CN112442074A - Reactive flame retardant and preparation method and application thereof - Google Patents

Reactive flame retardant and preparation method and application thereof Download PDF

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CN112442074A
CN112442074A CN201910803181.4A CN201910803181A CN112442074A CN 112442074 A CN112442074 A CN 112442074A CN 201910803181 A CN201910803181 A CN 201910803181A CN 112442074 A CN112442074 A CN 112442074A
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flame retardant
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潘庆崇
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Guangdong Guangshan New Materials Co ltd
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Guangdong Guangshan New Materials Co ltd
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Abstract

The invention relates to a reactive flame retardant, a preparation method and application thereof.

Description

Reactive flame retardant and preparation method and application thereof
Technical Field
The invention belongs to the field of high polymer materials, and relates to a reactive flame retardant, and a preparation method and application thereof.
Background
Electronic products represented by mobile phones, computers, video cameras, and electronic game machines, home and office electric products represented by air conditioners, refrigerators, television images, audio products, and various products used in other fields are required to have flame retardancy and heat resistance for safety in most of the products.
In the traditional technology, inorganic flame-retardant substances such as aluminum hydroxide hydrate, magnesium hydroxide hydrate and other metal hydroxides containing crystal water are generally added into a material system, and organic flame-retardant substances with higher halogen content such as brominated bisphenol A, brominated bisphenol A epoxy resin and the like are added into the material system, so that the product reaches the required flame-retardant performance or grade. To improve the flame retardancy of these organic halogen-containing chemicals, inorganic flame retardant substances such as antimony trioxide, which are not environmentally friendly, are often added to the system.
The halogen-containing flame retardant substances can generate non-degradable or difficultly degradable toxic substances (such as dioxin organic halogen chemical substances) during combustion, pollute the environment and influence the health of human beings and animals.
The halogen-free flame retardant in the prior art has the defects of poor identity with a flame retardant main body, poor water resistance, poor operability, non-uniform flame retardant effect and the like.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a reactive flame retardant, a preparation method and application thereof.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention aims to provide a reactive flame retardant, which is obtained by reacting a compound shown in a formula I with a compound containing a reactive group to remove at least one molecule of R '-O-R';
Figure BDA0002182893920000021
wherein X is a group VI element or is absent, R1And R2Each independently is any group which satisfies the chemical environment, R' comprises any one of hydrogen and isotope thereof and substituted or unsubstituted alkyl, aryl or heteroaryl, a, b and c are each independently integers which are more than or equal to 0, and a + b + c is less than or equal to 3;
wherein, R' comprises any one of hydrogen and isotopes thereof, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl.
Wherein a may be 0,1,2 or 3, b may be 0,1,2 or 3, and c may be 1,2 or 3.
Are preferred techniques of the present inventionScheme of the invention, said R1And R2Each independently preferably includes any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted cycloalkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, or a substituted or unsubstituted heteroarylmercapto group.
As a preferred embodiment of the present invention, R preferably includes any one of substituted or unsubstituted alkylene, cycloalkylene, arylene, heteroarylene, alkylenecycloalkyl, alkylenearyl, alkyleneheteroaryl, cycloalkylenearyl, cycloalkyleneheteroaryl, or aryleneheteroaryl.
In a preferred embodiment of the present invention, X is O or S.
In a preferred embodiment of the present invention, the reactive group-containing compound includes any one or a combination of at least two of a hydroxyl group, a phenolic hydroxyl group, a thiol group, an aldehyde group, a carboxyl group, an ester group, a cyano group, an amino group, or a substituted or unsubstituted unsaturated group.
In the present invention, the substituted or unsubstituted alkyl group is preferably a substituted or unsubstituted alkyl group having from C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group of C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted aryl group is preferably an aryl group of C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).
The substituted or unsubstituted heteroaryl group is preferably a C4-C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaryl group.
The substituted or unsubstituted alkoxy group is preferably a C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted alkoxy group.
The substituted or unsubstituted cycloalkoxy group is preferably a C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted cycloalkoxy group.
The substituted or unsubstituted aryloxy group is preferably a C6-C13 (e.g., C7, C8, C9, C10, C11, or C12) substituted or unsubstituted aryloxy group.
The substituted or unsubstituted heteroaryloxy group is preferably a C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaryloxy group.
The substituted or unsubstituted alkylamino group is preferably a substituted or unsubstituted alkylamino group having at least one carbon atom selected from the group consisting of C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, and C11).
The substituted or unsubstituted cycloalkylamino group is preferably a C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted cycloalkylamino group.
The substituted or unsubstituted arylamino group is preferably a C6-C13 (e.g., C7, C8, C9, C10, C11, or C12) substituted or unsubstituted arylamino group.
The substituted or unsubstituted heteroaralmino group is preferably a C4-C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaralmino group.
The substituted or unsubstituted arylalkylamino group is preferably a C7-C12 (e.g., C8, C9, C10, or C11) substituted or unsubstituted arylalkylamino group.
The substituted or unsubstituted heteroarylalkylamino group is preferably a C7-C13 (e.g., C8, C9, C10, C11, or C12) substituted or unsubstituted heteroarylalkylamino group.
Substituted or unsubstituted alkylmercapto groups C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted arylmercapto group is preferably a substituted or unsubstituted arylmercapto group having from C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).
The substituted or unsubstituted heteroarylmercapto group is preferably a C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroarylmercapto group.
The substituted or unsubstituted alkylene group is preferably an alkylene group having from C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted cycloalkylene group is preferably a cycloalkylene group of C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted arylene group is preferably an arylene group having from C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).
The substituted or unsubstituted heteroarylene is preferably a C5-C13 (e.g., C6, C7, C8, C9, C10, C11, or C12) substituted or unsubstituted heteroarylene.
The substituted or unsubstituted alkylenearyl group is preferably a C7-C13 (e.g., C8, C9, C10, C11, or C12) substituted or unsubstituted alkylenearylene group.
The substituted or unsubstituted cycloalkylene group is preferably a substituted or unsubstituted cycloalkylene group of C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11).
Substituted or unsubstituted alkyleneheteroaryl groups C6 to C12 (e.g., C7, C8, C9, C10, or C11).
Substituted or unsubstituted cycloalkylenearyl groups C9 to C12 (e.g., C10 or C11).
Substituted or unsubstituted cycloalkyleneheteroaryl of substituted or unsubstituted cycloalkyleneheteroaryl C9 to C12 (e.g., C10 or C11).
Substituted or unsubstituted aryleneheteroaryl of C11 to C12 of substituted or unsubstituted aryleneheteroaryl.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring.
The second object of the present invention is to provide a method for preparing the above reactive flame retardant, the method comprising:
the compound shown in the formula I reacts with the compound containing the reactive group to remove at least one molecule of R' -O-R ″.
The invention also aims to provide application of the flame retardant, and the reactive flame retardant is used for preparing molding materials and composite materials.
As a preferred technical scheme of the invention, the reactive flame retardant is used for preparing epoxy resin compositions, polyurethane compositions, polyester compositions, unsaturated resin compositions, phenolic resins and silicone resins.
As a preferable technical scheme of the invention, the reactive flame retardant is used for preparing high polymer materials.
Preferably, the polymer material includes polyester, polyurethane, alkyd, polyamide, amino resin, unsaturated resin, and silicone resin.
In the invention, the provided reactive flame retardant is applied to a high polymer material, and can be added as a monomer as a fragment of the high polymer material when the high polymer material is prepared; or the reactive flame retardant is prepared into a high molecular compound firstly, and then is added into a high molecular material, for example, the reactive flame retardant containing two or more amino groups provided by the invention reacts with a compound containing at least two carboxyl groups to prepare a polyamide compound, and then the polyamide compound is added into the high molecular material as a flame retardant additive.
As the preferable technical scheme of the invention, the reactive flame retardant is used for copper-clad plates, glass fiber reinforced plastics, nylon flame retardants and potting materials.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the reactive flame retardant provided by the invention has excellent flame retardant property and excellent compatibility with a flame retardant main body, and is excellent in operability, water resistance and electrical property, and the preparation method saves resources and is green and environment-friendly;
(2) the reactive flame retardant provided by the invention can be used in various fields such as engineering plastics, epoxy resin curing agents, phenolic resins, unsaturated resins, polyurethane and the like, and can greatly improve the flame retardant property of the material;
(3) the epoxy resin cured by the reactive flame retardant provided by the invention has excellent performances in all aspects, such as flame retardance, mechanical strength and water resistance;
(4) after the reactive flame retardant provided by the invention is added into the silicone resin, the flame retardant property of the silicone resin reaches V-0, and the mechanical property and the water resistance are improved;
(5) compared with the polyurethane foam plastic prepared by the traditional flame retardant additive, the polyurethane foam plastic prepared by using the reactive flame retardant prepared by the invention as the additive has the flame retardant property reaching V-0 level and has more excellent mechanical property;
(6) the flame retardance of the polyurethane leather prepared by using the reactive flame retardant provided by the invention as an additive can reach V-0 level, and the polyurethane leather has excellent moisture permeability and hydrolysis resistance;
(7) the phenolic resin prepared by using the reactive flame retardant provided by the invention as an additive has the flame retardant property of V-0 and excellent tensile strength and water resistance;
(8) by using the reactive flame retardant provided by the invention as an additive, the flame retardance of the acrylic resin can reach V-0, and the acrylic resin has excellent tensile property;
(9) the acrylic resin composition prepared by using the reactive flame retardant provided by the invention as an additive has the flame retardance reaching V-0 and excellent mechanical properties.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a reactive flame retardant, which has a structure shown in formula II:
Figure BDA0002182893920000071
the synthesis method of the compound shown in the formula II comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mL of chloroform, adding 1.2mol of glycol amine, adding 0.01mol of potassium carbonate and 0.01mol of potassium iodide, heating, refluxing, mechanically stirring, reacting for 12h, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula II.
1H NMR(CDCl3,500MHz):δ4.68～4.62(d，4H，CH2)，3.75～3.68(s，6H，CH3)，3.62～3.57(t，2H，OH)，2.79～2.72(s，2H，CH2)。
Example 2
The present embodiment provides a reactive flame retardant, which has a structure shown in formula III:
Figure BDA0002182893920000081
the synthesis method of the compound shown in the formula III comprises the following steps: dissolving 1mol of diethyl phosphite in 50mL of chloroform, adding 1.2mol of ethylene oxide and 2mL of hydrochloric acid (1mol/L), mechanically stirring at room temperature for reaction for 2h, after the reaction is finished, removing the solvent by rotary evaporation to obtain a solid, washing the obtained solid with water for 5 times, and drying to obtain the diethyl hydroxyethyl phosphite. Dissolving 1mol of diethyl hydroxyethyl phosphite in chloroform, adding 1.2mol of melamine, adding 0.01mol of potassium carbonate and 0.01mol of potassium iodide, heating, refluxing, mechanically stirring and reacting for 12 hours, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula III.
1H NMR(CDCl3,500MHz):δ7.03～6.96(s，4H，NH2)，4.55～4.48(t，H，NH)，4.25～4.17(m，4H，CH2)，3.36～3.31(m，2H，CH2)，2.03～1.95(t，2H，CH2)，1.37～1.31(s，6H，CH3)。
Example 3
The present embodiment provides a reactive flame retardant, which has a structure as shown in formula IV:
Figure BDA0002182893920000091
the synthesis method of the compound shown in the formula IV comprises the following steps: dissolving 1mol of diethyl hydroxymethyl phosphite in 50mL of chloroform, adding 1.2mol of 3-aminopropene, adding 0.01mol of sodium methoxide, heating, refluxing, mechanically stirring, reacting for 8 hours, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula IV.
1H NMR(CDCl3,500MHz):δ5.83～5.77(m，H，CH2＝CH)，5.25～5.15(t，2H，CH 2＝CH)，4.22～4.15(m，4H，CH2)，3.28～3.21(t，2H，CH2)，2.97～2.91(d，2H，CH2)，2.35～2.30(m，H，NH)，1.39～1.33(s，6H，CH3)。
Example 4
The present embodiment provides a reactive flame retardant, which has a structure shown in formula V:
Figure BDA0002182893920000092
the synthesis method of the compound shown in the formula V comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mL of chloroform, adding 1.2mol of valine, adding 0.01mol of sodium methoxide, heating, refluxing, mechanically stirring, reacting for 10 hours, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula V.
1H NMR(CDCl3,500MHz):δ11.32～11.25(s，H，COOH)，3.71～3.65(s，6H，CH3)，3.50～3.44(d，H，CH)，3.11～3.03(d，2H，CH2)，2.47～2.43(m，H，NH)，2.30～2.22(t，H，CH)，0.91～0.83(t，6H，CH3)。
Example 5
The present embodiment provides a reactive flame retardant, which has a structure as shown in formula VI:
Figure BDA0002182893920000101
the synthesis method of the compound shown in the formula VI comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mL of tetrahydrofuran, adding 1.1mol of diethyl succinate and 0.1mol of sodium hydroxide, reacting for 24h at room temperature, removing the solvent by rotary evaporation after the reaction is finished to obtain a solid, purifying by adopting a physical method, and drying to obtain the compound shown in the formula VI.
1H NMR(CDCl3,500MHz):δ4.61～4.55(s，2H，CH2)，4.20～4.12(m，2H，CH2)，3.58～3.51(s，6H，CH3)，2.77～2.69(t，4H，CH2)，1.37～1.30(t，3H，CH3)。
Example 6
This embodiment provides a reactive flame retardant, which has a structure shown in formula VII:
Figure BDA0002182893920000102
the synthesis method of the compound shown in the formula VII comprises the following steps: diethyl hydroxyethyl phosphite is prepared according to the method described in example 2, 1mol of diethyl hydroxyethyl phosphite is dissolved in 50mL of tetrahydrofuran, 1.1mol of 6-hydroxyhexanal and 0.1mol of sodium hydroxide are added to react for 24h at room temperature, after the reaction is finished, the solvent is removed by rotary evaporation to obtain a solid, and the solid is purified by a physical method and dried to obtain the compound shown in formula VI.
1H NMR(CDCl3,500MHz):δ9.81～9.75(t，H，CHO)，4.27～4.21(m，4H，CH2)，3.38～3.29(t，4H，CH2)，2.43～2.36(m，2H，CH2)，1.99～1.93(t，2H，CH2)，1.61～1.52(m，4H，CH2)，1.37～1.31(m，2H，CH2)，1.23～1.16(t，6H，CH3)。
Example 7
This embodiment provides a reactive flame retardant, which has a structure shown in formula VIII:
Figure BDA0002182893920000111
the synthesis method of the compound shown in the formula VIII comprises the following steps: dissolving 1mol of hydroxyethyl dimethyl phosphite in 50mL of chloroform, adding 1.3mol of 2-hydroxyisobutyronitrile and 0.02mol of sodium ethoxide, reacting for 15h under a reflux condition, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula VIII.
1H NMR(CDCl3,500MHz):δ4.25～4.16(m，4H，CH2)，3.93～3.85(s，2H，CH2)，1.64～1.56(s，6H，CH3)，1.37～1.30(t，6H，CH3)。
Example 8
This example provides a reactive flame retardant, which has a structure shown in formula IX:
Figure BDA0002182893920000121
the synthesis method of the compound shown in the formula IX comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 30mL of DMF, adding 1.2mol of ethanedithiol, adding 0.01mol of sodium ethoxide, heating, refluxing, mechanically stirring, reacting for 24 hours, purifying by adopting a physical method after the reaction is finished, and drying to obtain the compound shown in the formula IX.
1H NMR(CDCl3,500MHz):δ3.72～3.65(t，6H，CH3)，2.27～2.21(t，H，SH)，2.93～2.85(m，4H，CH2)，2.68～2.61(t，2H，CH2)。
Example 9
The present embodiment provides a reactive flame retardant, which has a structure as shown in formula X:
Figure BDA0002182893920000122
the synthesis method of the compound shown in the formula X comprises the following steps: preparing diethyl hydroxyethyl phosphite according to the method described in example 2, dissolving 1mol diethyl hydroxyethyl phosphite in 50mL DMSO, adding 1.2mol 2-hydroxymethyl hydroquinone, adding 0.1mol sodium hydroxide, heating, refluxing, mechanically stirring, reacting for 24h, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in formula X.
1H NMR(CDCl3,500MHz):δ7.05～6.92(m，2H，Ar-H)，6.78～6.71(m，H，Ar-H)，5.39～5.35(s，2H，OH)，4.81～4.76(s，2H，CH2)，4.16～4.10(m，4H，CH2)，3.84～3.77(t，2H，CH2)，2.09～2.02(t，2H，CH2)，1.37～1.30(t，6H，CH3)。
Example 10
This example provides a reactive flame retardant, which has a structure shown in formula XI:
Figure BDA0002182893920000131
the synthesis method of the compound shown in the formula XI comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mL of DMF, adding 1.2mol of hydroxyethyl methacrylate and 0.1mol of sodium hydroxide, heating, refluxing, mechanically stirring and reacting for 12 hours, purifying by adopting a physical method after the reaction is finished, and drying to obtain the compound shown in the formula XI.
1H NMR(CDCl3,500MHz):δ6.51～6.42(t，2H，CH2＝CH)，4.31～4.25(t，2H，CH2)，3.85～3.78(s，2H，CH2)，3.68～3.62(s，6H，CH3)，3.61～3.65(t，2H，CH2)，2.08～2.02(s，3H，CH3)。
Application of the epoxy resin curing agent:
example 11
In this example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was mixed with 40 parts by weight of the reactive flame retardant shown in example 2, and the mixture was cured at 50 ℃ for 3 hours to obtain an epoxy resin cured product a.
Example 12
In this example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was mixed with 33 parts by weight of the reactive flame retardant shown in example 4, and the mixture was cured at 50 ℃ for 3 hours to obtain an epoxy resin cured product b.
Example 13
In this example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was mixed with 42 parts by weight of the reactive flame retardant described in example 9, and the mixture was cured at 50 ℃ for 3 hours to obtain an epoxy resin cured product c.
Comparative example 1
In this comparative example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was added with 6 parts by weight of a dicyandiamide, 34 parts by weight of APP was added, and cured at 50 ℃ for 3 hours to obtain an epoxy resin cured product d.
Comparative example 2
In this comparative example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was added with 6 parts by weight of dicyandiamide, 34 parts by weight of MCA was added thereto, and cured at 50 ℃ for 3 hours to obtain an epoxy resin cured product e.
Comparative example 3
In this comparative example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was added with 6 parts by weight of dicyandiamide, and then 34 parts by weight of red phosphorus capsules were added and cured at 50 ℃ for 3 hours to obtain an epoxy resin cured product f.
The cured epoxy resins obtained in examples 11 to 13 and comparative examples 1 to 3 were tested for their properties, the flexural strength was measured by GB/T9341-2008, the impact strength was measured by GB/T1843-2008, the breakdown voltage was measured by GB/T1408.1-2006, the flame retardancy was measured by UL-94, the test conditions for weight loss after baking were 150 ℃ baking for 2 hours, and the test conditions for water resistance were immersion in boiling water for 2 hours. The test results are shown in Table 1.
TABLE 1
Figure BDA0002182893920000141
Figure BDA0002182893920000151
As can be seen from the test results in Table 1, the epoxy resin cured by using the reactive flame retardant of examples 2, 4 or 9 of the present invention has better properties, such as flame retardancy, mechanical strength and change of properties after absorbing water, than the cured epoxy resin with dicyandiamide as the curing agent and APP or MCA as the flame retardant. In contrast, comparative example 3, which also used dicyandiamide as the curing agent and red phosphorus capsules as the flame retardant, the cured epoxy resin had a flame retardancy of V-0, but the mechanical strength and the change in water absorption properties were still lower than those of the epoxy resin cured with the reactive flame retardant of the present invention provided in examples 2, 4 or 9. Therefore, the reactive flame retardant provided by the invention is applied to an epoxy resin curing agent, provides beneficial flame retardant performance, and has positive influence on the mechanical performance and the water-resistant stability of an epoxy resin cured product.
Application of the silicone resin:
example 14
In this example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 100 parts by weight of the reactive flame retardant prepared in example 2 were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin a.
Example 15
In this example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 84 parts by weight of the reactive flame retardant prepared in example 4 were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin b.
Comparative example 4
In this example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane and 50 parts by weight of sodium silicate nonahydrate were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin c.
Comparative example 5
In this example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 100 parts by weight of APP were mixed and cured at 20 ℃ for 5 hours to prepare silicone resin d.
The silicone resins obtained in examples 14 and 15 and comparative examples 4 and 5 were tested for their properties, tensile strength and elongation being measured by GB/T1701-2001, shear strength being measured by GB/T1700-2001, flame retardancy being measured by UL-94, and water resistance being measured by immersion in boiling water for 2 hours. The test results are shown in table 1.
TABLE 2
Figure BDA0002182893920000171
From the test results in Table 2, it can be seen that comparative example 4 is not added with any flame retardant, the flame retardant property is only V-2, the reactive flame retardants prepared in examples 2 and 4 are respectively added in examples 14 and 15, the flame retardant property of the prepared silicone resin reaches V-0, and the mechanical property and the water resistance of the silicone resin are improved compared with those of silicone resin c. Comparative example 5 has flame retardant APP added to silicone resin c, the flame retardant performance is improved to V-1, the mechanical properties are also improved, but the overall performance is inferior to that of silicone resin a and silicone resin b.
Use in polyurethane foams:
example 16
In this example, 45 parts by weight of the reactive flame retardant prepared in example 1 was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of a polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index of 1.3) to foam and prepare a polyurethane foam a.
Comparative example 6
In this comparative example, 45 parts by weight of triphenyl phosphate was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index 1.3) to foam and prepare polyurethane foam b.
Comparative example 7
In this comparative example, 45 parts by weight of red phosphorus capsule was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index 1.3) to foam and prepare polyurethane foam c.
The cured epoxy resin obtained in example 16 and comparative examples 6 and 7 were tested for properties, using GB/T20467-. The test results are shown in Table 3.
TABLE 3
Figure BDA0002182893920000191
As can be seen from the test results in Table 3, the polyurethane foam prepared using the reactive flame retardant prepared in example 1 of the present invention as an additive has a flame retardant property of V-0 grade and a mechanical property superior to that of a polyurethane foam prepared using triphenyl phosphate or red phosphorus as a flame retardant additive.
The application of the polyurethane leather comprises the following steps:
example 17
In this example, 50 parts by weight of the reactive flame retardant prepared in example 1 was mixed with 100 parts by weight of polyester polyurethane having a solid content (75%), 10 parts by weight of polyether polyurethane having a solid content (75%), 100 parts by weight of dimethylformamide, 10 parts by weight of lignocellulose, 5 parts by weight of a surfactant, 2 parts by weight of a modified silicone polymer, and 8 parts by weight of a coloring material, and a polyurethane leather a was prepared by a dipping cloth base and a coating cloth base process.
Comparative example 8
In this example, 50 parts by weight of dimethyl methylphosphonate was mixed with 100 parts by weight of polyester polyurethane having a solid content of 75%, 10 parts by weight of polyether polyurethane having a solid content of 75%, 100 parts by weight of dimethylformamide, 10 parts by weight of lignocellulose, 5 parts by weight of a surfactant, 2 parts by weight of a modified silicone polymer, and 8 parts by weight of a coloring material, and a polyurethane leather b was prepared by a cloth-impregnated and cloth-coated process.
Comparative example 9
In this example, 50 parts by weight of MCA, 100 parts by weight of polyester urethane having a solid content (75%), 10 parts by weight of polyether urethane having a solid content (75%), 100 parts by weight of dimethylformamide, 10 parts by weight of lignocellulose, 5 parts by weight of a surfactant, 2 parts by weight of a modified silicone polymer, and 8 parts by weight of a coloring material were mixed, and a polyurethane leather c was prepared by a dipping cloth base and a coating cloth base process.
The polyurethane leather prepared in example 17 and comparative examples 8 and 9 were tested for moisture permeability, peel strength, hydrolysis resistance and flammability, and the results are shown in table 4. The hydrolysis resistance is that the polyurethane leather after the peel strength test is soaked in boiling water for 2 hours, and then the peel strength test is carried out again.
TABLE 4
Item Moisture permeability/g/(m)2·24h) Peel strength/N Hydrolysis resistance/N Flame retardancy
Detection standard GB/T-12704.1-2009 QB/T-419-2011 QB/T-41952001 UL-94
Polyurethane leather a 2572 142 135 V-0
Polyurethane leather b 2315 109 67 V-1
Polyurethane leather c 2328 103 71 V-2
As can be seen from the test results in Table 4, the flame retardance of the polyurethane leather prepared by using the reactive flame retardant prepared in example 1 of the invention as an additive can reach V-0 level and has excellent moisture permeability and hydrolysis resistance, while the flame retardance of the polyurethane leather prepared in comparative examples 8 and 9 respectively using dimethyl methylphosphonate and MCA as flame retardant additives are respectively V-1 and V-2, and the moisture permeability and the hydrolysis resistance are reduced compared with those of example 17.
The application of the thermosetting phenolic resin comprises the following steps:
example 18
In this example, 260 parts by weight of the reactive flame retardant prepared in example 5, 500 parts by weight of phenol, 539 parts by weight of formaldehyde, and 10 parts by weight of triethanolamine catalyst were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and 1 part by weight of silane coupling agent was added to obtain thermosetting phenol-formaldehyde resin a.
Example 19
In this example, 320 parts by weight of the reactive flame retardant prepared in example 6, 500 parts by weight of phenol, 539 parts by weight of formaldehyde, and 10 parts by weight of triethanolamine catalyst were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and 1 part by weight of silane coupling agent was added to obtain thermosetting phenol resin b.
Comparative example 10
In the embodiment, APP 260 weight parts, phenol 500 weight parts, formaldehyde 539 weight parts, and triethanolamine catalyst 10 weight parts are reacted at 50 ℃ for 2 hours, and after the reaction is finished, the temperature is reduced to 30 ℃, and silane coupling agent 1 weight part is added to obtain thermosetting phenolic resin c.
Comparative example 11
In this example, MCA 260 parts by weight, phenol 500 parts by weight, formaldehyde 539 parts by weight, and triethanolamine catalyst 10 parts by weight were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and silane coupling agent 1 part by weight was added to obtain thermosetting phenol resin d.
The properties of the thermosetting epoxy resins prepared in examples 18 and 19 and comparative examples 10 and 11 were measured, and the results are shown in Table 5. The test method of the tensile strength is GB/T1040.1-2006, the test method of the impact strength adopts GB/T1843-2008, the test method of the flame retardance is UL-94, and the test of the water resistance is the result obtained by soaking the thermosetting phenolic resin prepared in the embodiment and the comparative example in boiling water for 2 hours after the tensile strength is tested and then carrying out the tensile strength test again.
TABLE 5
Figure BDA0002182893920000211
Figure BDA0002182893920000221
As can be seen from the test data in Table 5, the phenolic resins prepared by using the reactive flame retardants obtained in examples 5 and 6 as additives have flame retardant properties of V-0 and excellent tensile strength and water resistance, while comparative example 10 using APP as a flame retardant additive has flame retardant properties of V-0 but poor mechanical properties and water resistance, while comparative example 11 using MCA as a flame retardant additive has flame retardant properties of V-0.
Application of acrylic resin:
example 20
In this example, 30 parts by weight of the reactive flame retardant prepared in example 6 was mixed with 120 parts by weight of methyl methacrylate, 15 parts by weight of MBS, 15 parts by weight of methacrylic acid, 12 parts by weight of chloroprene rubber, 3 parts by weight of 1, 4-hydroquinone and 5 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive a.
Example 21
In this example, 30 parts by weight of the reactive flame retardant prepared in example 7 was mixed with 120 parts by weight of methyl methacrylate, 15 parts by weight of MBS, 15 parts by weight of methacrylic acid, 12 parts by weight of chloroprene rubber, 3 parts by weight of 1, 4-hydroquinone and 5 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive b.
Comparative example 12
In the comparative example, 30 parts by weight of the reactive flame retardant prepared from the red phosphorus capsule was mixed with 120 parts by weight of methyl methacrylate, 15 parts by weight of MBS, 15 parts by weight of methacrylic acid, 12 parts by weight of chloroprene rubber, 3 parts by weight of 1, 4-hydroquinone and 5 parts by weight of dicumyl peroxide to prepare the acrylic resin adhesive c.
Comparative example 13
In the comparative example, 30 parts by weight of a reactive flame retardant prepared from triphenyl phosphate was mixed with 120 parts by weight of methyl methacrylate, 15 parts by weight of MBS, 15 parts by weight of methacrylic acid, 12 parts by weight of chloroprene rubber, 3 parts by weight of 1, 4-hydroquinone and 5 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive d.
The acrylic resins prepared in examples 20 and 21 and comparative examples 12 and 13 were tested for their properties and the results are shown in Table 6. Wherein, the test method of tensile shear strength is GB/T7124-.
TABLE 6
Figure BDA0002182893920000231
Figure BDA0002182893920000241
From the test results of Table 6, it can be seen that examples 20 and 21, using the reactive flame retardants prepared in examples 6 and 7 as additives, can make the flame retardancy of acrylic resin to V-0 and have excellent tensile properties, while examples 12 and 13, using red phosphorus and triphenyl phosphate as flame retardant additives, respectively, give acrylic resins having tensile properties inferior to those of examples 20 and 21, and acrylic resins using triphenyl phosphate having flame retardancy of V-1.
Use in unsaturated resins:
example 22
In this example, 40 parts by weight of the reactive flame retardant prepared in example 3 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition a.
Example 23
In this example, 40 parts by weight of the reactive flame retardant prepared in example 10 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition b.
Comparative example 14
In this example, 40 parts by weight of APP was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition c.
Comparative example 15
In this example, a crosslinked acrylic resin composition d was prepared by mixing 40 parts by weight of MCA with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone.
The acrylic resin compositions prepared in examples 31 and 32 and comparative example 8 were tested for compressive strength, tensile strength, thermal conductivity, water resistance and flammability, and the results are shown in Table 7. The method for testing the compression resistance adopts GB/T20467-2008, the method for testing the tensile strength adopts GB/T6344-2008, and the method for testing the flame resistance is UL-94. The water resistance is that the acrylic resin composition after the compressive strength test is soaked in boiling water for 2 hours and then the compressive strength test is carried out again.
TABLE 7
Figure BDA0002182893920000251
Figure BDA0002182893920000261
As can be seen from the test results of Table 7, the acrylic resin compositions prepared in examples 22 and 23 using the reactive flame retardants provided in examples 3 and 10 as additives exhibited flame retardancy up to V-0 and excellent mechanical properties, while the acrylic resin compositions prepared in comparative examples 14 and 15 using APP and MCA as flame retardant additives exhibited flame retardancy of V-1 and decreased mechanical properties as compared to those of examples 22 and 23.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A reactive flame retardant is characterized in that the flame retardant is obtained by reacting a compound shown in a formula I with a compound containing a reactive group to remove at least one molecule of R '-O-R';
Figure FDA0002182893910000011
wherein X is a group VI element or is absent, R1And R2Each independently is any group which satisfies its chemical environment, R' includes any one of hydrogen and its isotope, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl, a, b and c areEach independently is an integer of 0 or more, and a + b + c is 3 or more;
wherein, R' comprises any one of hydrogen and isotopes thereof, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl.
2. The flame retardant of claim 1, wherein R is1And R2Each independently preferably includes any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted cycloalkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, or a substituted or unsubstituted heteroarylmercapto group.
3. The flame retardant of claim 1 or 2, wherein R preferably comprises any one of substituted or unsubstituted alkylene, cycloalkylene, arylene, heteroarylene, alkylenecycloalkyl, alkylenearyl, alkyleneheteroaryl, cycloalkylenearyl, cycloalkyleneheteroaryl, or aryleneheteroaryl.
4. The flame retardant of any one of claims 1-3, wherein X is O or S.
5. The flame retardant of any one of claims 1 to 4, wherein the reactive group-containing compound comprises any one or a combination of at least two of a hydroxyl group, a phenolic hydroxyl group, a mercapto group, an aldehyde group, a carboxyl group, an ester group, a cyano group, an amino group, or a substituted or unsubstituted unsaturated group.
6. A method for preparing the flame retardant of any one of claims 1-5, comprising: the compound shown in the formula I reacts with the compound containing the reactive group to remove at least one molecule of R' -O-R ″.
7. Use of the reactive flame retardant according to any of claims 1 to 5 for the preparation of engineering plastics, shaped materials and composites.
8. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of epoxy resin compositions, polyurethane compositions, polyester compositions, unsaturated resin compositions, phenolic resin compositions and silicone resin compositions.
9. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of a polymeric material;
preferably, the polymer material includes polyester, polyurethane, alkyd, polyamide, amino resin, unsaturated resin, and silicone resin.
10. Use of a reactive flame retardant according to any of claims 1 to 5 for an epoxy resin curing agent.
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