh) * 2002-09-11 2005-10-12 希尔和塞拉彻股份公司 环氧树脂的固化剂及其应用和以此固化的环氧树脂
CN103435652A (zh) * 2013-07-01 2013-12-11 北京化工大学 一种高含氮量新型含磷杂菲和磷腈双效官能团化合物的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086206A (en) * 1976-07-05 1978-04-25 Sanko Kaihatsu Kagaku Kenkyosho Organophosphorus compounds and process for the production thereof
CN1681865A (zh) * 2002-09-11 2005-10-12 希尔和塞拉彻股份公司 环氧树脂的固化剂及其应用和以此固化的环氧树脂
CN103435652A (zh) * 2013-07-01 2013-12-11 北京化工大学 一种高含氮量新型含磷杂菲和磷腈双效官能团化合物的制备方法

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