CN111499664A - Reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin and preparation method thereof - Google Patents
Reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin and preparation method thereof Download PDFInfo
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- CN111499664A CN111499664A CN202010346886.0A CN202010346886A CN111499664A CN 111499664 A CN111499664 A CN 111499664A CN 202010346886 A CN202010346886 A CN 202010346886A CN 111499664 A CN111499664 A CN 111499664A
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- flame retardant
- epoxy resin
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- dopo
- reactive flame
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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
- C07F9/657163—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
- C07F9/657181—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, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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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
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
Abstract
The invention discloses a reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin and a preparation method thereof, wherein the flame retardant has the structure that:
wherein R is (CH)2)xAnd x is any one of 2, 3, 4 or 5. The flame retardant is prepared from hydroxyethylamine and DOPO serving as raw materials by a one-pot method, and has the advantages of simple synthesis process, safe operation, short period, high yield, wide source of required raw materials and the like. Meanwhile, the flame retardant structure contains the phosphaphenanthrene, phosphorus-nitrogen, hydroxyl, amino and other groups, and both the hydroxyl and the amino can participate in the curing reaction of the epoxy resin, so that the compatibility of the flame retardant and the epoxy resin is improved, and the improvement of the compatibility of the flame retardant and the epoxy resin is realizedMechanical properties of epoxy resin cured products. The phosphaphenanthrene and phosphorus-nitrogen groups have good flame retardant effect, and can endow the cured epoxy resin with good flame retardant property, thereby widening the application field of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of flame retardance of epoxy resin, and particularly relates to a reactive flame retardant containing DOPO and hydroxyl and applied to epoxy resin and a preparation method thereof.
Background art:
epoxy resin is a common thermosetting polymer material and is widely applied to the fields of home decoration building materials, electronic equipment, aerospace and the like, but the epoxy resin has poor flame retardance, releases a large amount of smoke in the combustion process and severely restricts the application of the epoxy resin. Therefore, the fire hazard of the epoxy resin material is reduced, and the application field of the epoxy resin material can be widened. The conventional halogen flame retardant generates toxic substances such as dioxin, hydrogen halide and the like when being heated, and causes harm to the environment, and the use of the flame retardant is gradually limited in recent years. The development of halogen-free flame retardant has become the mainstream direction of the flame retardant field at present, wherein phosphorus flame retardant and nitrogen flame retardant are concerned, and the concentration of oxygen around a combustion object can be effectively diluted by non-combustible gas generated during the combustion of the nitrogen-containing flame retardant, and the heat on the surface of the combustion object can be taken away. For example, it has been reported that a nitrogen-containing flame retardant is used for flame-retardant modification of epoxy resin, and although the addition of the flame retardant improves the flame retardancy of the epoxy resin, the problems of long time consumption for flame retardant synthesis, high temperature requirement and low experimental safety exist (university of Hunan's journal (Nature science edition), 2006, 72-75). Phosphorus-containing flame retardants can generate phosphorus-containing derivatives such as metaphosphoric acid during combustion, and these can be used as dehydrating agents to promote the formation of carbon layers, for example, a phosphorus-containing additive flame retardant is used for flame-retardant modification of epoxy resins, and when the addition amount of the flame retardant is 9.1 wt%, the limiting oxygen index value is increased to 35%, but the impact strength is not well maintained (Industrial & Engineering Chemistry Research,2017, 1245-1255). Therefore, the flame retardant which has good flame retardant effect, simple synthesis process and safe operation and can give consideration to mechanical properties while resisting flame has important research significance and application value.
Disclosure of Invention
The invention aims to provide a reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin has the following structural formula:
wherein R is (CH)2)xAnd x may be any one of 2, 3, 4 or 5.
The preparation method of the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin comprises the following steps: under the protection of nitrogen, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), triethylamine and 1, 2-dichloroethane into a three-neck flask provided with a reflux condenser tube and a constant pressure funnel, stirring until the DOPO is completely dissolved, adding a mixed solution of hydroxyethylamine and 1, 2-dichloroethane through the constant pressure dropping funnel, after the dropwise addition is completed, slowly dropping carbon tetrachloride through the constant pressure dropping funnel, after the dropwise addition is completed, reacting for a period of time under a certain temperature condition, after the reaction is completed, filtering, washing and drying the obtained solution to obtain the reactive flame retardant containing DOPO and hydroxyl, wherein the reaction equation is as follows:
wherein R is (CH)2)xAnd x may be any one of 2, 3, 4 or 5.
The molar ratio of the hydroxyethyl amine to the DOPO is 1: 1-1.3, the total usage amount of the hydroxyethyl amine and the 1, 2-dichloroethane is 1: 19-25, the molar ratio of the hydroxyethyl amine to the triethylamine is 1: 1-1.2, the molar ratio of the hydroxyethyl amine to the carbon tetrachloride is 1: 0.4-0.5, the temperature during dropwise adding the carbon tetrachloride is controlled to be-10-0 ℃, the reaction temperature after dropwise adding the carbon tetrachloride is-10-25 ℃, and the reaction time is 6-9 h.
The invention has the following advantages:
1. the invention is carried out by reacting P-H of DOPO with-NH of hydroxyethylamine2The preparation method has the advantages of simple synthesis process, safe operation, short period, high yield, wide sources of required raw materials and the like.
2. The reactive flame retardant containing DOPO and hydroxyl is a halogen-free reactive flame retardant, the flame retardant structure contains phosphaphenanthrene, phosphorus-nitrogen, hydroxyl, amino and the like, wherein the hydroxyl and amino active groups can participate in the curing reaction of epoxy resin, so that the compatibility of the flame retardant and the epoxy resin is improved, and the mechanical property of a cured epoxy resin is favorably improved; the phosphaphenanthrene and phosphorus-nitrogen groups have good flame retardant effect, and can endow the cured epoxy resin with good flame retardant property, thereby widening the application field of the epoxy resin. The phosphorus-nitrogen group has a synergistic flame retardant effect in the flame retardant, phosphorus can generate phosphoric acid, polymetaphosphoric acid and the like, the phosphorus can be used as a dehydrating agent to promote carbonization, and nitrogen can generate ammonia and other non-combustible gases so as to dilute the oxygen concentration.
The specific implementation mode is as follows:
example 1:
under the protection of nitrogen, adding DOPO (0.02mol,4.32g),30m L1, 2-dichloroethane and triethylamine (0.023mol,3.2m L) into a three-necked flask provided with a reflux condenser tube and a constant pressure funnel, stirring until the DOPO is completely dissolved, slowly dropping 10m L1, 2-dichloroethane and N- (2-hydroxyethyl) ethylenediamine (0.02mol,2.02m L) mixed solution through the constant pressure dropping funnel, controlling the temperature to be-5 ℃ after the dropping is finished, then dropping 10m L mol,2.13m L) through the constant pressure dropping funnel, heating to 25 ℃ after the dropping is finished, reacting for 6 hours, after the reaction is finished, filtering, washing and drying the obtained solution to obtain the reaction type flame retardant containing the DOPO and hydroxyl, wherein the structural formula of the reaction type flame retardant is as follows:
infrared spectrum of-OH (3467 cm)-1),-NH(3367cm-1),Ar-H(3036cm-1),-CH2(2973cm-1),P-Ph(1601,1447cm-1),P＝O(1214cm-1),P-O-C(980cm-1)。
Diaminodiphenylmethane is used as a curing agent, the epoxy resin is modified by the synthesized flame retardant, the limit oxygen index of the obtained flame-retardant modified epoxy resin condensate reaches 44 percent and passes the V-0 grade of U L-94 (the limit oxygen index of the epoxy resin condensate without the flame retardant is 26 percent and cannot pass the test of U L-94), and the cone calorimetry test result shows that the total smoke emission (TSR), the heat release rate (THR) and the ignition time (TTI) are 2074m respectively2/m2，78MJ/m2And 92s (TSR, THR and TTI of the epoxy resin cured product to which no flame retardant was added are 2512m each2/m2，97MJ/m2And 68 s); the bending strength and the tensile strength are respectively 135MPa and 91MPa (the bending strength and the tensile strength of the epoxy resin condensate without the flame retardant are respectively 82MPa and 70MPa), and the flame retardant has excellent flame retardant property and mechanical property.
Example 2:
under the protection of nitrogen, adding DOPO (0.02mol,4.32g),30m L1, 2-dichloroethane and triethylamine (0.023mol,3.2m L) into a three-necked flask provided with a reflux condenser tube and a constant pressure funnel, stirring until the DOPO is completely dissolved, slowly dropping 10m L1, 2-dichloroethane and N- (2-hydroxyethyl) propanediamine (0.02mol,2.34m L) mixed solution through the constant pressure dropping funnel, controlling the temperature to be-10 ℃ after the dropping is finished, then dropping 10m L mol,2.13m L through the constant pressure dropping funnel, heating to 5 ℃ after the dropping is finished, reacting for 7 hours, after the reaction is finished, filtering, washing and drying the obtained solution to obtain the reaction type flame retardant containing the DOPO and hydroxyl, wherein the structural formula of the reaction type flame retardant is as follows:
infrared spectrum of-OH (3412 cm)-1),-NH(3321cm-1),Ar-H(3031cm-1),-CH2(2993cm-1),P-Ph(1608,1451cm-1),P＝O(1234cm-1),P-O-C(985cm-1).
Diaminodiphenylmethane is used as a curing agent, the epoxy resin is modified by the synthesized flame retardant, the limit oxygen index of the obtained flame-retardant modified epoxy resin condensate reaches 40 percent and passes the V-0 grade of U L-94 (the limit oxygen index of the epoxy resin condensate without the flame retardant is 26 percent and can not pass the test of U L-94), and the cone calorimetric test result shows that the total smoke emission (TSR), the heat release rate (THR) and the ignition time (TTI) are 2174m respectively2/m2,83MJ/m2And 90s (TSR, THR and TTI of the epoxy resin cured product to which no flame retardant was added are 2512m each2/m2，97MJ/m2And 68 s); the bending strength and the tensile strength are respectively 132MPa and 90MPa (the bending strength and the tensile strength of the epoxy resin condensate without the flame retardant are respectively 82MPa and 70MPa), and the flame retardant has excellent flame retardant property and mechanical property.
Example 3:
under the protection of nitrogen, adding DOPO (0.02mol,4.32g),30m L1, 2-dichloroethane and triethylamine (0.023mol,3.2m L) into a three-necked flask provided with a reflux condenser tube and a constant pressure funnel, stirring until the DOPO is completely dissolved, slowly dropping 10m L1, 2-dichloroethane and N- (2-hydroxyethyl) butanediamine (0.02mol,2.75m L) through the constant pressure dropping funnel, controlling the temperature to be 0 ℃ after the dropping is finished, then dropping carbon tetrachloride (0.008mol,2.13m L) through the constant pressure dropping funnel, after the dropping is finished, heating to-10 ℃ for reaction for 9 hours, after the reaction is finished, filtering, washing and drying the obtained solution to obtain the reactive flame retardant containing the DOPO and hydroxyl, wherein the structural formula is as follows:
infrared spectrum of-OH (3461 cm)-1),-NH(3366cm-1),Ar-H(3036cm-1),-CH2(2988cm-1),P-Ph(1611,1449cm-1),P＝O(1244cm-1),P-O-C(978cm-1).
Diaminodiphenylmethane is used as a curing agent, the epoxy resin is modified by the synthesized flame retardant, the limit oxygen index of the obtained flame-retardant modified epoxy resin condensate reaches 38 percent and passes the V-0 grade of U L-94 (the limit oxygen index of the epoxy resin condensate without the flame retardant is 26 percent and can not pass the test of U L-94), and the cone calorimetry test result shows that the total smoke emission (TSR), the heat release rate (THR) and the ignition time (TTI) are 2374m respectively2/m2,85MJ/m2And 89s (TSR, THR and TTI of the epoxy resin cured product without flame retardant are 2512m each2/m2，97MJ/m2And 68 s); the bending strength and the tensile strength are respectively 128MPa and 88MPa (the bending strength and the tensile strength of the epoxy resin condensate without the flame retardant are respectively 82MPa and 70MPa), and the flame retardant has excellent flame retardant property and mechanical property.
Claims (8)
1. A reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin is characterized in that: the structure of the flame retardant is as follows:
wherein R is (CH)2)xAnd x is any one of 2, 3, 4 or 5.
2. A method for preparing the reactive flame retardant containing DOPO and hydroxyl group for epoxy resin according to claim 1, wherein: under the protection of nitrogen, adding DOPO, 1, 2-dichloroethane and triethylamine into a three-necked flask provided with a condenser tube and a constant-pressure funnel, continuously stirring until the DOPO is dissolved, adding a mixed solution of hydroxyethylamine and 1, 2-dichloroethane, after dropwise adding, slowly adding carbon tetrachloride dropwise at a certain temperature, reacting at a certain temperature for a period of time after dropwise adding, and carrying out suction filtration, washing and drying to obtain the reactive flame retardant containing DOPO and hydroxyl.
3. The method for preparing the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin as claimed in claim 2, wherein: the molar ratio of the hydroxyethyl amine to the DOPO is 1: 1-1.3.
4. The method for preparing the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin as claimed in claim 2, wherein: the molar ratio of the total amount of the hydroxyethylamine to the 1, 2-dichloroethane is 1: 19-25.
5. The method for preparing the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin as claimed in claim 2, wherein: the molar ratio of the hydroxyethyl amine to the triethylamine is 1: 1-1.2.
6. The method for preparing the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin as claimed in claim 2, wherein: the molar ratio of the hydroxyethylamine to the carbon tetrachloride is 1: 0.4-0.5.
7. The method for preparing the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin as claimed in claim 2, wherein: the temperature of the carbon tetrachloride is controlled to be-10-0 ℃.
8. The method for preparing the reactive flame retardant containing DOPO and hydroxyl applied to the epoxy resin as claimed in claim 2, wherein: the reaction temperature after the carbon tetrachloride is dripped is-10 to 25 ℃, and the reaction time is 6 to 9 hours.
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| CN202010346886.0A CN111499664A (en) | 2020-04-27 | 2020-04-27 | Reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin and preparation method thereof |
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| CN202010346886.0A CN111499664A (en) | 2020-04-27 | 2020-04-27 | Reactive flame retardant containing DOPO and hydroxyl applied to epoxy resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805441A (en) * | 2022-03-31 | 2022-07-29 | 北京理工大学 | Reactive flame retardant applied to epoxy resin and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| US4178398A (en) * | 1975-05-15 | 1979-12-11 | Ciba-Geigy Corporation | Amidophosphate reaction products used as flameproofing agents |
| CN104024266A (en) * | 2011-08-08 | 2014-09-03 | 联邦材料测试与开发研究所 | Novel phosphonamidates-synthesis and flame retardant applications |
| CN109851639A (en) * | 2019-01-14 | 2019-06-07 | 贵州省材料产业技术研究院 | A kind of alkyl bridge chain DOPO derivative and its preparation method and application |
| CN110204572A (en) * | 2019-05-31 | 2019-09-06 | 福建师范大学 | One kind is containing double hydroxyl phosphorus nitrogen synergistic reactive flame retardants and preparation method thereof |
-
2020
- 2020-04-27 CN CN202010346886.0A patent/CN111499664A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4178398A (en) * | 1975-05-15 | 1979-12-11 | Ciba-Geigy Corporation | Amidophosphate reaction products used as flameproofing agents |
| CN104024266A (en) * | 2011-08-08 | 2014-09-03 | 联邦材料测试与开发研究所 | Novel phosphonamidates-synthesis and flame retardant applications |
| CN109851639A (en) * | 2019-01-14 | 2019-06-07 | 贵州省材料产业技术研究院 | A kind of alkyl bridge chain DOPO derivative and its preparation method and application |
| CN110204572A (en) * | 2019-05-31 | 2019-09-06 | 福建师范大学 | One kind is containing double hydroxyl phosphorus nitrogen synergistic reactive flame retardants and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| KHALIFAH A. SALMEIA等: "Industrial Upscaling of DOPO-Based Phosphonamidates and Phosphonates Derivatives Using Cl2 Gas as a Chlorinating Agent", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805441A (en) * | 2022-03-31 | 2022-07-29 | 北京理工大学 | Reactive flame retardant applied to epoxy resin and preparation method thereof |
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Application publication date: 20200807 |